Scientific Output

Over 10.000 scientific papers have been published by members of the Materials Chain since the foundation of the University Alliance Ruhr in 2010. This tremendous output is proof of the excellent environment the Ruhr Area provides for research in the field of materials science and technology.

Below, you can either scroll through the complete list of our annually published material, or search for a specific author or term via the free text search to get to know our research strengths. You can also review the publication record of every Materials Chain member via his or her personal member’s page.

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  • 2023 • 312 Investigation on the crack formation in carbon concrete for the use in deck caps on cantilever slabs of bridges
    Farwig, Kristina and Schulte-Schrepping, Christoph and Curbach, Manfred and Breitenbücher, Rolf
    Structural Concrete 24 2563 – 2574 (2023)
    Deck caps of bridges—in Germany shortly known as “bridge caps”—are usually made of steel reinforced concrete to form the anchoring area for the guardrail of bridge deck edges on existing cantilever slabs. Combined with protective devices, the outside arranged deck caps provide safety against lateral breaking or crashes of vehicles. Due to their exposed position in the cross section of bridges and the particularly intensive stresses, the deck caps are considered as wear parts and have to be renewed several times during the service life of a bridge. The decisive factor here is the discrepancy between the frost resistance of the concrete and the crack width restriction. On the one hand, only very small cracks (<0.2 mm) can be accepted to prevent corrosion of the rebars under the strong exposure of these elements. To confine crack widths without applying an excessively high degree of reinforcement, a low concrete compressive strength is advantageous. On the other hand, a sufficient frost resistance requires a correspondingly high compressive strength. With carbon reinforcement, these contrary points could be defused and simultaneously the needed durability could be provided. Therefore, slightly modified deck cap concretes combined with a carbon reinforcement mesh were tested to examine the bond behavior with and without freeze–thaw attack. To prove the characteristics of this combined system, the crack formation and crack distribution were investigated experimentally. The test results were compared to calculated values from a mathematically tool to be able to develop different reinforcement concepts in future that can ensure an optimized crack formation and crack width for deck caps. © 2022 The Authors. Structural Concrete published by John Wiley & Sons Ltd on behalf of International Federation for Structural Concrete.
    view abstractdoi: 10.1002/suco.202200298
  • 2023 • 311 Standardizing OER Electrocatalyst Benchmarking in Aqueous Electrolytes: Comprehensive Guidelines for Accelerated Stress Tests and Backing Electrodes
    Zlatar, Matej and Escalera-López, Daniel and Rodríguez, Miquel Gamón and Hrbek, Tomáš and Götz, Carina and Mary Joy, Rani and Savan, Alan and Tran, Hoang Phi and Nong, Hong Nhan and Pobedinskas, Paulius and Briega-Martos, Va...
    ACS Catalysis 13 15375 – 15392 (2023)
    The scarcity of iridium, needed to catalyze the sluggish oxygen evolution reaction (OER), hinders large-scale hydrogen production with proton exchange membrane water electrolyzers (PEMWEs). Crucial steps require reducing its loading while improving its overall activity and stability. Despite knowledge transfer challenges, cost and time constraints still favor aqueous model systems (AMSs) over real devices for the OER electrocatalyst testing. During AMS testing, benchmarking strategies such as accelerated stress tests (ASTs) aim at improving catalyst lifetime estimation compared to constant current loads. This study systematically evaluates a commercial Ir catalyst by modifying both AST parameters and the employed backing electrodes to examine their impact on activity-stability relationships. A comprehensive set of spectroscopy and microscopy techniques, including in situ inductively coupled plasma mass spectrometry, is employed to monitor Ir and backing electrode modifications. Our findings demonstrate that the choice of both lower potential limit (LPL) in ASTs and backing electrode significantly influences the estimation of Ir-based electrocatalysts’ activity and stability. Unique degradation mechanisms, such as passivation, redeposition on active sites, and contribution to the OER, were observed for different backing electrodes at varying LPLs. These results emphasize the importance of optimizing parameters and electrode selection in ASTs to accurately assess the electrocatalyst performance. Furthermore, they establish the foundation for developing relevant standardized test protocols, enabling the cost-effective development of high-performance catalysts for PEMWE applications. © 2023 The Authors. Published by American Chemical Society.
    view abstractdoi: 10.1021/acscatal.3c03880
  • 2023 • 310 The impact of plasma enhancement on the deposition of carbon-containing zirconia films by metalorganic chemical vapor deposition
    Maaß, Philipp A. and Bedarev, Vitali and Chauvet, Laura and Prenzel, Marina and Glauber, Jean-Pierre and Devi, Anjana and Böke, Marc and von Keudell, Achim
    Plasma Processes and Polymers 20 (2023)
    Zirconia layers are often used as thermal barriers. In recent years, depositions by chemical vapor deposition methods using a metalorganic precursor (MOCVD) have been primarily investigated. Here, we combine MOCVD with plasma activation - plasma-enhanced chemical vapor deposition (PECVD]) - of the gas phase and/or the growth surface to lower the growth temperature and to allow for a flexible coating design. PECVD causes the precursor to be transformed into a chemically active species, yielding thin films with a five times higher sticking coefficient compared to MOCVD. This leads to the onset of crystallization at lower surface temperatures. Carbon is incorporated at oxygen sites, so that the crystalline structure of zirconia is preserved, but the electrical conductivity is affected. The thermal conductivity is like that of pure zirconia. © 2023 The Authors. Plasma Processes and Polymers published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/ppap.202300050
  • 2022 • 309 Carbon-nitrogen bond formation on Cu electrodes during CO2 reduction in NO3- solution
    Krzywda, P.M. and Paradelo Rodríguez, A. and Benes, N.E. and Mei, B.T. and Mul, G.
    Applied Catalysis B: Environmental 316 (2022)
    We demonstrate by Raman Spectroscopy that simultaneous reduction of NO3- and CO2 on Cu surfaces leads to formation of Cu-C[tbnd]N–like species, showing Raman bands at 2080 and 2150 cm−1 when associated with reduced or oxidized Cu surfaces, respectively. Furthermore Cu-C[tbnd]N–like species are soluble, explaining vast restructuring of the Cu surface observed after co-electrolysis of CO2 and nitrate. Oxidation of deposited Cu-C[tbnd]N–like species results in the formation of NO. Cu-C[tbnd]N–like species do not form in electrolytes containing i) NH4+ and CO2, or ii) NO3- and HCOO-, suggesting these likely originate from Cu-CO, the commonly accepted intermediate in electrochemical reduction of CO2, and Cu-NHx species, previously identified in the literature as intermediate towards C-N bond formation. The implications of the previously unresolved formation of Cu-C[tbnd]N–like species for the development of electrodes and processes for electrochemical formation of carbon-nitrogen bonds, including urea, amines or amides, are briefly discussed. © 2022 The Authors
    view abstractdoi: 10.1016/j.apcatb.2022.121512
  • 2022 • 308 Green steel at its crossroads: Hybrid hydrogen-based reduction of iron ores
    Souza Filho, I.R. and Springer, H. and Ma, Y. and Mahajan, A. and da Silva, C.C. and Kulse, M. and Raabe, D.
    Journal of Cleaner Production 340 (2022)
    Iron- and steelmaking cause ∼7% of the global CO2 emissions, due to the use of carbon for the reduction of iron ores. Replacing carbon by hydrogen as the reductant offers a pathway to massively reduce these emissions. However, the production of hydrogen using renewable energy will remain as one of the bottlenecks at least during the next two decades, because making the gigantic annual crude steel production of 1.8 billion tons sustainable requires a minimum stoichiometric amount of ∼97 million tons of green hydrogen per year. Another fundamental aspect to render the ironmaking sector more sustainable lies in an optimal utilization of green hydrogen and energy, thus reducing efforts for costly in-process hydrogen recycling. We therefore demonstrate here how the efficiency in hydrogen and energy consumption during iron ore reduction can be dramatically improved by the knowledge-based combination of two technologies: partially reducing the ore at low temperature via solid-state direct reduction (DR) to a kinetically defined degree, and subsequently melting and completely transforming it to iron under a reducing plasma (i.e. via hydrogen plasma reduction, HPR). Results suggest that an optimal transition point between these two technologies occurs where their efficiency in hydrogen utilization is equal. We found that the reduction of hematite through magnetite into wüstite via DR is clean and efficient, but it gets sluggish and inefficient when iron forms at the outermost layers of the iron ore pellets. Conversely, HPR starts violent and unstable with arc delocalization, but proceeds smoothly and efficiently when processing semi-reduced oxides, an effect which might be related to the material's high electrical conductivity. We performed hybrid reduction experiments by partially reducing hematite pellets via DR at 700 °C to 38% global reduction (using a standard thermogravimetry system) and subsequently transferring them to HPR, conducted with a lean gas mixture of Ar-10%H2 in an arc-melting furnace, to achieve full conversion into liquid iron. This hybrid approach allows to exploit the specific characteristics and kinetically favourable regimes of both technologies, while simultaneously showing the potential to keep the consumption of energy and hydrogen low and improve both, process stability and furnace longevity by limiting its overexposure to plasma radiation. © 2022 Elsevier Ltd
    view abstractdoi: 10.1016/j.jclepro.2022.130805
  • 2022 • 307 High stress twinning in a compositionally complex steel of very high stacking fault energy
    Wang, Z. and Lu, W. and An, F. and Song, M. and Ponge, D. and Raabe, D. and Li, Z.
    Nature Communications 13 (2022)
    Deformation twinning is rarely found in bulk face-centered cubic (FCC) alloys with very high stacking fault energy (SFE) under standard loading conditions. Here, based on results from bulk quasi-static tensile experiments, we report deformation twinning in a micrometer grain-sized compositionally complex steel (CCS) with a very high SFE of ~79 mJ/m2, far above the SFE regime for twinning (&lt;~50 mJ/m2) reported for FCC steels. The dual-nanoprecipitation, enabled by the compositional degrees of freedom, contributes to an ultrahigh true tensile stress up to 1.9 GPa in our CCS. The strengthening effect enhances the flow stress to reach the high critical value for the onset of mechanical twinning. The formation of nanotwins in turn enables further strain hardening and toughening mechanisms that enhance the mechanical performance. The high stress twinning effect introduces a so far untapped strengthening and toughening mechanism, for enabling the design of high SFEs alloys with improved mechanical properties. © 2022, The Author(s).
    view abstractdoi: 10.1038/s41467-022-31315-2
  • 2022 • 306 Hydrogen-based direct reduction of iron oxide at 700°C: Heterogeneity at pellet and microstructure scales
    Ma, Y. and Souza Filho, I.R. and Zhang, X. and Nandy, S. and Barriobero-Vila, P. and Requena, G. and Vogel, D. and Rohwerder, M. and Ponge, D. and Springer, H. and Raabe, D.
    International Journal of Minerals, Metallurgy and Materials 29 1901-1907 (2022)
    Steel production causes a third of all industrial CO2 emissions due to the use of carbon-based substances as reductants for iron ores, making it a key driver of global warming. Therefore, research efforts aim to replace these reductants with sustainably produced hydrogen. Hydrogen-based direct reduction (HyDR) is an attractive processing technology, given that direct reduction (DR) furnaces are routinely operated in the steel industry but with CH4 or CO as reductants. Hydrogen diffuses considerably faster through shaft-furnace pellet agglomerates than carbon-based reductants. However, the net reduction kinetics in HyDR remains extremely sluggish for high-quantity steel production, and the hydrogen consumption exceeds the stoichiometrically required amount substantially. Thus, the present study focused on the improved understanding of the influence of spatial gradients, morphology, and internal microstructures of ore pellets on reduction efficiency and metallization during HyDR. For this purpose, commercial DR pellets were investigated using synchrotron high-energy X-ray diffraction and electron microscopy in conjunction with electron backscatter diffraction and chemical probing. Revealing the interplay of different phases with internal interfaces, free surfaces, and associated nucleation and growth mechanisms provides a basis for developing tailored ore pellets that are highly suited for a fast and efficient HyDR. © 2022, The Author(s).
    view abstractdoi: 10.1007/s12613-022-2440-5
  • 2022 • 305 In Situ Carbon Corrosion and Cu Leaching as a Strategy for Boosting Oxygen Evolution Reaction in Multimetal Electrocatalysts
    Zhang, J. and Quast, T. and He, W. and Dieckhöfer, S. and Junqueira, J.R.C. and Öhl, D. and Wilde, P. and Jambrec, D. and Chen, Y.-T. and Schuhmann, W.
    Advanced Materials (2022)
    The number of active sites and their intrinsic activity are key factors in designing high-performance catalysts for the oxygen evolution reaction (OER). The synthesis, properties, and in-depth characterization of a homogeneous CoNiFeCu catalyst are reported, demonstrating that multimetal synergistic effects improve the OER kinetics and the intrinsic activity. In situ carbon corrosion and Cu leaching during the OER lead to an enhanced electrochemically active surface area, providing favorable conditions for improved electronic interaction between the constituent metals. After activation, the catalyst exhibits excellent activity with a low overpotential of 291.5 ± 0.5 mV at 10 mA cm−2 and a Tafel slope of 43.9 mV dec−1. It shows superior stability compared to RuO2 in 1 m KOH, which is even preserved for 120 h at 500 mA cm−2 in 7 m KOH at 50 °C. Single particles of this CoNiFeCu after their placement on nanoelectrodes combined with identical location transmission electron microscopy before and after applying cyclic voltammetry are investigated. The improved catalytic performance is due to surface carbon corrosion and Cu leaching. The proposed catalyst design strategy combined with the unique single-nanoparticle technique contributes to the development and characterization of high-performance catalysts for electrochemical energy conversion. © 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/adma.202109108
  • 2022 • 304 Investigation of the combustion chemistry in laminar, low-pressure oxymethylene ether flames (OME0–4)
    Gaiser, N. and Zhang, H. and Bierkandt, T. and Schmitt, S. and Zinsmeister, J. and Kathrotia, T. and Hemberger, P. and Shaqiri, S. and Kasper, T. and Aigner, M. and Oßwald, P. and Köhler, M.
    Combustion and Flame (2022)
    Quantitative speciation data for alternative fuels is highly desired to assess their emission potential and to develop and validate chemical kinetic models. In terms of substitute choices for fossil diesel are oxymethylene ethers (OMEs) strongly discussed. Due to the absence of carbon-carbon bonds, soot emissions from combustion of OMEs are low, but significant emissions of unregulated pollutants such as aldehydes emerge. The combustion behavior of OME fuels with different chain lengths, OME0–4, was investigated in laminar premixed low-pressure flames using complementary molecular-beam mass spectrometry (MBMS) techniques. MBMS sampling provides an in-situ access directly into the reaction zone of the flame. Almost all chemical species involved in the oxidation process can be detected and quantified simultaneously. Neat OME0–3 flames were analyzed by electron ionization (EI) MBMS with high mass resolution (R ≈ 3900) providing exact elementary composition. To obtain isomer-specific information, an OME1-doped hydrogen flame and a stochiometric OME4 flame were studied by double-imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy. Both, EI-MBMS detection and i2PEPICO spectroscopy, enables a complete overview of all intermediates. The results show a dominance of oxygenated intermediates for all measured conditions. Mole fraction profiles for the most important species are presented (i.e. formaldehyde, methanol, methyl formate and formic acid) and compared to modeling results. Hydrocarbons with more than four carbon atoms were not detected under the investigated conditions. Isomers such as ethanol/dimethyl ether (m/z = 46) and ethenol/acetaldehyde (m/z = 44) could be separated using threshold photoelectron spectra for clear identification and photoionization efficiency curves for quantification. This investigation permits the discussion and analysis of systematic trends, including intermediate species, for the combustion of the studied series of oxymethylene ether fuels. © 2022 The Combustion Institute
    view abstractdoi: 10.1016/j.combustflame.2022.112060
  • 2022 • 303 Investigation of the effect of carbon post- vs pre-coated metallic bipolar plates for PEMFCs – start-up and shut-down
    Müller, M.-V. and Giorgio, M. and Hausmann, P. and Kinlechner, L. and Heinzel, A. and Schwämmlein, J.
    International Journal of Hydrogen Energy 47 8532-8548 (2022)
    In this work, the influence of increased potentials during the start-up/shut-down process on metallic bipolar plates (316L) with the coating system Cr/a-C based on graphite-like carbon is investigated. In comparison to commonly applied post-coated bipolar plates, a new low-cost manufacturing process based on pre-coated metal sheets for bipolar plates was evaluated. By developing a vehicle near start-up/shut-down cycle, a relative humidity of 140% and anode residence time of 0.94 s show the greatest damage potential of the cycle variations. After 2000 start-up/shut-down cycles, pre-coated metallic bipolar plates show no increased voltage loss compared to conventional coatings. Nevertheless, the resistances increase for Cr/a-C post- and pre-coating at the H2 outlet. This correlates with an increased surface roughness of the bipolar plate but otherwise only minor surface changes can be observed. The coating variation has no effect on the extent of catalyst coated membrane thinning or increased content of metal ions. © 2021 Hydrogen Energy Publications LLC
    view abstractdoi: 10.1016/j.ijhydene.2021.12.179
  • 2022 • 302 On the diversity of fossil and alternative gasoline combustion chemistry: A comparative flow reactor study
    Zinsmeister, J. and Gaiser, N. and Melder, J. and Bierkandt, T. and Hemberger, P. and Kasper, T. and Aigner, M. and Köhler, M. and Oßwald, P.
    Combustion and Flame 243 (2022)
    Recent progress in molecular combustion chemistry allows for detailed investigation of the intermediate species pool even for complex chemical fuel compositions, as occur for technical fuels. This study provides detailed investigation of a comprehensive set of complex alternative gasoline fuels obtained from laminar flow reactors equipped with molecular-beam sampling techniques for observation of the combustion intermediate species pool in homogeneous gas phase reactions. The combination of ionization techniques including double-imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy enables deeper mechanistic insights into the underlying reaction network relevant to technical fuels. The selected fuels focus on contemporary automotive engine application as drop-in fuels compliant to European EN 228 specification for gasoline. Therefore, potential alternative gasoline blends containing oxygenated hydrocarbons as octane improvers obtainable from bio-technological production routes, e.g., ethanol, iso-butanol, methyl tert‑butyl ether (MTBE), and ethyl tert‑butyl ether (ETBE), as well as a Fischer-Tropsch surrogate were investigated. The fuel set is completed by two synthetic naphtha fractions obtained from Fischer-Tropsch and methanol-to-gasoline processes alongside with a fossil reference gasoline. In total, speciation data for 11 technical fuels from two atmospheric flow reactor setups are presented. Detailed main and intermediate species profiles are provided for slightly rich (ϕ = 1.2) and lean (ϕ = 0.8) conditions for intermediate to high temperatures. Complementary, the isomer distribution on different mass channels, like m/z = 78 u fulvene/benzene, of four gasolines was investigated. Experimental findings are analyzed in terms of the detailed fuel composition and literature findings for molecular combustion chemistry. Influences of oxygenated fuel components as well as composition of the hydrocarbon fractions are examined with a particular focus on the soot precursor chemistry. This dataset is available for validation of chemical kinetic mechanisms for realistic gasolines containing oxygenated hydrocarbons. © 2021
    view abstractdoi: 10.1016/j.combustflame.2021.111961
  • 2022 • 301 Revealing the influence of Mo addition on interphase precipitation in Ti-bearing low carbon steels
    Dong, H. and Chen, H. and Riyahi khorasgani, A. and Zhang, B. and Zhang, Y. and Wang, Z. and Zhou, X. and Wang, W. and Wang, H. and Li, T. and Yang, Z. and van der Zwaag, S.
    Acta Materialia 223 (2022)
    Mo is widely used as an effective microalloying element to improve mechanical performance of interphase precipitation steels, but the precise role of Mo in interphase precipitation behavior is not fully understood. In this contribution, interphase precipitation behavior in a series of Ti-Mo-bearing low carbon steels is systematically studied, and the role of Mo in interphase precipitates and its coarsening behavior is revisited. It is found that (Ti, Mo)C precipitates instead of TiC are formed in the Mo-containing alloys, and the average site fraction of Mo in (Ti, Mo)C is almost independent of the bulk Mo content. Moreover, the number density of interphase precipitates can be substantially enhanced by a minor addition of Mo, albeit it does not further rise with increasing the bulk Mo content. This is because the Mo fraction in (Ti, Mo)C rather than the bulk Mo content governs the driving force for precipitation nucleation and the interfacial energy of the (Ti, Mo)C/α and (Ti, Mo)C/γ interfaces. In addition to the reduced interfacial energy, decrease of Ti trans-interface diffusivity has been identified as another key reason for the enhanced carbide coarsening resistance in Mo-containing alloys. © 2021 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2021.117475
  • 2022 • 300 Scale-Up of Solvent-Free, Mechanochemical Precursor Synthesis for Nanoporous Carbon Materials via Extrusion
    Rensch, T. and Chantrain, V. and Sander, M. and Grätz, S. and Borchardt, L.
    ChemSusChem (2022)
    The mechanochemical synthesis of nitrogen-rich nanoporous carbon materials has been scaled up using an extruder. Lignin, urea, and K2CO3 were extruded under heat and pressure to yield nanoporous carbons with up to 3500 m2 g−1 specific surface area after pyrolysis. The route was further broadened by applying different nitrogen sources as well as sawdust as a low-cost renewable feedstock to receive carbons with a C/N ratio of up to 15 depending on nitrogen source and extrusion parameters. The texture of obtained carbons was investigated by scanning electron microscopy as well as argon and nitrogen physisorption, while the chemical structure was analyzed by X-ray photoelectron spectroscopy. The received carbon was tested as a supercapacitor electrode, showing comparable performance to similar ball-mill-synthesized materials. Lastly, the space-time yield was applied to justify the use of a continuous reactor versus the ball mill. © 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/cssc.202200651
  • 2022 • 299 Sodiation Of Hard Carbon: How Separating Enthalpy And Entropy Contributions Can Find Transitions Hidden In The Voltage Profile
    Mercer, M.P. and Affleck, S. and Gavilán-Arriazu, E.M. and Zülke, A.A. and Maughan, P.A. and Trivedi, S. and Fichtner, M. and Reddy Munnangi, A. and Leiva, E.P.M. and Hoster, H.E.
    ChemPhysChem 23 (2022)
    Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge. © 2021 Wiley-VCH GmbH
    view abstractdoi: 10.1002/cphc.202100748
  • 2021 • 298 Cobalt Metal ALD: Understanding the Mechanism and Role of Zinc Alkyl Precursors as Reductants for Low-Resistivity Co Thin Films
    Zanders, D. and Liu, J. and Obenlüneschloß, J. and Bock, C. and Rogalla, D. and Mai, L. and Nolan, M. and Barry, S.T. and Devi, A.
    Chemistry of Materials (2021)
    In this work, we report a new and promising approach toward the atomic layer deposition (ALD) of metallic Co thin films. Utilizing the simple and known CoCl2(TMEDA) (TMEDA = N,N,N′,N′-tetramethylethylenediamine) precursor in combination with the intramolecularly stabilized Zn aminoalkyl compound Zn(DMP)2 (DMP = dimethylaminopropyl) as an auxiliary reducing agent, a thermal ALD process is developed that enables the deposition of Zn-free Co thin films. ALD studies demonstrate the saturation behavior of both precursors and linearity depending on the applied number of cycles as well as temperature dependency of film growth in a regime of 140-215 °C. While the process optimization is carried out on Si with native oxide, additional growth studies are conducted on Au and Pt substrates. This study is complemented by initial reactivity and suitability tests of several potential Zn alkyl-reducing agents. For the CoCl2(TMEDA)-Zn(DMP)2 combination, these findings allow us to propose a series of elemental reaction steps hypothetically leading to pure Co film formation in the ALD process whose feasibility is probed by a set of density functional theory (DFT) calculations. The DFT results show that for reactions of the precursors in the gas phase and on Co(111) substrate surfaces, a pathway involving C-C coupling and diamine formation through reductive elimination of an intermediate Co(II) alkyl species is preferred. Co thin films with an average thickness of 10-25 nm obtained from the process are subjected to thorough analysis comprising atomic force microscopy, scanning electron microscopy, and Rutherford backscattering spectrometry/nuclear reaction analysis as well as depth profiling X-ray photoemission spectroscopy (XPS). From XPS analysis, it was found that graphitic and carbidic carbon coexist in the Co metal film bulk. Despite carbon concentrations of ∼20 at. % in the Co thin film bulk, resistivity measurements for ∼22 nm thick films grown on a defined SiO2 insulator layer yield highly promising values in a range of 15-20 μω cm without any postgrowth treatment. © 2021 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemmater.1c00877
  • 2021 • 297 Effect of Carbon-Doping on Microstructure and Nanomechanical/Tribological Behavior of Ti–B–C Coatings onto H13 Steel
    Contreras, E. and Grisales, D. and Tillmann, W. and Hurtado-Macias, A. and Gómez-Botero, M.A.
    Metals and Materials International (2021)
    Abstract: Due to its high hardness, chemical and thermal resistance, TiB2 has become a great candidate to be used as a protective coating. However, high residual stresses after the deposition and brittleness have become the main obstacles for implementation at industrial levels. In the present work, the incorporation of graphite was studied as an alternative to improve the performance of the TiB2 coatings and study the influence in the microstructure, Nano mechanical and tribological properties. Ti–B–C coatings were deposited with different carbon contents of 10, 20, 28 and 38 at%. XRD results showed that the carbon atoms enter within the crystal lattice of the TiB2 forming a solid solution, and consequently, deforming crystal and modifying its lattice parameter of 3.2237–3.3414 Å. HRTEM images and selected area electron diffraction patterns analysis display the low crystallite or degree of amorphosity due to the carbon concentration (C1.9 mol). Compressive residual stresses decrease in the coatings containing the higher amounts of carbon. The formation of a TiB2-C solid solution contributed to the increment of nanohardness (H = 25 GPa) and improvement of the resistance to plastic deformation (H3/E2) of coatings. Regarding the tribological behaviour of the coatings, higher friction coefficient than those obtained on the uncoated substrate were observed. However, a reduction of the wear rate was also evident. The presence of a high amount of debris and severe wear of the counterpart material indicates a highly aggressive tribological contact. Roll-like debris with a shape of needles was found within the tribological tracks perpendicular to the sliding direction. Graphic Abstract: [Figure not available: see fulltext.]. © 2021, The Korean Institute of Metals and Materials.
    view abstractdoi: 10.1007/s12540-021-01104-5
  • 2021 • 296 Influence of microstructure and atomic-scale chemistry on the direct reduction of iron ore with hydrogen at 700°C
    Kim, S.-H. and Zhang, X. and Ma, Y. and Souza Filho, I.R. and Schweinar, K. and Angenendt, K. and Vogel, D. and Stephenson, L.T. and El-Zoka, A.A. and Mianroodi, J.R. and Rohwerder, M. and Gault, B. and Raabe, D.
    Acta Materialia 212 (2021)
    Steel is the most important material class in terms of volume and environmental impact. While it is a sustainability enabler, for instance through lightweight design, magnetic devices, and efficient turbines, its primary production is not. Iron is reduced from ores by carbon, causing 30% of the global CO2 emissions in manufacturing, qualifying it as the largest single industrial greenhouse gas emission source. Hydrogen is thus attractive as alternative reductant. Although this reaction has been studied for decades, its kinetics is not well understood, particularly during the wüstite reduction step which is much slower than hematite reduction. Some rate-limiting factors of this reaction are determined by the microstructure and local chemistry of the ores. Here, we report on a multi-scale structure and composition analysis of iron reduced from hematite with pure H2, reaching down to near-atomic scale. During reduction a complex pore- and microstructure evolves, due to oxygen loss and non-volume conserving phase transformations. The microstructure after reduction is an aggregate of nearly pure iron crystals, containing inherited and acquired pores and cracks. We observe several types of lattice defects that accelerate mass transport as well as several chemical impurities (Na, Mg, Ti, V) within the Fe in the form of oxide islands that were not reduced. With this study, we aim to open the perspective in the field of carbon-neutral iron production from macroscopic processing towards better understanding of the underlying microscopic transport and reduction mechanisms and kinetics. © 2021
    view abstractdoi: 10.1016/j.actamat.2021.116933
  • 2021 • 295 Influence of sub-monolayer quantities of carbon nanoparticles on the melting and crystallization behavior of polyamide 12 powders for additive manufacturing
    Sommereyns, A. and Hupfeld, T. and Gann, S. and Wang, T. and Wu, C. and Zhuravlev, E. and Lüddecke, A. and Baumann, S. and Rudloff, J. and Lang, M. and Gökce, B. and Barcikowski, S. and Schmidt, M.
    Materials and Design 201 (2021)
    In this paper, the influence of 0.005 vol% and 0.05 vol% of carbon nanoparticles on the surface of polyamide 12 powder particles by dry coating and colloidal additivation is evaluated in great detail concerning thermal and microstructural properties. The dispersion of the nanoparticles on the polymer surface influences the flowability of the feedstock powder already during the additivation process. When analyzing the composite powders dynamically and isothermally with fast scanning and differential scanning calorimetry, carbon nanoparticles influence the crystallization behavior of the feedstock material significantly by acting as nucleation seeds, already at a few percent of a monolayer coating, while showing no effect on the fast heating process. The difference in calorimetric properties and crystallization behavior between the additivation methods of different abrasive forces is discussed. The surface-additivated carbon nanoparticles significantly increase the crystalline area by up to a threefold and the crystallization rate by up to a hundredfold. Furthermore, they change the crystal growth from a typical two- to three-dimensional growth of spherulites to a one- to two-dimensional growth of ellipsoidal impinged lamellar structures. Between 0.005 vol% and 0.05 vol% of well-dispersed carbon nanoparticles should be added to polyamide 12 to trigger an anisotropic heterogeneous nucleation while avoiding agglomerates. © 2021 The Authors
    view abstractdoi: 10.1016/j.matdes.2021.109487
  • 2021 • 294 Laser-generated high entropy metallic glass nanoparticles as bifunctional electrocatalysts
    Johny, J. and Li, Y. and Kamp, M. and Prymak, O. and Liang, S.-X. and Krekeler, T. and Ritter, M. and Kienle, L. and Rehbock, C. and Barcikowski, S. and Reichenberger, S.
    Nano Research (2021)
    High entropy metallic glass nanoparticles (HEMG NPs) are very promising materials for energy conversion due to the wide tuning possibilities of electrochemical potentials offered by their multimetallic character combined with an amorphous structure. Up until now, the generation of these HEMG NPs involved tedious synthesis procedures where the generated particles were only available on highly specialized supports, which limited their widespread use. Hence, more flexible synthetic approaches to obtain colloidal HEMG NPs for applications in energy conversion and storage are highly desirable. We utilized pulsed laser ablation of bulk high entropy alloy targets in acetonitrile to generate colloidal carbon-coated CrCoFeNiMn and CrCoFeNiMnMo HEMG NPs. An in-depth analysis of the structure and elemental distribution of the obtained nanoparticles down to single-particle levels using advanced transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) methods revealed amorphous quinary and senary alloy phases with slight manganese oxide/hydroxide surface segregation, which were stabilized within graphitic shells. Studies on the catalytic activity of the corresponding carbon-HEMG NPs during oxygen evolution and oxygen reduction reactions revealed an elevated activity upon the incorporation of moderate amounts of Mo into the amorphous alloy, probably due to the defect generation by atomic size mismatch. Furthermore, we demonstrate the superiority of these carbon-HEMG NPs over their crystalline analogies and highlight the suitability of these amorphous multi-elemental NPs in electrocatalytic energy conversion. [Figure not available: see fulltext.] © 2021, The Author(s).
    view abstractdoi: 10.1007/s12274-021-3804-2
  • 2021 • 293 Perspective: Increasing blue carbon around Antarctica is an ecosystem service of considerable societal and economic value worth protecting
    Bax, N. and Sands, C.J. and Gogarty, B. and Downey, R.V. and Moreau, C.V.E. and Moreno, B. and Held, C. and Paulsen, M.L. and McGee, J. and Haward, M. and Barnes, D.K.A.
    Global Change Biology 27 5-12 (2021)
    Precautionary conservation and cooperative global governance are needed to protect Antarctic blue carbon: the world's largest increasing natural form of carbon storage with high sequestration potential. As patterns of ice loss around Antarctica become more uniform, there is an underlying increase in carbon capture-to-storage-to-sequestration on the seafloor. The amount of carbon captured per unit area is increasing and the area available to blue carbon is also increasing. Carbon sequestration could further increase under moderate (+1°C) ocean warming, contrary to decreasing global blue carbon stocks elsewhere. For example, in warmer waters, mangroves and seagrasses are in decline and benthic organisms are close to their physiological limits, so a 1°C increase in water temperature could push them above their thermal tolerance (e.g. bleaching of coral reefs). In contrast, on the basis of past change and current research, we expect that Antarctic blue carbon could increase by orders of magnitude. The Antarctic seafloor is biophysically unique and the site of carbon sequestration, the benthos, faces less anthropogenic disturbance than any other ocean continental shelf environment. This isolation imparts both vulnerability to change, and an avenue to conserve one of the world's last biodiversity refuges. In economic terms, the value of Antarctic blue carbon is estimated at between £0.65 and £1.76 billion (~2.27 billion USD) for sequestered carbon in the benthos around the continental shelf. To balance biodiversity protection against society's economic objectives, this paper builds on a proposal incentivising protection by building a ‘non-market framework’ via the 2015 Paris Agreement to the United Nations Framework Convention on Climate Change. This could be connected and coordinated through the Antarctic Treaty System to promote and motivate member states to value Antarctic blue carbon and maintain scientific integrity and conservation for the positive societal values ingrained in the Antarctic Treaty System. © 2020 John Wiley & Sons Ltd
    view abstractdoi: 10.1111/gcb.15392
  • 2021 • 292 Residual stresses and tribomechanical behaviour of TiAlN and TiAlCN monolayer and multilayer coatings by DCMS and HiPIMS
    Tillmann, W. and Grisales, D. and Stangier, D. and Thomann, C.-A. and Debus, J. and Nienhaus, A. and Apel, D.
    Surface and Coatings Technology 406 (2021)
    The deposition of ternary nitrides with the incorporation of carbon atoms into its structure has demonstrated to be a promising approach in the pursuit of wear-resistant and self-lubricating coatings. Firstly, both TiAlN and TiAlCN monolayers were deposited using direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) onto quenched and tempered AISI H11 tool steel to be used as references. Acetylene was used as a carbon precursor, producing DCMS and HiPIMS TiAlCN coatings with 9.0 and 21.7 at.% C, respectively. Subsequently, TiAlN/TiAlCN multilayers of various designs were also developed as follows: 5×[10/500], 5×[50/500] and 5×[100/500] nm. Residual stresses of the coating systems were determined by X-ray radiation utilising an ETA-diffractometer with a Cu-Kα radiation source applying the sin2ψ method. Additionally, residual stresses depth gradients of the substrate before and after the deposition of the coatings were determined in a LEDDI 8-circle diffractometer equipped with a W-X-ray tube and operated in the energy-dispersive mode of diffraction. Great reduction of the compressive residual stresses in the coatings was observed after the introduction of carbon into the TiAlN coating structure, shifting from −1047 ± 149 to −307 ± 211 MPa for the DCMS and from −7035 ± 1361 to +989 ± 187 MPa for the HiPIMS coatings. In the multilayer coatings, compressive residual stresses increase along with the increment of the TiAlN interlayer. Additionally, residual stresses of the substrate in the near-surface are dragged from low compressive stresses (−218 ± 61) to tensile stresses in the range of 1000 to 2000 MPa for all the DCMS/substrate systems, a behaviour only presented in HiPIMS by the TiAlN monolayer. Wear coefficients of all the evaluated HiPIMS systems are notoriously lower than their DCMS counterparts. Compared to TiAlN, TiAlCN HiPIMS presented a lower coefficient of friction but a higher wear coefficient, which in turn was not reduced by the introduction of the multilayer systems. Finally, Scratch test and Rockwell C adhesion tests have shown higher adhesion of DCMS coatings than HiPIMS coatings, and a detriment of the monolayers adhesion by the implementation of TiAlN/TiAlCN multilayer systems. The understanding of the residual stresses, both in the coating and in the substrate, and the way they affect the tribomechanical performance of the system coating/substrate continues to be of great importance, especially for coatings deposited by new technologies such as HiPIMS and self-lubricating coatings. © 2020 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2020.126664
  • 2021 • 291 Revealing the Impact of Hierarchical Pore Organization in Supercapacitor Electrodes by Coupling Ionic Dynamics at Micro- and Macroscales
    Dvoyashkin, M. and Leistenschneider, D. and Evans, J.D. and Sander, M. and Borchardt, L.
    Advanced Energy Materials 11 (2021)
    The rate of charging of supercapacitors depends on how quickly ions can reach and accommodate the surface of electrodes. Diffusivity, a parameter reflecting the speed of ions’ migration, is believed to be crucial in designing supercapacitor electrodes. Herein, this belief is questioned, shedding light on a puzzling and potentially critical feature of ionic dynamics denoted as confinement-induced ion–solvent separation. This effect can lead to a strong slowdown of the ion mobility inside hierarchical pore networks. Explanations for when such an effect occurs and how it can be circumvented are provided. Furthermore, this microscopic picture of diffusion seen by NMR is bridged with the macroscopic charging behavior of supercapacitors investigated by impedance spectroscopy. Quantifying the average residence time of ions within carbon particles shows that the nanopore environment may not be the rate-limiting factor for the overall ion mobility and thus performance of a cell—as commonly expected. Combining direct diffusion studies performed with neat and solvated ionic liquids and those on organic electrolytes, the so far lacking criteria for the rational selection of electrolyte–carbon systems is developed and recommendations for the preparation of transport-optimized materials for supercapacitors to minimize ionic diffusion limitations are given. © 2021 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/aenm.202100700
  • 2021 • 290 Single-Entity Electrocatalysis of Individual “Picked-and-Dropped” Co3O4 Nanoparticles on the Tip of a Carbon Nanoelectrode
    Quast, T. and Aiyappa, H.B. and Saddeler, S. and Wilde, P. and Chen, Y.-T. and Schulz, S. and Schuhmann, W.
    Angewandte Chemie - International Edition 60 3576-3580 (2021)
    Nano-electrochemical tools to assess individual catalyst entities are critical to comprehend single-entity measurements. The intrinsic electrocatalytic activity of an individual well-defined Co3O4 nanoparticle supported on a carbon-based nanoelectrode is determined by employing an efficient SEM-controlled robotic technique for picking and placing a single catalyst particle onto a modified carbon nanoelectrode surface. The stable nanoassembly is microscopically investigated and subsequently electrochemically characterized. The hexagonal-shaped Co3O4 nanoparticles demonstrate size-dependent electrochemical activity and exhibit very high catalytic activity with a current density of up to 11.5 A cm−2 at 1.92 V (vs. RHE), and a turnover frequency of 532±100 s−1 at 1.92 V (vs. RHE) towards catalyzing the oxygen evolution reaction. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/anie.202014384
  • 2021 • 289 Trace Metal Loading of B-N-Co-doped Graphitic Carbon for Active and Stable Bifunctional Oxygen Reduction and Oxygen Evolution Electrocatalysts
    Sikdar, N. and Schwiderowski, P. and Medina, D. and Dieckhöfer, S. and Quast, T. and Brix, A.C. and Cychy, S. and Muhler, M. and Masa, J. and Schuhmann, W.
    ChemElectroChem 8 1685-1693 (2021)
    Understanding the structure-property relations of non-precious metal heteroatom co-doped carbon electrocatalysts exhibiting high activity as well as long-term durability for both ORR and OER remains challenging but is indispensable for the development of bifunctional ORR/OER electrocatalysts. We propose B-N-co-doped graphitic 2D carbon nanostructures impregnated with controlled amount of transition metals (M-BCN; M=Co, Ni, Fe, Cu) as bifunctional ORR/OER electrocatalysts. Co-BCN outperformed the Ni-, Fe-, Cu-based BCN catalysts exhibiting potential values of 0.87 V and 1.62 V at −1 mA/cm2 and 10 mA/cm2 during ORR and OER, respectively. Importantly, Co-BCN shows bifunctional cyclic stability (Δη; EOER−EORR=0.75 V) of up to 300 cycles in 1 M KOH for a duration of 20 h with total activity loss of only 10.2 % (ORR) and 6.2 % (OER), respectively. A low loading of the metal precursors was used to preserve porosity and to facilitate the formation of metal nanoparticles or M−NxB/C type species embedded in the graphitic carbon layers. The B-N-co-doped graphitic layers also protect the embedded metal nanoparticles explaining the observed long-term stability. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/celc.202100374
  • 2020 • 288 A hydrogen-dependent geochemical analogue of primordial carbon and energy metabolism
    Preiner, M. and Igarashi, K. and Muchowska, K.B. and Yu, M. and Varma, S.J. and Kleinermanns, K. and Nobu, M.K. and Kamagata, Y. and Tüysüz, H. and Moran, J. and Martin, W.F.
    Nature Ecology and Evolution 4 534-542 (2020)
    Hydrogen gas, H2, is generated by alkaline hydrothermal vents through an ancient geochemical process called serpentinization, in which water reacts with iron-containing minerals deep within the Earth’s crust. H2 is the electron donor for the most ancient and the only energy-releasing route of biological CO2 fixation, the acetyl-CoA pathway. At the origin of metabolism, CO2 fixation by hydrothermal H2 within serpentinizing systems could have preceded and patterned biotic pathways. Here we show that three hydrothermal minerals—greigite (Fe3S4), magnetite (Fe3O4) and awaruite (Ni3Fe)—catalyse the fixation of CO2 with H2 at 100 °C under alkaline aqueous conditions. The product spectrum includes formate (up to 200 mM), acetate (up to 100 µM), pyruvate (up to 10 µM), methanol (up to 100 µM) and methane. The results shed light on both the geochemical origin of microbial metabolism and the nature of abiotic formate and methane synthesis in modern hydrothermal vents. © 2020, The Author(s), under exclusive licence to Springer Nature Limited.
    view abstractdoi: 10.1038/s41559-020-1125-6
  • 2020 • 287 Analysis of the nanoparticle dispersion and its effect on the crystalline microstructure in carbon-additivated PA12 feedstock material for laser powder bed fusion
    Hupfeld, T. and Sommereyns, A. and Riahi, F. and Doñate-Buendía, C. and Gann, S. and Schmidt, M. and Gökce, B. and Barcikowski, S.
    Materials 13 (2020)
    Driven by the rapid development of additive manufacturing technologies and the trend towards mass customization, the development of new feedstock materials has become a key aspect. Additivation of the feedstock with nanoparticles is a possible route for tailoring the feedstock material to the printing process and to modify the properties of the printed parts. This study demonstrates the colloidal additivation of PA12 powder with laser-synthesized carbon nanoparticles at >95% yield, focusing on the dispersion of the nanoparticles on the polymer microparticle surface at nanoparticle loadings below 0.05 vol%. In addition to the descriptors "wt%" and "vol%", the descriptor "surf%" is discussed for characterizing the quantity and quality of nanoparticle loading based on scanning electron microscopy. The functionalized powders are further characterized by confocal dark field scattering, differential scanning calorimetry, powder rheology measurements (avalanche angle and Hausner ratio), and regarding their processability in laser powder bed fusion (PBF-LB). We find that heterogeneous nucleation is induced even at a nanoparticle loading of just 0.005 vol%. Finally, analysis of the effect of low nanoparticle loadings on the final parts' microstructure by polarization microscopy shows a nanoparticle loading-dependent change of the dimensions of the lamellar microstructures within the printed part. © 2020 by the authors.
    view abstractdoi: 10.3390/ma13153312
  • 2020 • 286 Anchoring of palladium nanoparticles on N-doped mesoporous carbon
    Warczinski, L. and Hu, B. and Eckhard, T. and Peng, B. and Muhler, M. and Hättig, C.
    Physical Chemistry Chemical Physics 22 21317-21325 (2020)
    Pd nanoparticles deposited on nitrogen-doped mesoporous carbon are promising catalysts for highly selective and effective catalytic hydrogenation reactions. To design and utilize these novel catalysts, it is essential to understand the effect of N doping on the metal-support interactions. A combined experimental (X-ray photoelectron spectroscopy) and computational (density functional theory) approach is used to identify preferential adsorption sites and to give detailed explanations of the corresponding metal-support interactions. Pyridinic N atoms turned out to be the preferential adsorption sites for Pd nanoparticles on nitrogen-doped mesoporous carbon, interacting through their lone pairs (LPs) with the Pd atoms via N-LP-Pd dσ and N-LP-Pd s and Pd dπ-π∗ charge transfer, which leads to a change in the Pd oxidation state. Our results evidence the existence of bifunctional palladium nanoparticles containing Pd0 and Pd2+ centers. © the Owner Societies.
    view abstractdoi: 10.1039/d0cp03234d
  • 2020 • 285 Carbon Isotope Fractionation of Substituted Benzene Analogs during Oxidation with Ozone and Hydroxyl Radicals: How Should Experimental Data Be Interpreted?
    Willach, S. and Lutze, H.V. and Somnitz, H. and Terhalle, J. and Stojanovic, N. and Lüling, M. and Jochmann, M.A. and Hofstetter, T.B. and Schmidt, T.C.
    Environmental Science and Technology 54 6713-6722 (2020)
    Oxidative processes frequently contribute to organic pollutant degradation in natural and engineered systems, such as during the remediation of contaminated sites and in water treatment processes. Because a systematic characterization of abiotic reactions of organic pollutants with oxidants such as ozone or hydroxyl radicals by compound-specific stable isotope analysis (CSIA) is lacking, stable isotope-based approaches have rarely been applied for the elucidation of mechanisms of such transformations. Here, we investigated the carbon isotope fractionation associated with the oxidation of benzene and several methylated and methoxylated analogs, namely, toluene, three xylene isomers, mesitylene, and anisole, and determined their carbon isotope enrichments factors (ϵC) for reactions with ozone (ϵC = -3.6 to -4.6 ‰) and hydroxyl radicals (ϵC = 0.0 to -1.2‰). The differences in isotope fractionation can be used to elucidate the contribution of the reactions with ozone or hydroxyl radicals to overall transformation. Derivation of apparent kinetic isotope effects (AKIEs) for the reaction with ozone, however, was nontrivial due to challenges in assigning reactive positions in the probe compounds for the monodentate attack leading to an ozone adduct. We present several options for this step and compare the outcome to quantum chemical characterizations of ozone adducts. Our data show that a general assignment of reactive positions for reactions of ozone with aromatic carbons in ortho-, meta-, or para-positions is not feasible and that AKIEs of this reaction should be derived on a compound-by-compound basis. © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acs.est.0c00620
  • 2020 • 284 Carbon Supported Phosphoric Acid Catalysts for Gas-Phase Synthesis of Diesel Additives
    Grünert, A. and Schmidt, W. and Schüth, F.
    Catalysis Letters (2020)
    Abstract: Carbon supported phosphoric acid (H3PO4/C) was found to be a more productive catalyst for the gas-phase synthesis of the diesel fuel additive/substitute oxymethylene ethers (OME) as compared to benchmark zeolite catalysts. In this contribution, the performance of catalysts H3PO4/C and related H2PO4 −/C and HPO4 2−/C materials in OME synthesis from methanol and formaldehyde is described. Graphic Abstract: [Figure not available: see fulltext.]. © 2020, The Author(s).
    view abstractdoi: 10.1007/s10562-020-03200-4
  • 2020 • 283 Chemical boundary engineering: A new route toward lean, ultrastrong yet ductile steels
    Ding, R. and Yao, Y. and Sun, B. and Liu, G. and He, J. and Li, T. and Wan, X. and Dai, Z. and Ponge, D. and Raabe, D. and Zhang, C. and Godfrey, A. and Miyamoto, G. and Furuhara, T. and Yang, Z. and van der Zwaag, S. and Chen, H.
    Science Advances 6 (2020)
    For decades, grain boundary engineering has proven to be one of the most effective approaches for tailoring the mechanical properties of metallic materials, although there are limits to the fineness and types of microstructures achievable, due to the rapid increase in grain size once being exposed to thermal loads (low thermal stability of crystallographic boundaries). Here, we deploy a unique chemical boundary engineering (CBE) approach, augmenting the variety in available alloy design strategies, which enables us to create a material with an ultrafine hierarchically heterogeneous microstructure even after heating to high temperatures. When applied to plain steels with carbon content of only up to 0.2 weight %, this approach yields ultimate strength levels beyond 2.0 GPa in combination with good ductility (>20%). Although demonstrated here for plain carbon steels, the CBE design approach is, in principle, applicable also to other alloys. Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).
    view abstractdoi: 10.1126/sciadv.aay1430
  • 2020 • 282 Differentiation between Carbon Corrosion and Oxygen Evolution Catalyzed by NixB/C Hybrid Electrocatalysts in Alkaline Solution using Differential Electrochemical Mass Spectrometry
    Möller, S. and Barwe, S. and Dieckhöfer, S. and Masa, J. and Andronescu, C. and Schuhmann, W.
    ChemElectroChem 7 2680-2686 (2020)
    Carbon is a frequently used electrode material and an important additive in catalyst films. Its corrosion is often reported during electrocatalysis at high anodic potentials, especially in acidic electrolyte. Investigation of the carbon corrosion in alkaline environment is difficult due to the CO2/CO32− equilibrium. We report the on-line determination of electrolysis products generated on NixB/C hybrid electrocatalysts in alkaline electrolyte at anodic potentials using differential electrochemical mass spectrometry (DEMS). NixB/C catalyst films were obtained from mixtures containing different ratios of NiXB and benzoxazine monomers followed by polymerization and pyrolysis. The impact of the composition of the electrocatalyst on the dominant electrolysis process allows to distinguish between the oxygen evolution reaction and carbon corrosion using DEMS results as well as the catalyst surface composition evaluated from X-ray photoelectron spectra. At the imposed highly oxidative conditions, an increasing amount of NixB in the electrocatalyst leads to a suppression of carbon corrosion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/celc.202000697
  • 2020 • 281 Experimental flat flame study of monoterpenes: Insights into the combustion kinetics of α-pinene, β-pinene, and myrcene
    Bierkandt, T. and Hoener, M. and Gaiser, N. and Hansen, N. and Köhler, M. and Kasper, T.
    Proceedings of the Combustion Institute (2020)
    Pinenes and pinene dimers have similar energy densities to petroleum-based fuels and are regarded as alternative fuels. The pyrolysis of the pinenes is well studied, but information on their combustion kinetics is limited. Three stoichiometric, flat premixed flames of the C10H16 monoterpenes α-pinene, β-pinene, and myrcene were investigated by synchrotron-based photoionization molecular-beam mass spectrometry (PI-MBMS) at the Advanced Light Source (ALS). This technique allows isomer-resolved identification and quantification of the flame species formed during the combustion process. Flame-sampling molecular-beam mass spectrometry even enables the detection of very reactive radical species. Myrcene was chosen because of its known formation during β-pinene pyrolysis. The quantitative speciation data and the discussed decomposition steps of the fuels provide important information for the development of future chemical kinetic reaction mechanisms concerning pinene combustion. The main decomposition of myrcene starts with the unimolecular cleavage of the carbon-carbon single bond between the two allylic carbon atoms. Further decompositions by β-scission to stable combustion intermediates such as isoprene (C5H8), 1,2,3-butatriene (C4H4) or allene (aC3H4) are consistent with the observed species pool. Concentrations of all detected hydrocarbons in the β-pinene flame are closer to the myrcene flame than to the α-pinene flame. These similarities and the direct identification of myrcene by its photoionization efficiency spectrum during β-pinene combustion indicate that β-pinene undergoes isomerization to myrcene under the studied flame conditions. Aromatic species such as phenylacetylene (C8H6), styrene (C8H8), xylenes (C8H10), and indene (C9H8) could be clearly identified and have higher concentrations in the α-pinene flame. Consequently, a higher sooting tendency can generally be expected for this monoterpene. The presented quantitative speciation data of flat premixed flames of the three monoterpenes α-pinene, β-pinene, and myrcene give insights into their combustion kinetics. © 2020 The Combustion Institute.
    view abstractdoi: 10.1016/j.proci.2020.06.204
  • 2020 • 280 Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
    Hu, B. and Warczinski, L. and Li, X. and Lu, M. and Bitzer, J. and Heidelmann, M. and Eckhard, T. and Fu, Q. and Schulwitz, J. and Merko, M. and Li, M. and Kleist, W. and Hättig, C. and Muhler, M. and Peng, B.
    Angewandte Chemie - International Edition (2020)
    Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H−. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/anie.202012816
  • 2020 • 279 Hard Cladding by Supersolidus Liquid Phase Sintering: An Experimental and Simulation Study on Martensitic Stainless Steels
    Farayibi, P.K. and Blüm, M. and Weber, S.
    Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 51 5818-5835 (2020)
    Martensitic stainless steels are suitable for diverse structural applications but degrade when subjected to wear-prone activities in service. To enhance their service life, the densification of high Cr, martensitic, X190CrVMo20-4-1 tool steel powder on two different martensitic stainless steel substrates via supersolidus liquid-phase sinter (SLPS) cladding was investigated. The objective was to assess the influence of the difference in compositions of the martensitic stainless steels employed as substrates on the interfacial diffusion, microstructure, hardness and bonding strength of the steel-to-steel claddings. Computational thermodynamics and diffusion simulations were employed to supplement experimental findings. Owing to interdiffusion, a M7C3 carbide-free, banded region exists in the X190 adjacent to the interface with the width dictated by chemical potential gradient of carbon. The hardness of the substrate was lower near the interface region because of carbon enrichment, which promoted the presence of retained austenite. An interfacial strength of 798 MPa was achieved with fairly ductile X190 matrix near the cladding interface as the fracture surface was characterized by mixed fracture modes of dimple rupture and cleavage with localized quasi-cleavage features. Experimental observations and computational simulations are in agreement. The implications of the SLPS cladding technique are discussed in the context of tool development. © 2020, The Author(s).
    view abstractdoi: 10.1007/s11661-020-05953-4
  • 2020 • 278 On the agglomeration tendency of carbonaceous fuels in fluidized beds
    Urciuolo, M. and Solimene, R. and Ammendola, P. and Krusch, S. and Scherer, V. and Salatino, P. and Chirone, R. and Senneca, O.
    Fuel 277 (2020)
    Single particle pyrolysis and combustion experiments have been carried out in a lab scale fluidized bed reactor at temperatures of 600–850 °C. The behavior of three different fuels is compared: a bituminous coal (Auguste Victoria), a typical bitumen used in the cement industry, a carbon rich solid waste from the refinery industry, characterized by a very high content of metals. The bituminous coal and the refinery waste particles, during the pyrolysis stage, produce interesting carbon-sand aggregates. The outer shell of these aggregates is constituted by quartz sand particles embedded in a carbon matrix. The aggregates are hollow inside. The size of the cavity is comparable with that of the original coal particles, while the outer shell is larger. The increase of particle size due to aggregate formation slows down the combustion rate. For bitumen, no carbon-sand aggregates are observed. The relations between the fuel properties and aggregates formation are discussed, in particular the chemical composition and the pyrolysis kinetics are examined. It is concluded that heavy/tarry species formed in the early pyrolysis stages are most likely responsible for the capture of the sand particles and formation of aggregates. © 2020 Elsevier Ltd
    view abstractdoi: 10.1016/j.fuel.2020.118187
  • 2020 • 277 On the role of chemical heterogeneity in phase transformations and mechanical behavior of flash annealed quenching & partitioning steels
    Liu, G. and Li, T. and Yang, Z. and Zhang, C. and Li, J. and Chen, H.
    Acta Materialia 201 266-277 (2020)
    The microstructure of advanced high-strength steels (AHSSs) is usually designed via adjusting austenite decomposition behavior upon cooling, while relatively less attention was paid to austenite formation upon heating. Here we explore the potentials of flash heating in tuning the microstructure and mechanical behavior of Quenching & Partitioning (Q&P) steels with an emphasis on the role of chemical heterogeneity. Besides substantially refining intercritical austenite grains (e.g. austenite formed during intercritical annealing), it was interestingly found that flash heating can also allow intercritical austenite to inherit Mn heterogeneity in the original pearlite-ferrite microstructure due to the kinetic mismatch between the sluggish diffusion of Mn and the rapid austenite formation. Chemical heterogeneity can to a large extent alter the decomposition of intercritical austenite and carbon partitioning upon cooling, and plays a notable role in enhancing thermal stability of austenite. The role of chemical heterogeneity in austenite decomposition and carbon partitioning behavior was explained via phase field simulations. The flash treated Q&P (FQP) steels have a broad range of tensile strength (from 980 MPa to 1180 MPa) and good ductility, which outperforms the conventional Q&P (CQP) steels. The current study demonstrates that flash heating opens alternative routes to create unique microstructures and improve the mechanical performance of AHSSs. © 2020
    view abstractdoi: 10.1016/j.actamat.2020.10.007
  • 2020 • 276 One-step synthesis of carbon-supported electrocatalysts
    Tigges, S. and Wöhrl, N. and Radev, I. and Hagemann, U. and Heidelmann, M. and Nguyen, T.B. and Gorelkov, S. and Schulz, S. and Lorke, A.
    Beilstein Journal of Nanotechnology 11 1419-1431 (2020)
    Cost-efficiency, durability, and reliability of catalysts, as well as their operational lifetime, are the main challenges in chemical energy conversion. Here, we present a novel, one-step approach for the synthesis of Pt/C hybrid material by plasma-enhanced chemical vapor deposition (PE-CVD). The platinum loading, degree of oxidation, and the very narrow particle size distribution are precisely adjusted in the Pt/C hybrid material due to the simultaneous deposition of platinum and carbon during the process. The as-synthesized Pt/C hybrid materials are promising electrocatalysts for use in fuel cell applications as they show significantly improved electrochemical long-term stability compared to the industrial standard HiSPEC 4000. The PE-CVD process is furthermore expected to be extendable to the general deposition of metal-containing carbon materials from other commercially available metal acetylacetonate precursors. © 2020 Tigges et al.; licensee Beilstein-Institut.
    view abstractdoi: 10.3762/BJNANO.11.126
  • 2020 • 275 Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry
    Möller, S. and Barwe, S. and Masa, J. and Wintrich, D. and Seisel, S. and Baltruschat, H. and Schuhmann, W.
    Angewandte Chemie - International Edition 59 1585-1589 (2020)
    Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long-term functionality of electrodes. In-depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO2 into CO3 2−. We report the adaptation of a DEMS system for online CO2 detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO3 2− as CO2 in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon-supported nickel boride (NixB/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201909475
  • 2020 • 274 Phase boundary segregation-induced strengthening and discontinuous yielding in ultrafine-grained duplex medium-Mn steels
    Ma, Y. and Sun, B. and Schökel, A. and Song, W. and Ponge, D. and Raabe, D. and Bleck, W.
    Acta Materialia 200 389-403 (2020)
    The combination of different phase constituents to realize a mechanical composite effect for superior strength-ductility synergy has become an important strategy in microstructure design in advanced high-strength steels. Introducing multiple phases in the microstructure essentially produces a large number of phase boundaries. Such hetero-interfaces affect the materials in various aspects such as dislocation activity and damage formation. However, it remains a question whether the characteristics of phase boundaries, such as their chemical decoration states, would also have an impact on the mechanical behavior in multiphase steels. Here we reveal a phase boundary segregation-induced strengthening effect in ultrafine-grained duplex medium-Mn steels. We found that the carbon segregation at ferrite-austenite phase boundaries can be manipulated by adjusting the cooling conditions after intercritical annealing. Such phase boundary segregation in the investigated steels resulted in a yield strength enhancement by 100–120 MPa and simultaneously promoted discontinuous yielding. The sharp carbon segregation at the phase boundaries impeded interfacial dislocation emission, thus increasing the stress required to activate such dislocation nucleation process and initiate plastic deformation. This observation suggests that the enrichment of carbon at the phase boundaries can enhance the energy barrier for dislocation emission, which provides a favorable condition for plastic flow avalanches and thus discontinuous yielding. These findings extend the current understanding of the yielding behavior in medium-Mn steels, and more importantly, shed light on utilizing and manipulating phase boundary segregation to improve the mechanical performance of multiphase metallic materials. © 2020
    view abstractdoi: 10.1016/j.actamat.2020.09.007
  • 2020 • 273 Photochemical Approach to the Cyclohepta[b]indole Scaffold by Annulative Two-Carbon Ring-Expansion
    Tymann, D.C. and Benedix, L. and Iovkova, L. and Pallach, R. and Henke, S. and Tymann, D. and Hiersemann, M.
    Chemistry - A European Journal 26 11974-11978 (2020)
    We report on the implementation of the concept of a photochemically elicited two-carbon homologation of a π-donor–π-acceptor substituted chromophore by triple-bond insertion. Implementing a phenyl connector between the slide-in module and the chromophore enabled the synthesis of cylohepta[b]indole-type building blocks by a metal-free annulative one-pot two-carbon ring expansion of the five-membered chromophore. Post-irradiative structural elaboration provided founding members of the indolo[2,3-d]tropone family of compounds. Control experiments in combination with computational chemistry on this multibond reorganization process founded the basis for a mechanistic hypothesis. © 2020 The Authors. Published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/chem.202002581
  • 2020 • 272 Polymer/enzyme-modified HF-etched carbon nanoelectrodes for single-cell analysis
    Marquitan, M. and Ruff, A. and Bramini, M. and Herlitze, S. and Mark, M.D. and Schuhmann, W.
    Bioelectrochemistry 133 (2020)
    Carbon-based nanoelectrodes fabricated by means of pyrolysis of an alkane precursor gas purged through a glass capillary and subsequently etched with HF were modified with redox polymer/enzyme films for the detection of glucose at the single-cell level. Glucose oxidase (GOx) was immobilized and electrically wired by means of an Os-complex-modified redox polymer in a sequential dip coating process. For the synthesis of the redox polymer matrix, a poly(1-vinylimidazole-co-acrylamide)-based backbone was used that was first modified with the electron transfer mediator [Os(bpy)2Cl]+ (bpy = 2,2′-bipyridine) followed by the conversion of the amide groups within the acrylamide monomer into hydrazide groups in a polymer-analogue reaction. The hydrazide groups react readily with bifunctional epoxide-based crosslinkers ensuring high film stability. Insertion of the nanometre-sized polymer/enzyme modified electrodes into adherently growing single NG108-15 cells resulted in a positive current response correlating with the intracellular glucose concentration. Moreover, the nanosensors showed a stable current output without significant loss in performance after intracellular measurements. © 2020
    view abstractdoi: 10.1016/j.bioelechem.2020.107487
  • 2020 • 271 Protecting Antarctic blue carbon: as marine ice retreats can the law fill the gap?
    Gogarty, B. and McGee, J. and Barnes, D.K.A. and Sands, C.J. and Bax, N. and Haward, M. and Downey, R. and Moreau, C. and Moreno, B. and Held, C. and Paulsen, M.L.
    Climate Policy 20 149-162 (2020)
    As marine-ice around Antarctica retracts, a vast ‘blue carbon’ sink, in the form of living biomass, is emerging. Properly protected and promoted Antarctic blue carbon will form the world’s largest natural negative feedback on climate change. However, fulfilling this promise may be challenging, given the uniqueness of the region and the legal systems that govern it. In this interdisciplinary study, we explain: the global significance of Antarctic blue carbon to international carbon mitigation efforts; the urgent need for international legal protections for areas where it is emerging; and the hurdles that need to be overcome to realize those goals. In order to progress conservation efforts past political blockages we recommend the development of an inter-instrument governance framework that quantifies the sequestration value of Antarctic blue carbon for attribution to states’ climate mitigation commitments under the 2015 Paris Agreement. Key policy insights Blue-carbon emergence around Antarctica’s coastlines will potentially store up to 160,000,000 tonnes of carbon annually. Blue-carbon will emerge in areas of rich biomass that will make it vulnerable to harvesting and other human activities; it is essential to incentivise conserving, rather than commercial exploitation of newly ice-free areas of the Southern Ocean. Antarctic blue carbon is a practical and prime candidate to build a cooperative, inter-instrument, non-market mitigation around; this should be considered at the ‘blue COP’ UN Climate change discussions in Spain. Allowing Antarctic fishing states to account for the carbon storage value of blue carbon zones through a non-market approach under the Paris Agreement could provide a vital incentive to their protection under the Antarctic Treaty System. The Scientific Committee on Antarctic Research would be the ideal body to facilitate the necessary connections between the relevant climate and Antarctic governance regimes. © 2019, © 2019 Informa UK Limited, trading as Taylor & Francis Group.
    view abstractdoi: 10.1080/14693062.2019.1694482
  • 2020 • 270 Repair of concrete traffic areas with slim carbon reinforced concrete layers [Instandsetzung von gefugten Betonflächen mit einer dünnen Schicht aus Carbonbeton]
    Farwig, K. and Neumann, J. and Schneider, R. and Breitenbücher, R. and Curbach, M.
    Beton- und Stahlbetonbau 115 768-778 (2020)
    Repair of concrete traffic areas with slim carbon reinforced concrete layers. Concrete pavements are exposed to high loads from existing traffic volumes and extreme weather conditions. In order to prevent wild cracking caused by the resulting constraining stresses, transverse joints are usually installed. However, these are also weak points in the concrete pavement, so that continuous maintenance and upkeeping is necessary. An ecologically and economically viable alternative to renewing the entire concrete slab is to rehabilitate the concrete runway with the aid of a jointless as well as thin top layer of carbon reinforced concrete. By separating the bond between the old concrete layer and the carbon concrete layer in the area of the transverse joint, a distribution of cracks is ensured and the crack width of the individual cracks in the carbon reinforced concrete pavement is reduced by multiple crack formation. Liquids can therefore penetrate less deeply into the concrete and damage neither the old concrete layer nor the corrosion-resistant carbon reinforcement. © 2020, Ernst und Sohn. All rights reserved.
    view abstractdoi: 10.1002/best.202000048
  • 2020 • 269 Tribological behaviour of low carbon-containing TiAlCN coatings deposited by hybrid (DCMS/HiPIMS) technique
    Tillmann, W. and Grisales, D. and Marin Tovar, C. and Contreras, E. and Apel, D. and Nienhaus, A. and Stangier, D. and Lopes Dias, N.F.
    Tribology International 151 (2020)
    TiAlN monolayers and TiAlN/TiAlCN bilayers were successfully deposited by hybrid (DCMS/HiPIMS) technology. The increase in the acetylene flow has linearly augmented the percentage of carbon incorporated into the coating systems. The TiAlCN with the highest carbon content significantly increased roughness and reduced hardness and Young's modulus. Additionally, a great reduction of the compressive residual stress has been noticed. Response surface methodology has been used from a full factorial design of experiments in order to create friction and wear maps varying sliding velocity and normal load for each of the coating systems. Tribological results showed that the coefficient of friction is not as dependent on the carbon content as it is on both the sliding velocity and normal load. © 2020 Elsevier Ltd
    view abstractdoi: 10.1016/j.triboint.2020.106528
  • 2019 • 268 A Novel Nanoconjugate of Landomycin A with C 60 Fullerene for Cancer Targeted Therapy: In Vitro Studies
    Bilobrov, V. and Sokolova, V. and Prylutska, S. and Panchuk, R. and Litsis, O. and Osetskyi, V. and Evstigneev, M. and Prylutskyy, Y. and Epple, M. and Ritter, U. and Rohr, J.
    Cellular and Molecular Bioengineering 12 41-51 (2019)
    Introduction: Landomycins are a subgroup of angucycline antibiotics that are produced by Streptomyces bacteria and possess strong antineoplastic potential. Literature data suggest that enhancement of the therapeutic activity of this drug may be achieved by means of creating specific drug delivery systems. Here we propose to adopt C 60 fullerene as flexible and stable nanocarrier for landomycin delivery into tumor cells. Methods: The methods of molecular modelling, dynamic light scattering and Fourier transform infrared spectroscopy were used to study the assembly of C 60 fullerene and the anticancer drug Landomycin A (LA) in aqueous solution. Cytotoxic activity of this nanocomplex was studied in vitro towards two cancer cell lines in comparison to human mesenchymal stem cells (hMSCs) using 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide (MTT) test and a live/dead assay. The morphology of the cells incubated with fullerene–drug nanoparticles and their uptake into target cells were studied by scanning electron microscopy and fluorescence light microscopy. Results: The viability of primary cells (hMSCs, as a model for healthy cells) and cancer cell lines (human osteosarcoma cells, MG-63, and mouse mammary cells, 4T1, as models for cancer cells) was studied after incubation with water-soluble C 60 fullerenes, LA and the mixture C 60 + LA. The C 60 + LA nanocomplex in contrast to LA alone showed higher toxicity towards cancer cells and lower toxicity towards normal cells, whereas the water-soluble C 60 fullerenes at the same concentration were not toxic for the cells. Conclusions: The obtained physico-chemical data indicate a complexation between the two compounds, leading to the formation of a C 60 + LA nanocomposite. It was concluded that immobilization of LA on C 60 fullerene enhances selectivity of action of this anticancer drug in vitro, indicating on possibility of further preclinical studies of novel C 60 + LA nanocomposites on animal tumor models. © 2018, Biomedical Engineering Society.
    view abstractdoi: 10.1007/s12195-018-0548-5
  • 2019 • 267 Cobalt metalloid and polybenzoxazine derived composites for bifunctional oxygen electrocatalysis
    Barwe, S. and Andronescu, C. and Engels, R. and Conzuelo, F. and Seisel, S. and Wilde, P. and Chen, Y.-T. and Masa, J. and Schuhmann, W.
    Electrochimica Acta 297 1042-1051 (2019)
    The development of bifunctional oxygen electrodes is a key factor for the envisaged application of rechargeable metal-air batteries. In this work, we present a simple procedure based on pyrolysis of polybenzoxazine/metal metalloid nanoparticles composites into efficient bifunctional oxygen reduction and oxygen evolution electrocatalysts. This procedure generates nitrogen-doped carbon with embedded metal metalloid nanoparticles exhibiting high activity towards both, oxygen reduction and oxygen evolution, in 0.1 M KOH with a roundtrip voltage of as low as 0.81 V. Koutecký-Levich analysis coupled with scanning electrochemical microscopy reveals that oxygen is preferentially reduced in a 4e− transfer pathway to hydroxide rather than to hydrogen peroxide. Furthermore, the polybenzoxazine derived carbon matrix allows for stable catalyst fixation on the electrode surface, resulting in unattenuated activity during continuous alternate polarisation between oxygen evolution at 10 mA cm−2 and oxygen reduction at −1.0 mA cm−2. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.electacta.2018.12.047
  • 2019 • 266 Deformation behavior and dominant abrasion micro mechanisms of tempering steel with varying carbon content under controlled scratch testing
    Pöhl, F. and Hardes, C. and Theisen, W.
    Wear 422-423 212-222 (2019)
    The objective of this paper is the investigation of the abrasive wear behavior of tempering steel by the analysis of its deformation behavior and dominant abrasion micro mechanisms under controlled single scratch testing. We analyzed single scratches induced by a sphero-conical diamond tip with constant and progressively increasing load in tempering steel with varying carbon content in the as quenched condition. Among scratch and hardness testing the analysis and characterization included the optical determination of the deformation behavior (SEM, CLSM, AFM). The results show that the deformation behavior strongly depends on applied normal load and strength (yield stress, ultimate tensile strength) as it varies with carbon content. It was shown that an increasing load leads to the transition of predominant abrasion micro mechanisms from ideal micro ploughing to wedge and chip formation. The scratch resistance increased with increasing carbon content until for higher carbon contents a saturation tendency due to the presence of retained austenite is observed. An increasing carbon content also shifted the aforementioned transition of dominant micro mechanisms not only to higher applied normal loads, but also to higher scratch depths. © 2019 Elsevier B.V.
    view abstractdoi: 10.1016/j.wear.2019.01.073
  • 2019 • 265 Influence of plasma nitriding pretreatments on the tribo-mechanical properties of DLC coatings sputtered on AISI H11
    Tillmann, W. and Lopes Dias, N.F. and Stangier, D.
    Surface and Coatings Technology 357 1027-1036 (2019)
    The duplex treatment, consisting of plasma nitriding and the deposition of a DLC coating, was carried out on the hot-work tool steel AISI H11. The coating structure, composed of Cr-based interlayers and a hydrogenated carbon layer, was sputtered on non-nitrided, nitrided, as well as nitrided-repolished AISI H11 steel with an either annealed or quenched and tempered base condition to examine the influence of the pretreatment condition on the tribo-mechanical properties of the DLC coating. Besides the graded hardness profile, plasma nitriding leads to a roughness increase, which affects the microstructure as well as the mechanical properties of the DLC coating. The rougher surface favors a film growth of a carbon layer with larger cluster-like structures. As a result, these DLC coatings exhibit hardness values below 22 GPa, while the coating systems sputtered on substrates with smoother surfaces reach values of approximately 26 GPa and showed a good adherence. The heat treatment condition influences the load-bearing capacity of the nitrided substrate as the higher core hardness enhances the mechanical support of the coating and reaches the highest adhesion class HF1 in the Rockwell C tests. Due to the lower film adhesion and the low hardness of the DLC coatings sputtered on nitrided non-repolished AISI H11, high coefficients of frictions and wear coefficients of up to 0.59 and 3.19 ∗ 10−5 mm3/N∗m were determined in tribometer tests against WC/Co counterparts. In contrast, the nitrided repolished steel exhibits a low coefficient of friction of 0.12 as well as a low wear coefficient of 0.06 ∗ 10−5 mm3/N∗m. Therefore, a repolishing of the nitrided AISI H11 with quenched and tempered base condition ensures the highest load-bearing capability of the substrate as well as an improved friction and wear behavior of the DLC coating. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2018.11.002
  • 2019 • 264 Ionic liquid - Electrode materials interactions studied by NMR spectroscopy, cyclic voltammetry, and impedance spectroscopy
    Zhang, E. and Fulik, N. and Paasch, S. and Borchardt, L. and Kaskel, S. and Brunner, E.
    Energy Storage Materials 19 432-438 (2019)
    The interactions between two selected porous carbon materials and ionic-liquid based electrolyte solutions consisting of the ionic liquid 1-Ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4)diluted with acetonitrile are investigated within the present paper by combined use of cyclic voltammetry, electrochemical impedance spectroscopy, and NMR spectroscopy. The commercially available microporous YP50F and the hierarchically organized micro- and mesoporous OM-CDC (ordered mesoporous carbide derived carbon)are selected as model materials to achieve a better understanding of the electrolyte behavior, especially its mobility, in porous carbons. The ionic liquid chosen as electrolyte leads to high specific capacitance approaching 180 F g-1 for OM-CDC. Due to the hierarchical pore system, OM-CDC shows a better rate performance than YP50F. NMR analyses provide an understanding of the molecular processes giving rise to the above-mentioned observations. They reveal a limited accessibility of the narrow pores in YP50F for pure EmimBF4 in contrast to OM-CDC. It was found that about 30% of the entire pore volume of YP50F remain unfilled by electrolyte ions without dilution. Dilution with acetonitrile significantly increased the anion mobility as the NMR signal of adsorbed ions becomes narrower. A mixture containing 60% EmimBF4 and 40% acetonitrile was identified as the optimum for electrochemical applications. © 2019 Elsevier B.V.
    view abstractdoi: 10.1016/j.ensm.2019.03.015
  • 2019 • 263 Mechanochemical synthesis of N-doped porous carbon at room temperature
    Casco, M.E. and Kirchhoff, S. and Leistenschneider, D. and Rauche, M. and Brunner, E. and Borchardt, L.
    Nanoscale 11 4712-4718 (2019)
    We report the one-pot mechanochemical synthesis of N-doped porous carbons at room temperature using a planetary ball mill. The fast reaction (5 minutes) between calcium carbide and cyanuric chloride proceeds in absence of any solvent and displays a facile bottom-up strategy that completely avoids typical thermal carbonization steps and directly yields a N-doped porous carbon containing 16 wt% of nitrogen and exhibiting a surface area of 1080 m2 g-1. © 2019 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c9nr01019j
  • 2019 • 262 Nanoporous carbon: Liquid-free synthesis and geometry-dependent catalytic performance
    Xu, R. and Kang, L. and Knossalla, J. and Mielby, J. and Wang, Q. and Wang, B. and Feng, J. and He, G. and Qin, Y. and Xie, J. and Swertz, A.-C. and He, Q. and Kegnæs, Sø. and Brett, D.J.L. and Schüth, F. and Wang, F.R.
    ACS Nano 13 2463-2472 (2019)
    Nanostructured carbons with different pore geometries are prepared with a liquid-free nanocasting method. The method uses gases instead of liquid to disperse carbon precursors, leach templates, and remove impurities, minimizing synthetic procedures and the use of chemicals. The method is universal and demonstrated by the synthesis of 12 different porous carbons with various template sources. The effects of pore geometries in catalysis can be isolated and investigated. Two of the resulted materials with different pore geometries are studied as supports for Ru clusters in the hydrogenolysis of 5-hydroxymethylfurfural (HMF) and electrochemical hydrogen evolution (HER). The porous carbon-supported Ru catalysts outperform commercial ones in both reactions. It was found that Ru on bottleneck pore carbon shows a highest yield in hydrogenolysis of HMF to 2,5-dimethylfuran (DMF) due to a better confinement effect. A wide temperature operation window from 110 to 140 °C, with over 75% yield and 98% selectivity of DMF, has been achieved. Tubular pores enable fast charge transfer in electrochemical HER, requiring only 16 mV overpotential to reach current density of 10 mA·cm-2. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acsnano.8b09399
  • 2019 • 261 Nitrogen-Doped Biomass-Derived Carbon Formed by Mechanochemical Synthesis for Lithium–Sulfur Batteries
    Schneidermann, C. and Kensy, C. and Otto, P. and Oswald, S. and Giebeler, L. and Leistenschneider, D. and Grätz, S. and Dörfler, S. and Kaskel, S. and Borchardt, L.
    ChemSusChem 12 310-319 (2019)
    Nitrogen-doped carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis by using renewable biomass waste. Three solid materials are used: sawdust as a carbon source, urea and/or melamine as a nitrogen source, and potassium carbonate as an activation agent. The resulting nitrogen-doped porous carbons offer a very high specific surface area of up to 3000 m 2 g −1 and a large pore volume up to 2 cm 3 g −1 . Also, a high nitrogen content of 4 wt % (urea only) up to 12 wt % (melamine only) is generated, depending on the nitrogen and carbon sources. The mechanochemical reaction and the impact of different wood components on the porosity and surface functionalities are investigated by nitrogen physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). These N-doped carbons are highly suitable as cathode materials for Li–S batteries, showing high initial discharge capacities of up to 1300 mAh g sulfur −1 (95 % coulombic efficiency) and &gt;75 % capacity retention within the first 50 cycles at low electrolyte volume. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201801997
  • 2019 • 260 Nitrogen-Doped Mesostructured Carbon-Supported Metallic Cobalt Nanoparticles for Oxygen Evolution Reaction
    Bähr, A. and Moon, G.-H. and Tüysüz, H.
    ACS Applied Energy Materials 2 6672-6680 (2019)
    A series of metallic cobalt nanoparticles supported on mesostructured nitrogen-doped carbons was successfully synthesized through soft-templating by using poly(ethylene oxide)-b-polystyrene (PEO-b-PS) as a structure directing agent. The formation of metallic cobalt nanoparticles and nitrogen-doping into carbon structures were simultaneously achieved by ammonia treatment. The physicochemical properties of the resulting materials and consequently their performance for the oxygen evolution were systematically altered by varying the cobalt loading (5-89 wt %), pyrolysis atmosphere (argon or ammonia), and temperature (600-800 °C). Thereby, up to 37 wt % of the cobalt nanoparticles were confined in the pores of the mesostructured nitrogen-doped carbon materials with a high BET surface area. At temperatures above 700 °C, the cobalt additionally catalyzes the graphitization of the carbon support. The catalyst with a cobalt loading of 37 wt % pyrolyzed at 700 °C under an ammonia atmosphere shows the highest turnover frequency (TOF) of 311 h-1 in the oxygen evolution reaction due to the improved electronic properties of the carbon support from the incorporation of nitrogen atoms combined with a large amount of accessible cobalt sites. This class of materials shows even higher activity in comparison with ordered mesoporous Co3O4. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acsaem.9b01183
  • 2019 • 259 Nitrogen-Doped Metal-Free Carbon Materials Derived from Cellulose as Electrocatalysts for the Oxygen Reduction Reaction
    Wütscher, A. and Eckhard, T. and Hiltrop, D. and Lotz, K. and Schuhmann, W. and Andronescu, C. and Muhler, M.
    ChemElectroChem 6 514-521 (2019)
    Development of metal-free carbon-based electrocatalysts for reducing oxygen to water (ORR), preferentially following a 4 electron transfer pathway, is of high importance. We present a two-step synthesis of N-doped carbon-based ORR electrocatalysts by using an efficient thermal treatment of hydrothermally carbonized cellulose in ammonia combining devolatilization, reduction and nitrogen doping. The influence of the synthesis temperature as well as of the ammonia concentration used during the synthesis on the electrocatalytic ORR activity was analyzed using bulk- and surface-sensitive techniques. Correlation of electrocatalytic activity with structural features of the catalysts provided deeper mechanistic understanding and enabled us to optimize the synthesis conditions. The nitrogen-doped metal-free catalyst originating from the treatment in 100 % NH3 at 800 °C achieved a current density of −1 mA cm−2 at 0.83 V vs. RHE positioning it among the most active noble-metal free and biomass-based ORR catalysts reported so far. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/celc.201801217
  • 2019 • 258 On the origin of mesopore collapse in functionalized porous carbons
    Zhang, E. and Casco, M.E. and Xu, F. and Sheng, W.-B. and Oswald, S. and Giebeler, L. and Wegner, K. and Borchardt, L. and Kaskel, S.
    Carbon 149 743-749 (2019)
    Heteroatom functionalization of ordered mesoporous carbon (OMC)represents an important strategy towards electrocatalytic and battery applications. Such functionalization frequently leads to degradation or even collapse of mesopores, which is generally attributed to the harsh conditions used or the successfully doped functional groups or the entrapment of guest species into mesopores. However, in this report, we find the structural deterioration of functionalized OMC is mainly induced by the water evaporation during the drying process, beyond the usually accepted concept mentioned above. We report two types of well-defined OMCs, resembling comparable pore architectures but varying in surface chemistry, namely the hydrophobic OMC (Cmeso)and hydrophilic one (HCmeso). After washing and drying processes, Cmeso remains intact regardless of the drying processes. In sharp contrast, HCmeso shows gradual porosity deterioration or even totally collapse under continuous washing-drying cycles. Lyophilization can however well preserve the porosity due to the reduced stress exerted by water on carbon walls. Such a distinct phenomenon is elaborately characterized by N2 physisorption, H2O physisorption, TEM and SAXS and further validated by well-known CMK-3, which undergoes surface functionalization by concentrated HNO3. Our finding reveals an important but neglected issue addressing the drying process in particular for polar functionalized porous carbons. © 2019 Elsevier Ltd
    view abstractdoi: 10.1016/j.carbon.2019.04.116
  • 2019 • 257 Photocatalytic one-step synthesis of Ag nanoparticles without reducing agent and their catalytic redox performance supported on carbon
    Shui, L. and Zhang, G. and Hu, B. and Chen, X. and Jin, M. and Zhou, G. and Li, N. and Muhler, M. and Peng, B.
    Journal of Energy Chemistry 36 37-46 (2019)
    Synthesis of silver nanoparticles (Ag NPs) with state-of-the-art chemical or photo-reduction methods generally takes several steps and requires both reducing agents and stabilizers to obtain NPs with narrow size distribution. Herein, we report a novel method to synthesize Ag NPs rapidly in one step, achieving typical particle sizes in the range from 5 to 15 nm. The synthesis steps only involve three chemicals without any reducing agent: AgNO3 as precursor, polyvinylpyrrolidone (PVP) as stabilizer, and AgCl as photocatalyst. The Ag NPs were supported on carbon and showed excellent performance in thermal catalytic p-nitrophenol reduction and nitrobenzene hydrogenation, and as electrocatalyst for the oxygen reduction reaction. © 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
    view abstractdoi: 10.1016/j.jechem.2019.04.006
  • 2019 • 256 Slip factors for slip-resistant connections made of stainless steel
    Stranghöner, N. and Afzali, N. and de Vries, P. and Schedin, E. and Pilhagen, J.
    Journal of Constructional Steel Research 152 235-245 (2019)
    Stainless steels are becoming more and more popular as a construction material in both building and civil engineering structures, because of their high material strength, ductility and corrosion resistance. In this frame, the execution of slip-resistant connections made of stainless steel is necessary, e. g. in footbridges, facades etc. As no design regulations exist in any code, special experimental testing has to be performed in each case. Stainless steel alloys are thought to suffer more than carbon steels from time dependent viscoplastic deformation at room temperature. It could lead to higher preload losses and consequently to lower slip factors than achieved for carbon steels with comparable surface treatment. However, no evidence of this behaviour can be found in literature for preloaded bolted connections. For this reason, slip factors for the various stainless steel grades have to be determined experimentally if they want to be used in the steel structures. In the frame of the European RFCS-research project SIROCO, the preloading behaviour of stainless steel bolted connections as well as the slip-resistant behaviour of slip-resistant connections made of austenitic, various duplex and ferritic stainless steels have been investigated. In this paper, the results of slip factor tests on four stainless steel grades are presented and the influence of different surface treatments and the preload level on the slip factor of stainless steel slip-resistant connections is discussed. Finally, slip factors for various stainless steel grades with different surface treatments are proposed for a future implementation in the next revision of EN 1090-2. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.jcsr.2018.07.005
  • 2019 • 255 Structures of carbonaceous nanoparticles formed in various pyrolysis systems
    Jander, H. and Borchers, C. and Böhm, H. and Emelianov, A. and Schulz, C.
    Carbon 150 244-258 (2019)
    In the pyrolysis of different hydrocarbon/carbon suboxid fuels formation of carbon particles with the special view to their structures was examined. For this, the following three very different pyrolysis systems were investigated experimentally i)a pyrolysis reactor, ii)a shock tube and iii)a plasma reactor with respect to the influence of varying reaction parameters on the carbonaceous nanoparticles. The particles formed in these reaction systems were studied in view of their morphology and state of crystallization by use of electron microscopy (Philips CM30)at low- and high resolution combined with micro-diffraction measurements. As to be seen at low resolution of the transmission electron microscopy studies, the particle sizes in the pyrolysis reactor and shock tube do not differ significantly, but distinguished considerably from those particle sizes obtained in the plasma reactor. While the particles obtained in the pyrolysis reactor and shock-tube had particle diameters of about d≈ 30 nm, the particles in the plasma reactor consisted of fluffy-like units, and their sizes were about d≈ 4 nm. The various carbon layers consisted of different polyaromatic hydrocarbon units with variable sizes arranged to diverse states in the course of graphitization. © 2019 Elsevier Ltd
    view abstractdoi: 10.1016/j.carbon.2019.02.034
  • 2019 • 254 Tailoring the Adsorption of ACE-Inhibiting Peptides by Nitrogen Functionalization of Porous Carbons
    Huettner, C. and Hagemann, D. and Troschke, E. and Hippauf, F. and Borchardt, L. and Oswald, S. and Henle, T. and Kaskel, S.
    Langmuir 35 9721-9731 (2019)
    Bioactive peptides, such as isoleucyl-tryptophan (IW), exhibit a high potential to inhibit the angiotensin-converting enzyme (ACE). Adsorption on carbon materials provides a beneficial method to extract these specific molecules from the complex mixture of an α-lactalbumin hydrolysate. This study focuses on the impact of nitrogen functionalization of porous carbon adsorbents, either via pre- or post-treatment, on the adsorption behavior of the ACE-inhibiting peptide IW and the essential amino acid tryptophan (W). The commercially activated carbon Norit ROX 0.8 is compared with pre- and postsynthetically functionalized N-doped carbon in terms of surface area, pore size, and surface functionality. For prefunctionalization, a covalent triazine framework was synthesized by trimerization of an aromatic nitrile under ionothermal conditions. For the postsynthetic approach, the activated carbon ROX 0.8 was functionalized with the nitrogen-rich molecule melamine. The batch adsorption results using model mixtures containing the single components IW and W could be transferred to a more complex mixture of an α-lactalbumin hydrolysate containing a huge number of various peptides. For this purpose, reverse-phase high-pressure liquid chromatography with fluorescence detection was used for identification and quantification. The treatment with the three different carbon materials leads to an increase in the ACE-inhibiting effect in vitro. The modified surface structure of the carbon via pre- or post-treatment allows separation of IW and W due to the certain selectivity for either the amino acid or the dipeptide. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acs.langmuir.9b00996
  • 2019 • 253 Tailoring the porosity of a mesoporous carbon by a solvent-free mechanochemical approach
    Leistenschneider, D. and Wegner, K. and Eßbach, C. and Sander, M. and Schneidermann, C. and Borchardt, L.
    Carbon 147 43-50 (2019)
    The synthesis of mesoporous carbons with well-defined and tailored pores conventionally involves the use of solvents and proceeds via multiple synthesis steps such as template synthesis and precursor infiltration. In this work, a solvent-free mechanochemical polymerization is used to derive mesoporous carbons with narrow pore size distributions and specific surface areas of up to 1660 m 2 g −1 . The size of the mesopores can be tailored by simply adjusting milling parameters like the milling speed. Finally, the carbons have been applied as supercapacitors through a new approach - the ‘in situ electrolyte’ concept. This holistic concept does not treat the accumulating by-products of the carbon synthesis as waste, but rather utilizes them directly as electrolyte salts. With this, washing steps are circumvented and the use of any solvent becomes obsolete. © 2019 Elsevier Ltd
    view abstractdoi: 10.1016/j.carbon.2019.02.065
  • 2019 • 252 The effect of feedstock origin and temperature on the structure and reactivity of char from pyrolysis at 1300–2800 °C
    Surup, G.R. and Foppe, M. and Schubert, D. and Deike, R. and Heidelmann, M. and Timko, M.T. and Trubetskaya, A.
    Fuel 235 306-316 (2019)
    This study reports the effect of feedstock origin, residence time, and heat treatment temperature on CO2 and O2 reactivities, nanostructure and carbon chemistry of chars prepared at 1300, 1600, 2400, and 2800 °C in a slow pyrolysis reactor. The structure of char was characterized by transmission electron microscopy and Raman spectroscopy. The CO2 and O2 reactivity of char was investigated by thermogravimetric analysis. Results showed that the ash composition and residence time influence the char reactivity less than the heat treatment temperature. The heat treatment temperature and co-pyrolysis of pinewood char with biooil decreased the CO2 reactivity, approaching that of metallurgical coke. Importantly from a technological standpoint, the reactivities of char from high temperature pyrolysis (2400–2800 °C) were similar to those of metallurgical coke, emphasizing the importance of graphitizing temperatures on the char behavior. Moreover, graphitization of chars from wood and herbaceous biomass increased with the increasing heat treatment temperature, leading to formation of graphitizing carbon. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.fuel.2018.07.093
  • 2019 • 251 Upcycling of polyurethane waste by mechanochemistry: Synthesis of N-doped porous carbon materials for supercapacitor applications
    Schneidermann, C. and Otto, P. and Leistenschneider, D. and Grätz, S. and Eßbach, C. and Borchardt, L.
    Beilstein Journal of Nanotechnology 10 1618-1627 (2019)
    We developed an upcycling process of polyurethane obtaining porous nitrogen-doped carbon materials that were applied in supercapacitor electrodes. In detail, a mechanochemical solvent-free one-pot synthesis is used and combined with a thermal treatment. Polyurethane is an ideal precursor already containing nitrogen in its backbone, yielding nitrogen-doped porous carbon materials with N content values of 1-8 wt %, high specific surface area values of up to 2150 m2·g-1 (at a N content of 1.6 wt %) and large pore volume values of up to 0.9 cm3·g-1. The materials were tested as electrodes for supercapacitors in aqueous 1 M Li2SO4 electrolyte (100 F·g-1), organic 1 M TEA-BF4 (ACN, 83 F·g-1) and EMIM-BF4 (70 F·g-1). © 2019 Schneidermann et al.
    view abstractdoi: 10.3762/bjnano.10.157
  • 2018 • 250 A fully protected hydrogenase/polymer-based bioanode for high-performance hydrogen/glucose biofuel cells
    Ruff, A. and Szczesny, J. and Marković, N. and Conzuelo, F. and Zacarias, S. and Pereira, I.A.C. and Lubitz, W. and Schuhmann, W.
    Nature Communications 9 (2018)
    Hydrogenases with Ni- and/or Fe-based active sites are highly active hydrogen oxidation catalysts with activities similar to those of noble metal catalysts. However, the activity is connected to a sensitivity towards high-potential deactivation and oxygen damage. Here we report a fully protected polymer multilayer/hydrogenase-based bioanode in which the sensitive hydrogen oxidation catalyst is protected from high-potential deactivation and from oxygen damage by using a polymer multilayer architecture. The active catalyst is embedded in a low-potential polymer (protection from high-potential deactivation) and covered with a polymer-supported bienzymatic oxygen removal system. In contrast to previously reported polymer-based protection systems, the proposed strategy fully decouples the hydrogenase reaction form the protection process. Incorporation of the bioanode into a hydrogen/glucose biofuel cell provides a benchmark open circuit voltage of 1.15 V and power densities of up to 530 µW cm−2 at 0.85 V. © 2018, The Author(s).
    view abstractdoi: 10.1038/s41467-018-06106-3
  • 2018 • 249 Ab initio simulation of hydrogen-induced decohesion in cementite-containing microstructures
    McEniry, E.J. and Hickel, T. and Neugebauer, J.
    Acta Materialia 150 53-58 (2018)
    In high-strength carbon steels suitable for use in the automotive industry, hydrogen embrittlement (HE) is a potential barrier to the widespread application of these materials. The behaviour of hydrogen within the most prevalent carbide, namely cementite, has been investigated via ab initio simulation. In order to examine possible decohesion effects of hydrogen on carbon steels, the binding and diffusion of hydrogen at the interface between ferrite and cementite has been examined. In order to understand the effect of hydrogen on the mechanical properties of carbon steels, simulated ab initio tensile tests have been performed on the ferrite-cementite bicrystal. The results of the tensile tests can be combined with thermodynamic considerations in order to obtain the expected hydrogen concentrations at such ferrite-cementite phase boundaries. We find that the effect of hydrogen on the cohesion of the phase boundary may be significant, even when the bulk hydrogen concentration is low. © 2018 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2018.03.005
  • 2018 • 248 Bifunctional Oxygen Reduction/Oxygen Evolution Activity of Mixed Fe/Co Oxide Nanoparticles with Variable Fe/Co Ratios Supported on Multiwalled Carbon Nanotubes
    Elumeeva, K. and Kazakova, M.A. and Morales, D.M. and Medina, D. and Selyutin, A. and Golubtsov, G. and Ivanov, Y. and Kuznetzov, V. and Chuvilin, A. and Antoni, H. and Muhler, M. and Schuhmann, W. and Masa, J.
    ChemSusChem 11 1204-1214 (2018)
    A facile strategy is reported for the synthesis of Fe/Co mixed metal oxide nanoparticles supported on, and embedded inside, high purity oxidized multiwalled carbon nanotubes (MWCNTs) of narrow diameter distribution as effective bifunctional catalysts able to reversibly drive the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline solutions. Variation of the Fe/Co ratio resulted in a pronounced trend in the bifunctional ORR/OER activity. Controlled synthesis and in-depth characterization enabled the identification of an optimal Fe/Co composition, which afforded a low OER/OER reversible overvoltage of only 0.831 V, taking the OER at 10 mA cm−2 and the ORR at −1 mA cm−2. Importantly, the optimal catalyst with a Fe/Co ratio of 2:3 exhibited very promising long-term stability with no evident change in the potential for both the ORR and the OER after 400 charge/discharge (OER/ORR) cycles at 15 mA cm−2 in 6 m KOH. Moreover, detailed investigation of the structure, size, and phase composition of the mixed Fe/Co oxide nanoparticles, as well as their localization (inside of or on the surface of the MWCNTs) revealed insight of the possible contribution of the individual catalyst components and their synergistic interaction in the catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201702381
  • 2018 • 247 Carbon onion/sulfur hybrid cathodes: Via inverse vulcanization for lithium-sulfur batteries
    Choudhury, S. and Srimuk, P. and Raju, K. and Tolosa, A. and Fleischmann, S. and Zeiger, M. and Ozoemena, K.I. and Borchardt, L. and Presser, V.
    Sustainable Energy and Fuels 2 133-146 (2018)
    A sulfur-1,3-diisopropenylbenzene copolymer was synthesized by ring-opening radical polymerization and hybridized with carbon onions at different loading levels. The carbon onion mixing was assisted by shear in a two-roll mill to capitalize on the softened state of the copolymer. The sulfur copolymer and the hybrids were thoroughly characterized in structure and chemical composition, and finally tested by electrochemical benchmarking. An enhancement of specific capacity was observed over 140 cycles at higher content of carbon onions in the hybrid electrodes. The copolymer hybrids demonstrate a maximum initial specific capacity of 1150 mA h gsulfur-1 (850 mA h gelectrode-1) and a low decay of capacity to reach 790 mA h gsulfur-1 (585 mA h gelectrode-1) after 140 charge/discharge cycles. All carbon onion/sulfur copolymer hybrid electrodes yielded high chemical stability, stable electrochemical performance superior to conventional melt-infiltrated reference samples having similar sulfur and carbon onion content. The amount of carbon onions embedded in the sulfur copolymer has a strong influence on the specific capacity, as they effectively stabilize the sulfur copolymer and sterically hinder the recombination of sulfur species to the S8 configuration. © 2018 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7se00452d
  • 2018 • 246 Coherently strained [Fe-Co(C)/Au-Cu]n multilayers: A path to induce magnetic anisotropy in Fe-Co films over large thicknesses
    Giannopoulos, G. and Salikhov, R. and Varvaro, G. and Psycharis, V. and Testa, A.M. and Farle, M. and Niarchos, D.
    Journal of Physics D: Applied Physics 51 (2018)
    Among novel critical-element-free materials for permanent magnets, the nearly equiatomic Fe-Co alloy has recently attracted a great deal of attention as a large magneto-crystalline anisotropy can be induced by straining the Fe-Co unit cell. In thin film systems, the use of a suitable underlayer allows a tetragonal reconstruction of the Fe-Co to be triggered up to a critical thickness of few nanometers, above which the crystal structure relaxes to the magnetically soft cubic phase. Scaling-up the thickness of the metastable tetragonal Fe-Co phase is of crucial significance for different nanoscale applications, such as magnetic micro- and nano-electromechanical systems. To suppress the strain relaxation occurring at high thicknesses, we explored a novel approach based on Fe-Co(C)/Au-Cu multilayer films, where both Au-Cu interlayers and carbon (C) doping were used to stabilize the strained Fe-Co tetragonal phase over large thicknesses. Both doped and un-doped multilayer structures show a coherently strained regime, persisting up to a thickness of 60 nm, which leads, possibly in combination with the surface anisotropy induced at the Au-Cu interfaces, to the appearance of a large out-of-plane anisotropy (up to 0.4 MJ m-3), thus suggesting the potential of such an approach to develop critical-element-free thin film permanent magnets for a variety of nanoscale applications. © 2018 IOP Publishing Ltd.
    view abstractdoi: 10.1088/1361-6463/aaa41c
  • 2018 • 245 Control of the material flow in sheet-bulk metal forming using modifications of the tool surface
    Löffler, M. and Schulte, R. and Freiburg, D. and Biermann, D. and Stangier, D. and Tillmann, W. and Merklein, M.
    International Journal of Material Forming 1-10 (2018)
    Sheet-bulk metal forming (SBMF) processes are characterized by a successive and/or simultaneous occurrence of different load conditions such as the stress and strain states. These conditions influence the material flow and often lead to a reduced geometrical accuracy of the produced components. To improve the product quality, a control of the material flow is required. One suitable approach, the local adaption of tribological conditions by means of surface modifications of tool or workpiece, so-called tailored surfaces. To control the material flow and thus to improve the component accuracy, methods to reduce and to increase friction are needed. The aim of this study is to determine requirements for necessary adaptions of the friction, the identification of tribological mechanisms for different types of tool-sided tailored surfaces as well as the verification of the effectiveness of these surface modifications to improve the results of a specific SBMF process. The numerical analysis of a combined deep drawing and upsetting process revealed that this process is characterized by two areas of varying tribological load conditions. Using a numerical analysis, the friction factor gradient between these two areas was identified as a main influencing factor on the material flow. Based on this finding, Chromium-based hard coatings for the reduction of the friction and high-feed milled surfaces for an increase of the friction were investigated regarding their frictional behaviour. The results of the ring-compression tests revealed that the carbon content and the post treatment of coated tool surfaces are relevant to reduce the friction. The increased profile depth of the milled surfaces was identified as the main influencing factor on the tribological behaviour of this kind of tailored surfaces. The effectiveness of both types of tailored surfaces was verified for the combined deep drawing and upsetting process. © 2018 Springer-Verlag France SAS, part of Springer Nature
    view abstractdoi: 10.1007/s12289-018-1399-2
  • 2018 • 244 Fracture analysis of a metal to CFRP hybrid with thermoplastic interlayers for interfacial stress relaxation using in situ thermography
    Summa, J. and Becker, M. and Grossmann, F. and Pohl, M. and Stommel, M. and Herrmann, H.-G.
    Composite Structures 193 19-28 (2018)
    In this work a plane hybrid-structure composed of a metal and a carbon-fiber-reinforced-polymer (CFRP) constituent is introduced. Hereby an interlayer is inserted between the metal and the CFRP constituent, pursuing the task of stress relaxation. In order to study the effect of interfacial stress relaxation several thermoplastics are investigated. In situ passive thermography is used to assess the damage during quasi-static and fatigue mechanical loading. Thus, mechanical properties are correlated with corresponding damage-quantities from non-destructive testing (ndt). These results reveal that transversal cracking and mode-I delamination are the dominant failure processes, which strongly depend on the thermoplastic material. Additional finite element analysis describes strain-energy- and stressconcentrations, which coincide with the observed damage mechanisms and the origins of fracture. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.compstruct.2018.03.013
  • 2018 • 243 High resolution, binder-free investigation of the intrinsic activity of immobilized NiFe LDH nanoparticles on etched carbon nanoelectrodes
    Wilde, P. and Barwe, S. and Andronescu, C. and Schuhmann, W. and Ventosa, E.
    Nano Research 11 6034-6044 (2018)
    The determination of the intrinsic properties of nanomaterials is essential for their optimization as electrocatalysts, however it poses great challenges from the standpoint of analytical tools and methods. Herein, we report a novel methodology that allows for a binder-free investigation of electrocatalyst nanoparticles. The potential-assisted immobilization of a non-noble metal catalyst, i.e., nickel-iron layered double hydroxide (NiFe LDH) nanoparticles, was employed to directly attach small nanoparticle ensembles from a suspension to the surface of etched carbon nanoelectrodes. The dimensions of this type of electrodes allowed for the immobilization of the catalyst material below the picogram scale and resulted in a high resolution towards the faradaic current response. In addition the effect of the electrochemical aging on the intrinsic activity of the catalyst was investigated in alkaline media by means of continuous cyclic voltammetry. A change in the material properties could be observed, which was accompanied by a substantial decrease in its intrinsic activity. [Figure not available: see fulltext.] © 2018, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature.
    view abstractdoi: 10.1007/s12274-018-2119-4
  • 2018 • 242 Influence of Chain Length and Branching on the Structure of Functionalized Gold Nanoparticles
    Giri, A.K. and Spohr, E.
    Journal of Physical Chemistry C 122 26739-26747 (2018)
    Functionalized gold nanoparticles (GNPs) in aqueous NaCl solutions have been studied using molecular dynamics simulations to assess the suitability of various functionalization chemistries to effectively shield the metallic core. Alkane thiol chains of various chain length (Cl) containing 6, 12, 18, and 24 carbon atoms are grafted onto the surface of the gold core. We compare the properties of GNPs functionalized with nonpolar CH3-terminated and polar COO-- and NH3 +-terminated chains, where the nanoparticle charge is compensated by appropriate numbers of excess Na+ or Cl- counterions. In addition to linear chains, we also investigate branched Y-shaped chains with the branching sites at the 4th, 8th, or 12th carbon atom from the sulfur atom that connects the chain to the gold core. The penetration depth of water and ions into the diffuse hydrocarbon shell region and its dependence on chain length, branching, and terminating group is found to increase with decreasing chain length irrespective of termination. Long linear chains, however, tend to form bundles independent of terminal group and can thus leave fractions of the nanoparticle surface exposed to small molecules, whereas shorter and branched chains do not form bundles and can cover the GNPs more homogeneously. © 2018 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.8b08590
  • 2018 • 241 MC/MD coupling for scale bridging simulations of solute segregation in solids: An application study
    Ganesan, H. and Begau, C. and Sutmann, G.
    Communications in Computer and Information Science 889 112-127 (2018)
    A parallel hybrid Monte Carlo/Molecular Dynamics coupled framework has been developed to overcome the time scale limitation in simulations of segregation of interstitial atoms in solids. Simulations were performed using the proposed coupling approach to demonstrate its potential to model carbon segregation in ferritic steels with a single dislocation. Many simulations were carried out for different background carbon concentrations. This paper is a first step towards understanding the effect of segregation of interstitial atoms in solids and its influence on dislocation mobility in external fields. To this end, we carried out MD simulations, where shear forces were applied to mechanically drive screw dislocation on configurations with segregated carbon atoms. The results are compared with a reference system containing homogeneously distributed carbon atoms where the influence of segregated carbon on dislocation mobility could be observed. Simulation results gave qualitative evidence that the local concentration of interstitial solutes like carbon provides a significant pinning effect for the dislocation. © Springer Nature Switzerland AG 2018.
    view abstractdoi: 10.1007/978-3-319-96271-9_7
  • 2018 • 240 Modelling of the blanking process of high-carbon steel using Lemaitre damage model
    Isik, K. and Yoshida, Y. and Chen, L. and Clausmeyer, T. and Erman Tekkaya, A.
    Comptes Rendus - Mecanique 346 770-778 (2018)
    This paper presents a methodology to model a blanking process using a continuum mechanical damage model. A variant of the Lemaitre model, in which the quasi-unilateral conditions are taken into consideration to modify the damage behavior under compressive stress states, is selected as material model. S45C high-carbon steel is analyzed experimentally. To characterize the damage behavior of the material, notched round bar tensile tests with three different notch radii (6 mm, 10 mm, and 20 mm) using image analysis are performed. Using digital image processing, the strain at the deformation zone can be computed for the load–strain curves. Those curves are used as an objective function to determine the parameters of the Lemaitre damage model. The experimental results are compared with the results of the FE analysis of the tensile test. The identified model parameters are used in numerical investigations of axisymmetric blanking. The effect of the model's extension to quasi-unilateral damage evolution is discussed. The crack progress in high-carbon steel sheet during blanking and the final sheared part morphology are predicted and compared with the experimental results. Sheared surface and burr height obtained by the analysis coincide with the results of the blanking experiment. © 2018 Académie des sciences
    view abstractdoi: 10.1016/j.crme.2018.05.003
  • 2018 • 239 Nanoimprint lithography of nanoporous carbon materials for micro-supercapacitor architectures
    Lochmann, S. and Grothe, J. and Eckhardt, K. and Leistenschneider, D. and Borchardt, L. and Kaskel, S.
    Nanoscale 10 10109-10115 (2018)
    Nanoimprint lithography is proposed as a highly versatile method for the production of nanostructured supercapacitors (micro-supercapacitors, MSC). Liquid sucrose- and lignin-precursor printing produces patterns with high quality and a line width down to 500 nm. The liquid-carbon-precursor NIL-printing approach enables nitrogen doping to achieve an increased supercapacitor performance for aqueous electrolytes (Li2SO4). The lines are interconverted into nanoporous carbon materials (d ≈ 1 nm) with high specific surface area (&gt;1000 m2 g-1) to form stable structures reaching specific resistivities as low as ρ = 3.5 × 10-5 Ωm and capacitances up to 7 F cm-3. © 2018 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c8nr01535j
  • 2018 • 238 On the nature of spillover hydrogen species on platinum/nitrogen-doped mesoporous carbon composites: A temperature-programmed nitrobenzene desorption study
    Yang, F. and Hu, B. and Xia, W. and Peng, B. and Shen, J. and Muhler, M.
    Journal of Catalysis 365 55-62 (2018)
    Spillover hydrogen species were generated by dissociative H2 adsorption on Pt nanoparticles supported on nitrogen-doped mesoporous carbon. The spillover hydrogen species on the support can migrate back to the Pt nanoparticles and hydrogenate subsequently adsorbed nitrobenzene to aniline at 80 °C, which was detected during temperature-programmed desorption experiments from 80 to 300 °C in pure He. The amount of spillover hydrogen can be tuned mainly by the pre-reduction temperature rather than by other parameters. The absence of aniline formation during nitrobenzene desorption experiments in the presence of CO indicates that hydrogenation occurs exclusively on Pt and that the spillover hydrogen species are present on the carbon support in a chemically inactive state. Most likely, spillover hydrogen is reversibly stored on the carbon support as adsorbed protons on the surface and as electrons in the bulk. These findings provide a new perspective on Pt/C-based hydrogen storage materials and fuel cell catalysts. © 2018
    view abstractdoi: 10.1016/j.jcat.2018.06.020
  • 2018 • 237 Parallelization comparison and optimization of a scale-bridging framework to model Cottrell atmospheres
    Ganesan, H. and Teijeiro, C. and Sutmann, G.
    Computational Materials Science 155 439-449 (2018)
    Low carbon steels undergo strain aging when heat treated, which causes an increased yield strength that can be observed macroscopically. Such strengthening mechanism is driven by atomistic scale processes, i.e., solute segregation of carbon (C) or nitrogen interstitial atoms. Due to its low solubility, alloying elements can diffuse to defects (e.g., dislocations) and form the so-called Cottrell atmospheres. Consequently, the mobility of defects is strongly reduced because of the interaction with solutes, and higher stresses are needed to unpin them from the Cottrell atmosphere. As C segregation and atomistic motion take place at separate timescales, Classical Molecular Dynamics (MD) and Metropolis Monte Carlo (MC) are coupled in a unified framework to capture collective effects with underlying slow dynamics. The number of degrees of freedom and the need for large computational resources in this simulation requires the choice of an optimal parallelization technique for the MC part of such multi-scale simulations using an unbiased sampling of the configuration space. In the present work, two different parallel approaches for the MC routine applied to the simulation of Cottrell atmospheres are implemented and compared: (i) a manager-worker speculative scheme and (ii) a distributed manager-worker over a cell-based domain decomposition approach augmented by an efficient load balancing scheme. The parallel performance of different Fe-C containing defects with several millions of atoms is analyzed, and also the possible optimization of the efficiency of the MC solute segregation process is evaluated regarding energy minimization. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.commatsci.2018.08.055
  • 2018 • 236 Revising the Concept of Pore Hierarchy for Ionic Transport in Carbon Materials for Supercapacitors
    Borchardt, L. and Leistenschneider, D. and Haase, J. and Dvoyashkin, M.
    Advanced Energy Materials 8 (2018)
    Rapid motion of electrolyte ions is a crucial requirement to ensure the fast charging/discharging and the high power densities of supercapacitor devices. This motion is primarily determined by the pore size and connectivity of the used porous carbon electrodes. Here, the diffusion characteristics of each individual electrolyte component, that is, anion, cation, and solvent confined to model carbons with uniform and well-defined pore sizes are quantified. As a result, the contributions of micropores, mesopores, and hierarchical pore architectures to the overall transport of adsorbed mobile species are rationalized. Unexpectedly, it is observed that the presence of a network of mesopores, in addition to smaller micropores—the concept widely used in heterogeneous catalysis to promote diffusion of sorbates—does not necessarily enhance ionic transport in carbon materials. The observed phenomenon is explained by the stripping off the surrounding solvent shell from the electrolyte ions entering the micropores of the hierarchical material, and the resulting enrichment of solvent molecules preferably in the mesopores. It is believed that the presented findings serve to provide fundamental understanding of the mechanisms of electrolyte diffusion in carbon materials and depict a quantitative platform for the future designing of supercapacitor electrodes on a rational basis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/aenm.201800892
  • 2018 • 235 Simultaneous measurement of infrared absorption coefficient of Carbon doped Al0.33Ga0.67As thin film and thermal boundary resistance between thin film and heavily Zn doped GaAs substrate using spectrally-resolved modulated photothermal infrared radiometry
    Pawlak, M. and Horny, N. and Scholz, S. and Ebler, C. and Ludwig, Ar. and Wieck, A.D.
    Thermochimica Acta 667 73-78 (2018)
    In this paper, we investigated C doped Al0.33Ga0.67As thin film epitaxially grown on a Zn-doped GaAs substrate using spectrally resolved modulated photothermal infrared radiometry (SR-PTR). We assumed that thermal conductivity and diffusivity of the thin layer are known and estimate values of the infrared absorption coefficient of the thin layer and the thermal boundary resistance of the interface between the thin layer and the substrate. We found out that the thermal boundary resistance is two orders of magnitude greater than thermal boundary resistance of studied recently undoped AlGaAs/GaAs sample. We attribute this effect to formation of quasi 2-dimensional hole gas due to modulation doping. Finally, the infrared absorption coefficient of the thin layer decreases with increasing wavelength due to inter-valence band absorption. We found out that with increasing infrared absorption coefficient of the thin film, the sensitivity of the method for estimation of the infrared absorption coefficient increases, while the estimation error decreases. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.tca.2018.06.016
  • 2018 • 234 Structural Engineering of 3D Carbon Materials from Transition Metal Ion-Exchanged y Zeolite Templates
    Moon, G.-H. and Bähr, A. and Tüysüz, H.
    Chemistry of Materials 30 3779-3788 (2018)
    A series of three-dimensional ordered microporous carbon materials (3D CMs) were prepared through a nanocasting route by using transition metal ion-exchanged Y zeolite (M-Y) as template and ethylene gas a carbon source. The different d-π coordination and the formation of metal nanoparticles during thermal treatment altered textural parameters of the final carbon products. After a detailed structural analysis and characterization, the most promising cobalt-carbon sample was further treated with NH3 for nitrogen doping and evaluated for oxygen reduction reaction (ORR). This new class of material indicated good electrochemical stability and similar activity in comparison with those of commercial Pt/C (20 wt %) electrocatalyst. The protocol developed here allows in situ incorporation of diverse transition metals as well as the doping of various heteroelements into a three-dimensional carbon framework and has great potential for different catalytic applications. © 2018 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemmater.8b00861
  • 2018 • 233 Structure and size dependence of the magnetic properties of Ni@C nanocomposites
    Manukyan, A. and Elsukova, A. and Mirzakhanyan, A. and Gyulasaryan, H. and Kocharian, A. and Sulyanov, S. and Spasova, M. and Römer, F. and Farle, M. and Sharoyan, E.
    Journal of Magnetism and Magnetic Materials 467 150-159 (2018)
    Carbon-coated nickel (Ni) nanoparticles, Ni@C nanocomposites, have been synthesized using solid-state pyrolysis of nickel phthalocyanine and metal-free phthalocyanine (NiPc)x· (H2Pc)1−x solid solutions, 0⩽x⩽1. The Ni concentrations in carbon matrix (cNi) of the prepared samples continuously varied in the range of 0–3at.% (0–12wt.%). The average nanoparticle size varied within 4–40 nm range. All samples containing single domain Ni nanoparticles exhibit both ferromagnetic and superparamagnetic properties because of the wide range of size distribution. An abrupt drop of saturation magnetization has been observed with decrease in size of Ni nanoparticles from 40 nm to 12 nm. Nearly linear dependence of saturation magnetization on the nanoparticle surface/volume ratio can be interpreted as a result of contact interaction between Ni nanoparticles and the carbon matrix which provides an electron transfer from carbon matrix to nickel. However, further reductions in nanoparticle size increase magnetization growth of which can apparently contribute to the emergence of the giant paramagnetism due to large orbital moments of conductive electrons. The size effects and surface magnetic anisotropy in Ni@C nanocomposites are revealed in the measurements of coercive field, zero-field cooling (ZFC) susceptibility, blocking temperatures and ferromagnetic resonance spectra. Concentration dependencies of ferromagnetic and electron paramagnetic resonance parameters in Ni@C nanocomposites have also been investigated and their peculiarities highlighted. A correlation between concentration dependencies of FMR and SQUID magnetometry parameters, namely between the g-factor curves – geff, the resonance linewidth – ΔHFMR and coercive field – Hc, have been observed. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.jmmm.2018.07.056
  • 2018 • 232 Synthesis of carbon nanowalls from a single-source metal-organic precursor
    Giese, A. and Schipporeit, S. and Buck, V. and Wöhrl, N.
    Beilstein Journal of Nanotechnology 9 1895-1905 (2018)
    In this work, the deposition of carbon nanowalls (CNWs) by inductively coupled plasma enhanced chemical vapor deposition (ICPPECVD) is investigated. The CNWs are electrically conducting and show a large specific surface area, which is a key characteristic to make them interesting for sensors, catalytic applications or energy-storage systems. It was recently discovered that CNW films can be deposited by the use of the single-source metal-organic precursor aluminium acetylacetonate. This precursor is relatively unknown in combination with the ICP-PECVD deposition method in literature and, thus, based on our previous publication is further investigated in this work to better understand the influence of the various deposition parameters on the growth. Silicon, stainless steel, nickel and copper are used as substrate materials. The CNWs deposited are characterized by scanning electron microscopy (SEM), Raman spectroscopy and Auger electron spectroscopy (AES). The combination of bias voltage, the temperature of the substrate and the substrate material had a strong influence on the morphology of the graphitic carbon nanowall structures. With regard to these results, a first growth model for the deposition of CNWs by ICP-PECVD and aluminium acetylacetonate is proposed. This model explains the formation of four different morphologies (nanorods as well as thorny, straight and curled CNWs) by taking the surface diffusion into account. The surface diffusion depends on the particle energies and the substrate material and thus explains the influence of these parameters. © 2018 Giese et al.
    view abstractdoi: 10.3762/bjnano.9.181
  • 2018 • 231 The influence of hydrogen and methane on the growth of carbon particles during acetylene pyrolysis in a burnt-gas flow reactor
    Peukert, S. and Sallom, A. and Emelianov, A. and Endres, T. and Fikri, M. and Böhm, H. and Jander, H. and Eremin, A. and Schulz, C.
    Proceedings of the Combustion Institute (2018)
    The growth of carbon particles was studied in heated flows of a burnt-gas flow reactor containing mixtures of N2/C2H2, and N2/C2H2 with addition of H2 or CH4 surrounded by a rich C2H4/air flame. Soot particle sizes and volume fractions were measured by laser-induced incandescence (LII) between 50 and 130 mm above the nozzle exit. The measurements indicate a soot-inhibiting effect of adding H2 to the C2H2/N2 flow on both, particle sizes and soot volume fractions. The effect of CH4 addition to the C2H2/N2 flows was ambivalent, depending on the methane-to-acetylene ratio. At gas mixtures with N2:CH4:C2H2 = 0.42:0.35:0.23 and 0.39:0.32:0.29 by volume at fixed total flow rates, the measured soot volume fractions were substantially increased in presence of CH4, while the mean diameters of the particles were slightly decreased. Gas temperatures were measured by a generalized line-reversal method with Abel transformation. Temperatures of the surrounding C2H4/air flame were around 1600 K, and temperatures of the inner flows, where soot formation was measured, were between 1550 and 1630 K. Plug-flow reactor calculations provided a qualitative understanding of the influence of CH4 on the soot particle growth. © 2018.
    view abstractdoi: 10.1016/j.proci.2018.05.049
  • 2018 • 230 The mechanochemical Scholl reaction-a solvent-free and versatile graphitization tool
    Grätz, S. and Beyer, D. and Tkachova, V. and Hellmann, S. and Berger, R. and Feng, X. and Borchardt, L.
    Chemical Communications 54 5307-5310 (2018)
    Herein, we report on the mechanochemical Scholl reaction of dendritic oligophenylene precursors to produce benchmark nanographenes such as hexa-peri-hexabenzocoronene (HBC), triangular shaped C60 and expanded C222 under solvent-free conditions. The solvent-free approach overcomes the bottleneck of solubility limitation in this well-known and powerful reaction. The mechanochemical approach allows tracking the reaction process by in situ pressure measurements. The quality of produced nanographenes has been confirmed by MALDI-TOF mass spectrometry and UV-Vis absorption spectroscopy. This approach paves the way towards gram scale and environmentally benign synthesis of extended nanographenes and possibly graphene nanoribbons suitable for application in carbon based electronics or energy applications. © 2018 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c8cc01993b
  • 2018 • 229 Towards Reproducible Fabrication of Nanometre-Sized Carbon Electrodes: Optimisation of Automated Nanoelectrode Fabrication by Means of Transmission Electron Microscopy
    Wilde, P. and Quast, T. and Aiyappa, H.B. and Chen, Y.-T. and Botz, A. and Tarnev, T. and Marquitan, M. and Feldhege, S. and Lindner, A. and Andronescu, C. and Schuhmann, W.
    ChemElectroChem 5 3083-3088 (2018)
    The reproducible fabrication of nanometre-sized carbon electrodes poses great challenges. Especially, the field of single entity electrochemistry has strict requirements regarding the geometry of these electrochemical probes. Herein, an automated setup for the fabrication of carbon nanoelectrodes based on the pyrolysis of a propane/butane gas mixture within pulled quartz capillaries by means of a moving heating coil is presented. It is shown that mere electrochemical characterisation with conventional redox mediators does not allow for a reliable assessment of the electrode's geometry and quality. Therefore, high-throughput transmission electron microscopy is used in parallel to evaluate and optimise preparation parameters. Control of the latter gives access to three different electrode types: nanopipettes, nanosamplers and nanodisks. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/celc.201800600
  • 2018 • 228 Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy
    Beerwerth, J. and Storek, M. and Greim, D. and Lueg, J. and Siegel, R. and Cetinkaya, B. and Hiller, W. and Zimmermann, H. and Senker, J. and Böhmer, R.
    Journal of Magnetic Resonance 288 84-94 (2018)
    Polycrystalline dimethyl sulfone is studied using central-transition oxygen-17 exchange NMR. The quadrupolar and chemical shift tensors are determined by combining quantum chemical calculations with line shape analyses of rigid-lattice spectra measured for stationary and rotating samples at several external magnetic fields. Quantum chemical computations predict that the largest principal axes of the chemical shift anisotropy and electrical field gradient tensors enclose an angle of about 73°. This prediction is successfully tested by comparison with absorption spectra recorded at three different external magnetic fields. The experimental one-dimensional motionally narrowed spectra and the two-dimensional exchange spectrum are compatible with model calculations involving jumps of the molecules about their two-fold symmetry axis. This motion is additionally investigated by means of two-time stimulated-echo spectroscopy which allows for a determination of motional correlation functions over a wider temperature range than previously reported using carbon and deuteron NMR. On the basis of suitable second-order quadrupolar frequency distributions, sin-sin stimulated-echo amplitudes are calculated for a two-site model in the limit of vanishing evolution time and compared with experimental findings. The present study thus establishes oxygen-17 NMR as a powerful method that will be particularly useful for the study of solids and liquids devoid of nuclei governed by first-order anisotropies. © 2018 Elsevier Inc.
    view abstractdoi: 10.1016/j.jmr.2018.01.016
  • 2018 • 227 Water assisted atomic layer deposition of yttrium oxide using tris(N,N0-diisopropyl-2-dimethylamido-guanidinato) yttrium(III): Process development, film characterization and functional properties†
    Mai, L. and Boysen, N. and Subaşı, E. and De Los Arcos, T. and Rogalla, D. and Grundmeier, G. and Bock, C. and Lu, H.-L. and Devi, A.
    RSC Advances 8 4987-4994 (2018)
    We report a new atomic layer deposition (ALD) process for yttrium oxide (Y2O3) thin films using tris(N,N0-diisopropyl-2-dimethylamido-guanidinato) yttrium(III) [Y(DPDMG)3] which possesses an optimal reactivity towards water that enabled the growth of high quality thin films. Saturative behavior of the precursor and a constant growth rate of 1.1 Å per cycle confirm the characteristic self-limiting ALD growth in a temperature range from 175 C to 250 C. The polycrystalline films in the cubic phase are uniform and smooth with a root mean squared (RMS) roughness of 0.55 nm, while the O/Y ratio of 2.0 reveal oxygen rich layers with low carbon contaminations of around 2 at%. Optical properties determined via UV/Vis measurements revealed the direct optical band gap of 5.56 eV. The valuable intrinsic properties such as a high dielectric constant make Y2O3 a promising candidate in microelectronic applications. Thus the electrical characteristics of the ALD grown layers embedded in a metal insulator semiconductor (MIS) capacitor structure were determined which resulted in a dielectric permittivity of 11, low leakage current density (z107 A cm2 at 2 MV cm1) and high electrical breakdown fields (4.0–7.5 MV cm1). These promising results demonstrate the potential of the new and simple Y2O3 ALD process for gate oxide applications. © The Royal Society of Chemistry 2018.
    view abstractdoi: 10.1039/c7ra13417g
  • 2017 • 226 A coated inclusion-based homogenization scheme for viscoelastic composites with interphases
    Schöneich, M. and Dinzart, F. and Sabar, H. and Berbenni, S. and Stommel, M.
    Mechanics of Materials 105 89-98 (2017)
    A coated inclusion-based homogenization scheme is developed for three-phase viscoelastic composites in the Laplace–Carson domain. The interphase between inclusion and matrix is considered as a coating in a composite-like inclusion and shows altered viscoelastic behavior compared to the matrix. The strain concentration equations between the viscoelastic inclusion and the viscoelastic coating are derived with two different models: the double inclusion (denoted DI) model, and the reconsidered double inclusion (RDI) model. Then, the homogenization scheme is based on a modified Mori–Tanaka scheme for three-phase viscoelastic composites, which is validated with the exact analytical formulation in the case of spherical composite inclusions and isotropic behaviors for all constituents. The comparison of the proposed coated inclusion-based homogenization scheme based on the RDI model with the exact analytical solution shows a significant improvement compared to the one based on the DI model in the prediction of effective properties for composites with interphases. Finally, considering experimental dynamic mechanical analyses (DMA) in the frequency domain for a carbon-black filled styrene butadiene rubber from the literature, the effective viscoelastic behavior is estimated with a good accuracy in terms of the storage and loss moduli for different volume fractions of composite inclusions. © 2016
    view abstractdoi: 10.1016/j.mechmat.2016.11.009
  • 2017 • 225 A novel versatile microbiosensor for local hydrogen detection by means of scanning photoelectrochemical microscopy
    Zhao, F. and Conzuelo, F. and Hartmann, V. and Li, H. and Stapf, S. and Nowaczyk, M.M. and Rögner, M. and Plumeré, N. and Lubitz, W. and Schuhmann, W.
    Biosensors and Bioelectronics 94 433-437 (2017)
    The development of a versatile microbiosensor for hydrogen detection is reported. Carbon-based microelectrodes were modified with a [NiFe]-hydrogenase embedded in a viologen-modified redox hydrogel for the fabrication of a sensitive hydrogen biosensor By integrating the microbiosensor in a scanning photoelectrochemical microscope, it was capable of serving simultaneously as local light source to initiate photo(bio)electrochemical reactions while acting as sensitive biosensor for the detection of hydrogen. A hydrogen evolution biocatalyst based on photosystem 1-platinum nanoparticle biocomplexes embedded into a specifically designed redox polymer was used as a model for proving the capability of the developed hydrogen biosensor for the detection of hydrogen upon localized illumination. The versatility and sensitivity of the proposed microbiosensor as probe tip allows simplification of the set-up used for the evaluation of complex electrochemical processes and the rapid investigation of local photoelectrocatalytic activity of biocatalysts towards light-induced hydrogen evolution. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.bios.2017.03.037
  • 2017 • 224 A quantum chemical and kinetics modeling study on the autoignition mechanism of diethyl ether
    Sakai, Y. and Herzler, J. and Werler, M. and Schulz, C. and Fikri, M.
    Proceedings of the Combustion Institute 36 195-202 (2017)
    A detailed chemical kinetics model has been developed to elucidate the auto-ignition behavior of diethyl ether (DEE) under conditions relevant for internal combustion engines. The present model is composed of a C0-C4 base module from literature and a DEE module. For the low-temperature oxidation mechanism, the reactions of ROO and QOOH radicals were studied previously with a quantum-chemical and transition state theory approach by Sakai et al. (2015). In the present study, the potential energy surfaces for the unimolecular reactions of OOQOOH isomers and 1- and 2-ethoxyethyl radicals were determined with a CBSQB3 composite method. In the presence of an OOH group, the reaction barrier of the hydrogen shift from the β site (terminal carbon atom) decreases as it does in alkane oxidation but there is no effect on the hydrogen shift from the α site (next to the ether oxygen atom). Therefore, the reaction barriers of OOQOOH isomers have the same trend as the corresponding ROO radical and rate constants for the reactions of OOQOOH isomers were determined. The constructed model was validated against the recent data of ignition delay times provided in literature by Werler et al. (2015). The agreement is good over the temperature range 500-1300K and pressure range 1-40bar, although, open questions remain regarding the non-consensus at 900-1150K and 40bar. Reaction-path and sensitivity analyses attribute the importance of the reactivity at the α site to the decrease of the C H bond dissociation energy due to the ether oxygen atom. © 2016.
    view abstractdoi: 10.1016/j.proci.2016.06.037
  • 2017 • 223 A Self-Powered Ethanol Biosensor
    Ruff, A. and Pinyou, P. and Nolten, M. and Conzuelo, F. and Schuhmann, W.
    ChemElectroChem 4 890-897 (2017)
    We describe the fabrication of a self-powered ethanol biosensor comprising a β-NAD+-dependent alcohol dehydrogenase (ADH) bioanode and a bienzymatic alcohol oxidase (AOx) and horseradish peroxidase (HRP) biocathode. β-NAD+ is regenerated by means of a specifically designed phenothiazine dye (i.e. toluidine blue, TB) modified redox polymer in which TB was covalently anchored to a hexanoic acid tethered poly(4-vinylpyridine) backbone. The redox polymer acts as an immobilization matrix for ADH. Using a carefully chosen anchoring strategy through the formation of amide bonds, the potential of the TB-based mediator is shifted to more positive potentials, thus preventing undesired O2 reduction. To counterbalance the rather high potential of the TB-modified polymer, and thus the bioanode, a high-potential AOx/HRP-based biocathode is suggested. HRP is immobilized in a direct-electron-transfer regime on screen-printed graphite electrodes functionalized with multi-walled carbon nanotubes. The nanostructured cathode ensures the wiring of the iron-oxo complex within oxidized HRP, and thus a high potential for the reduction of H2O2 of about +550mV versus Ag/AgCl/3M KCl. The proposed biofuel cell exhibits an open-circuit voltage (OCV) of approximately 660mV and was used as self-powered device for the determination of the ethanol content in liquor. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201600864
  • 2017 • 222 Bridging Hydride at Reduced H-Cluster Species in [FeFe]-Hydrogenases Revealed by Infrared Spectroscopy, Isotope Editing, and Quantum Chemistry
    Mebs, S. and Senger, M. and Duan, J. and Wittkamp, F. and Apfel, U.-P. and Happe, T. and Winkler, M. and Stripp, S.T. and Haumann, M.
    Journal of the American Chemical Society 139 12157-12160 (2017)
    [FeFe]-Hydrogenases contain a H2-converting cofactor (H-cluster) in which a canonical [4Fe-4S] cluster is linked to a unique diiron site with three carbon monoxide (CO) and two cyanide (CN-) ligands (e.g., in the oxidized state, Hox). There has been much debate whether reduction and hydrogen binding may result in alternative rotamer structures of the diiron site in a single (Hred) or double (Hsred) reduced H-cluster species. We employed infrared spectro-electrochemistry and site-selective isotope editing to monitor the CO/CN- stretching vibrations in [FeFe]-hydrogenase HYDA1 from Chlamydomonas reinhardtii. Density functional theory calculations yielded vibrational modes of the diatomic ligands for conceivable H-cluster structures. Correlation analysis of experimental and computational IR spectra has facilitated an assignment of Hred and Hsred to structures with a bridging hydride at the diiron site. Pronounced ligand rotation during μH binding seems to exclude Hred and Hsred as catalytic intermediates. Only states with a conservative H-cluster geometry featuring a μCO ligand are likely involved in rapid H2 turnover. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/jacs.7b07548
  • 2017 • 221 Carbon onion-sulfur hybrid cathodes for lithium-sulfur batteries
    Choudhury, S. and Zeiger, M. and Massuti-Ballester, P. and Fleischmann, S. and Formanek, P. and Borchardt, L. and Presser, V.
    Sustainable Energy and Fuels 1 84-94 (2017)
    In this study, we explore carbon onions (diameter below 10 nm), for the first time, as a substrate material for lithium sulfur cathodes. We introduce several scalable synthesis routes to fabricate carbon onion-sulfur hybrids by adopting in situ and melt diffusion strategies with sulfur fractions up to 68 mass%. The conducting skeleton of agglomerated carbon onions proved to be responsible for keeping active sulfur always in close vicinity to the conducting matrix. Therefore, the hybrids are found to be efficient cathodes for Li-S batteries, yielding 97-98% Coulombic efficiency over 150 cycles with a slow fading of the specific capacity (ca. 660 mA h g-1 after 150 cycles) in long term cycle test and rate capability experiments. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6se00034g
  • 2017 • 220 Characterization of hybrid joining techniques for FRP/Steel-structures under combined mechanical and thermal loading
    Hoepfner, M. and Becker, T. and Hülsbusch, D. and Walther, F.
    Key Engineering Materials 742 KEM 358-365 (2017)
    In order to optimize the design of vibrating screening machines and realize significant weight reductions, the use of hybrid structures is gaining importance. In this context, the joining of FRP and steel and their interactions due to different material properties were investigated. Therefore, quasi-static tests with combined mechanical and thermal loads were carried out. To realize the simultaneous application of physical measurement techniques, e.g. optical and acoustic measurements, and thermal loads, short-wave infrared emitter technique was used instead of thermal chambers. Thus, the mechanical characteristics and acoustic emissions could be determined and assessed. The results show different structural mechanisms of hybrid joining at room and elevated temperatures. The characteristics of failure modes, shear stresses, strains and acoustic emissions could be correlated to determine the damage developments and mechanisms. © 2017 Trans Tech Publications, Switzerland.
    view abstractdoi: 10.4028/www.scientific.net/KEM.742.358
  • 2017 • 219 Chemical and structural analysis of gallstones from the Indian subcontinent
    Ramana Ramya, J. and Thanigai Arul, K. and Epple, M. and Giebel, U. and Guendel-Graber, J. and Jayanthi, V. and Sharma, M. and Rela, M. and Narayana Kalkura, S.
    Materials Science and Engineering C 78 878-885 (2017)
    Representative gallstones from north and southern parts of India were analyzed by a combination of physicochemical methods: X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), CHNS analysis, thermal analysis and Nuclear Magnetic Resonance (NMR) spectroscopy (1H and 13C). The stones from north Indian were predominantly consisting of cholesterol monohydrate and anhydrous cholesterol which was confirmed by XRD analysis. FTIR spectroscopy confirmed the presence of cholesterol and calcium bilirubinate in the south Indian gallstones. EDX spectroscopy revealed the presence of carbon, nitrogen, oxygen, calcium, sulfur, sodium and magnesium and chloride in both south Indian and north Indian gallstones. FTIR and NMR spectroscopy confirmed the occurrence of cholesterol in north Indian gallstones. The respective colour of the north Indian and south Indian gallstones was yellowish and black. The morphology of the constituent crystals of the north Indian and south Indian gallstones were platy and globular respectively. The appreciable variation in colour, morphology and composition of south and north Indian gallstones may be due to different food habit and habitat. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.msec.2017.04.004
  • 2017 • 218 Co3O4@Co/NCNT Nanostructure Derived from a Dicyanamide-Based Metal-Organic Framework as an Efficient Bi-functional Electrocatalyst for Oxygen Reduction and Evolution Reactions
    Sikdar, N. and Konkena, B. and Masa, J. and Schuhmann, W. and Maji, T.K.
    Chemistry - A European Journal 23 18049-18056 (2017)
    There has been growing interest in the synthesis of efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reactions (OER), for their potential use in a variety of renewable energy technologies, such as regenerative fuel cells and metal-air batteries. Here, a bi-functional electrocatalyst, derived from a novel dicyanamide based nitrogen rich MOF {[Co(bpe)2(N(CN)2)]⋅(N(CN)2)⋅(5 H2O)}n [Co-MOF-1, bpe=1,2-bis(4-pyridyl)ethane, N(CN)2 −=dicyanamide] under different pyrolysis conditions is reported. Pyrolysis of the Co-MOF-1 under Ar atmosphere (at 800 °C) yielded a Co nanoparticle-embedded N-doped carbon nanotube matrix (Co/NCNT-Ar) while pyrolysis under a reductive H2/Ar atmosphere (at 800 °C) and further mild calcination yielded Co3O4@Co core–shell nanoparticle-encapsulated N-doped carbon nanotubes (Co3O4@Co/NCNT). Both catalysts show bi-functional activity towards ORR and OER, however, the core–shell Co3O4@Co/NCNT nanostructure exhibited superior electrocatalytic activity for both the ORR with a potential of 0.88 V at a current density of −1 mA cm−2 and the OER with a potential of 1.61 V at 10 mA cm−2, which is competitive with the most active bi-functional catalysts reported previously. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201704211
  • 2017 • 217 Cobalt boride modified with N-doped carbon nanotubes as a high-performance bifunctional oxygen electrocatalyst
    Elumeeva, K. and Masa, J. and Medina, D. and Ventosa, E. and Seisel, S. and Kayran, Y.U. and Genç, A. and Bobrowski, T. and Weide, P. and Arbiol, J. and Muhler, M. and Schuhmann, W.
    Journal of Materials Chemistry A 5 21122-21129 (2017)
    The development of reversible oxygen electrodes, able to drive both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), is still a great challenge. We describe a very efficient and stable bifunctional electrocatalytic system for reversible oxygen electrodes obtained by direct CVD growth of nitrogen-doped carbon nanotubes (NCNTs) on the surface of cobalt boride (CoB) nanoparticles. A detailed investigation of the crystalline structure and elemental distribution of CoB before and after NCNT growth reveals that the NCNTs grow on small CoB nanoparticles formed in the CVD process. The resultant CoB/NCNT system exhibited outstanding activity in catalyzing both the OER and the ORR in 0.1 M KOH with an overvoltage difference of only 0.73 V between the ORR at -1 mA cm-2 and the OER at +10 mA cm-2. The proposed CoB/NCNT catalyst showed stable performance during 50 h of OER stability assessment in 0.1 M KOH. Moreover, CoB/NCNT spray-coated on a gas diffusion layer as an air-breathing electrode proved its high durability during 170 galvanostatic charge-discharge (OER/ORR) test cycles (around 30 h) at ±10 mA cm-2 in 6 M KOH, making it an excellent bifunctional catalyst for potential Zn-air battery application. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7ta06995b
  • 2017 • 216 Correlation between cavitation erosion resistance and cyclic mechanical properties of different metallic materials
    Kaufhold, C. and Pöhl, F. and Theisen, W.
    Journal of Physics: Conference Series 843 (2017)
    Machine components in contact with flowing fluids are especially prone to cavitation erosion, where plastic deformation and material loss occur due to the repeated implosion of cavitation bubbles in the vicinity of a solid surface. Identifying a correlation between experimentally derivable material properties and resistance against cavitation erosion could help improve the lifetime of cavitation-affected components. Cavitation erosion is a predominantly fatigue-driven phenomenon. In this investigation, we conducted nanoindentation experiments to examine cyclic micromechanical material properties in response to an increasing number of cycles. The experiments were performed on pure iron and different steel grades, i.e., austenitic stainless CrMnCN steels, interstitially alloyed with carbon and nitrogen. We confirmed the view, also proposed in literature, that indentation hardness is inappropriate for ordering the investigated materials by incubation period or maximum erosion rate. We found that the percentage increase of nanoindentation contact stiffness, after an increasing number of cycles, is a promising indicator in terms of the overall ranking of cavitation erosion resistance among the considered materials. Although a single cavitation impact is associated with a significantly higher strain rate than nanoindentation experiments, it is shown that the plastically deformed area around each indent exhibits indications of deformation, such as the formation of slip lines that are also observable after cavitation-induced impacts. © Published under licence by IOP Publishing Ltd.
    view abstractdoi: 10.1088/1742-6596/843/1/012037
  • 2017 • 215 Corrosion resistance of high-alloyed stainless steel membrane supports under flue gas conditions of a lignite-fueled power plant
    Bram, M. and Seifert, M. and Kot, A. and Wilkner, K. and Wulbieter, N. and Theisen, W.
    Materials and Corrosion (2017)
    Metal-supported silica membranes are attractive candidates for CO2 capture from the exhaust of coal-fueled power plants. Compared to their full ceramic counterparts, the introduction of the metal support facilitates sealing of the membrane by established technologies, such as welding, and enhances the robustness of the membrane in the harsh environment of the power plant. As well-known from other steel components in flue gas desulfurization units, long-term corrosion resistance of the metal support is mandatory for the success of this new membrane concept. In the present work, a research concept is introduced enabling a systematic benchmark of stainless steels regarding their suitability to be used for the metal support of the CO2 selective silica membranes. The study combines field tests of porous samples in direct contact with the exhaust gas of a lignite-fueled power plant and standardized corrosion tests of dense and porous samples in the laboratory according to DIN 50918 using exhaust gas condensate as the corrosive medium. Preliminary results are achieved on austenitic steel (AISI 316L) as well as on two ferritic steels (Crofer22APU, Plansee ITM). Ferritic steels are chosen due to their availability as substrates with well-defined porosity and with adapted thermal expansion coefficient enabling successful coating of the CO2 selective silica membrane. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/maco.201709456
  • 2017 • 214 Detection of adsorbed transition-metal porphyrins by spin-dependent conductance of graphene nanoribbon
    Kratzer, P. and Tawfik, S.A. and Cui, X.Y. and Stampfl, C.
    RSC Advances 7 29112-29121 (2017)
    Electronic transport in a zig-zag-edge graphene nanoribbon (GNR) and its modification by adsorbed transition metal porphyrins is studied by means of density functional theory calculations. The detachment reaction of the metal centre of the porphyrin is investigated both in the gas phase and for molecules adsorbed on the GNR. As most metal porphyrins are very stable against this reaction, it is found that these molecules bind only weakly to a perfect nanoribbon. However, interaction with a single-atom vacancy in the GNR results in chemical bonding by the transition metal centre being shared between nitrogen atoms in the porphyrin ring and the carbon atoms next to the vacancy in the GNR. For both the physisorbed and the chemisorbed geometry, the inclusion of van der Waals interaction results in a significant enlargement of the binding energy and reduction of the adsorption height. Electronic transport calculations using non-equilibrium Greens functions show that the conductivity of the GNR is altered by the chemisorbed porphyrin molecules. Since the metal centers of porphyrins carry an element-specific magnetic moment, not only the net conductance, but also the spin-dependent conductance of the GNR is affected. In particular, the adsorption of Ru-porphyrin on the single-atom vacancy results in a very large spin polarization of the current of 88% at small applied source-drain voltages. Based on our results, we suggest that a spin valve constructed from a GNR with ferromagnetic contacts could be used as a sensitive detector that could discriminate between various metal porphyrins. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7ra04594h
  • 2017 • 213 Diffusion processes during cementite precipitation and their impact on electrical and thermal conductivity of a heat-treatable steel
    Klein, S. and Mujica Roncery, L. and Walter, M. and Weber, S. and Theisen, W.
    Journal of Materials Science 52 375-390 (2017)
    The thermal conductivity of heat-treatable steels is highly dependent on their thermo-mechanical history and the alloying degree. Besides phase transformations like the martensitic γ → α ′ or the degree of deformation, the precipitation of carbides exerts a strong influence on the thermal conductivity of these steels. In the current work, thermal and electrical conductivity of a 0.45 mass% C steel is investigated during an isothermal heat treatment at 700 ∘C and correlated with the precipitation kinetics of cementite. To include processes in the short-term as well as in the long-term range, annealing times from 1 s to 200 h are applied. This investigation includes microstructural characterization, diffusion simulations, and electrical and thermal conductivity measurements. The precipitation of carbides is connected with various microstructural processes which separately influence the thermophysical properties of the steel from the solution state to the short-term and long-term annealing states. In the early stages of cementite growth, an interstitial-dominated diffusion reaction takes place (carbon diffusion in the metastable condition of local equilibrium non-partitioning). Afterwards, substitutional-dominated diffusion controls the kinetics of the reaction. The electrical and thermal conductivity increase differently during the two stages of the carbide precipitation. The increment is associated to the binding of alloying elements into the carbides and to the reduction of the distortion of the martensitic matrix. Both factors increase the electron density and reduce the electron and phonon scattering. The correlation of the precipitation kinetics and the thermophysical properties are of general interest for the design of heat-treatable steels. © 2016, The Author(s).
    view abstractdoi: 10.1007/s10853-016-0338-1
  • 2017 • 212 Effects of defects in series production of hybrid CFRP lightweight components – detection and evaluation of quality critical characteristics
    Berger, D. and Brabandt, D. and Bakir, C. and Hornung, T. and Lanza, G. and Summa, J. and Schwarz, M. and Herrmann, H.-G. and Pohl, M. and Stommel, M.
    Measurement: Journal of the International Measurement Confederation 95 389-394 (2017)
    The field of application of carbon fibre reinforced plastics (CFRP) is expanded successively by the insertion of additional components in manufactured parts. These inserts can be used as mechanical interfaces between CFRP and external forces, which is why it is necessary to ensure that the interface is free of defects. Especially the CFRP component is prone to defects due to process and material properties. Currently there are very limited possibilities to evaluate the quality of this type of innovative combination of components. Therefore this publication presents the optimized operation of both 3D and 2D measurement systems in series production, which are used to detect defects that appear in the production of hybrid metal components in the Resin Transfer Moulding Process. The severity of these defects is characterized in both destructive and non-destructive testing and helps to evaluate the necessity of in-line measurement systems and their allocation in the production process. © 2016 Elsevier Ltd
    view abstractdoi: 10.1016/j.measurement.2016.10.003
  • 2017 • 211 Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation
    Rösler, C. and Dissegna, S. and Rechac, V.L. and Kauer, M. and Guo, P. and Turner, S. and Ollegott, K. and Kobayashi, H. and Yamamoto, T. and Peeters, D. and Wang, Y. and Matsumura, S. and Van Tendeloo, G. and Kitagawa, H. and Mu...
    Chemistry - A European Journal 23 3583-3594 (2017)
    The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal-organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core-shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core-shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201603984
  • 2017 • 210 Energy Transfer Kinetics in Photosynthesis as an Inspiration for Improving Organic Solar Cells
    Nganou, C. and Lackner, G. and Teschome, B. and Deen, M.J. and Adir, N. and Pouhe, D. and Lupascu, D.C. and Mkandawire, M.
    ACS Applied Materials and Interfaces 9 19030-19039 (2017)
    Clues to designing highly efficient organic solar cells may lie in understanding the architecture of light-harvesting systems and exciton energy transfer (EET) processes in very efficient photosynthetic organisms. Here, we compare the kinetics of excitation energy tunnelling from the intact phycobilisome (PBS) light-harvesting antenna system to the reaction center in photosystem II in intact cells of the cyanobacterium Acaryochloris marina with the charge transfer after conversion of photons into photocurrent in vertically aligned carbon nanotube (va-CNT) organic solar cells with poly(3-hexyl)thiophene (P3HT) as the pigment. We find that the kinetics in electron hole creation following excitation at 600 nm in both PBS and va-CNT solar cells to be 450 and 500 fs, respectively. The EET process has a 3 and 14 ps pathway in the PBS, while in va-CNT solar cell devices, the charge trapping in the CNT takes 11 and 258 ps. We show that the main hindrance to efficiency of va-CNT organic solar cells is the slow migration of the charges after exciton formation. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acsami.7b04028
  • 2017 • 209 Improved CO2 Electroreduction Performance on Plasma-Activated Cu Catalysts via Electrolyte Design: Halide Effect
    Gao, D. and Scholten, F. and Roldan Cuenya, B.
    ACS Catalysis 7 5112-5120 (2017)
    As a sustainable pathway for energy storage and to close the carbon cycle, CO2 electroreduction has recently gained significant interest. We report here the role of the electrolyte, in particular of halide ions, on CO2 electroreduction over plasma-oxidized polycrystalline Cu foils. It was observed that halide ions such as I- can induce significant nanostructuring of the oxidized Cu surface, even at open circuit potential, including the formation of Cu crystals with well-defined shapes. Furthermore, the presence of Cl-, Br-, and I- was found to lower the overpotential and to increase the CO2 electroreduction rate on plasma-activated preoxidized Cu catalyst in the order Cl- &lt; Br- &lt; I-, without sacrificing their intrinsically high C2-C3 product selectivity (∼65% total Faradaic efficiency at -1.0 V vs RHE). This enhancement in catalytic performance is mainly attributed to the specific adsorption of halides with a higher coverage on our oxidized Cu surface during the reaction, which have been previously reported to facilitate the formation and stabilization of the carboxyl (∗COOH) intermediate by partial charge donation from the halide ions to CO2. (Graph Presented). © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.7b01416
  • 2017 • 208 Intermediate Product Regulation in Tandem Solid Catalysts with Multimodal Porosity for High-Yield Synthetic Fuel Production
    Duyckaerts, N. and Bartsch, M. and Trotuş, I.-T. and Pfänder, N. and Lorke, A. and Schüth, F. and Prieto, G.
    Angewandte Chemie - International Edition 56 11480-11484 (2017)
    Tandem catalysis is an attractive strategy to intensify chemical technologies. However, simultaneous control over the individual and concerted catalyst performances poses a challenge. We demonstrate that enhanced pore transport within a Co/Al2O3 Fischer–Tropsch (FT) catalyst with hierarchical porosity enables its tandem integration with a Pt/ZSM-5 zeolitic hydrotreating catalyst in a spatially distant fashion that allows for catalyst-specific temperature adjustment. Nevertheless, this system resembles the case of close active-site proximity by mitigating secondary reactions of primary FT α-olefin products. This approach enables the combination of in situ dewaxing with a minimum production of gaseous hydrocarbons (18 wt %) and an up to twofold higher (50 wt %) selectivity to middle distillates compared to tandem pairs based on benchmark mesoporous FT catalysts. An overall 80 % selectivity to liquid hydrocarbons from syngas is attained in one step, attesting to the potential of this strategy for increasing the carbon efficiency in intensified gas-to-liquid technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201705714
  • 2017 • 207 Introduction of an integrated turbo-electrical machine
    Schuster, S. and Kreischer, C. and Brillert, D.
    Proceedings of the ASME Turbo Expo 8 (2017)
    Turbomachines are commonly designed for a high mass flow rate. However, because of new cycle concepts, turbomachines are also required to compress or expand at small mass flow rates. One example is the supercritical carbon dioxide Brayton cycle. The mass flow rate can be in the range of one kg/s at an almost high fluid density at the inlet to the compressor. This results in a small through flow area. In this paper, a turbomachine concept is presented that integrates the turbomachine parts into an electrical machine. Specifically, the turbomachine is located in the gap between the rotor and the stator of the electrical machine. In that way, a very compact design can be achieved. This paper aims to explain the basic concept. An aerodynamic design study is performed that demonstrates the important parameters for machine performance. Additionally, the design of the electrical machine is discussed based on a realistic application. Finally, conclusions for further development are drawn. Copyright © 2017 ASME.
    view abstractdoi: 10.1115/GT2017-63526
  • 2017 • 206 Investigation of the tribological behaviour of HS6-5-3 type tool steels during high-temperature sliding wear
    Walter, M. and Egels, G. and Boes, J. and Röttger, A. and Theisen, W.
    HTM - Journal of Heat Treatment and Materials 72 105-114 (2017)
    The wear behaviour of work roll materials is an important issue during the hot rolling process of metals. For this reason, the present study investigates the mechanical properties and the sliding wear behaviour of HS6-5-3 type high-speed steels (HSS) at elevated temperatures. Influences on the performance of HSS discussed are the microstructural constitution (as-cast and electro-slag remelted condition), the heat-treatment condition and the overall tribological system (C60 carbon steel and X5CrNi18-10 stainless steel counter-body materials). The results of the study show, how mechanical and tribological properties of HSS depend on these aspects and how a modification of the processing route can lead to improved high-temperature properties of HSS. As a main aspect the investigations show that, the formation of tribochemical wear layers during high-temperature sliding wear needs to be regarded. Tribochemical wear layers dominate the high-temperature wear behavior of steels. Therefore, the formation, characteristics and stability of tribochemical wear layers are analysed [1]. Copyright © 2017 Carl Hanser Verlag GmbH & Co. KG.
    view abstractdoi: 10.3139/105.110315
  • 2017 • 205 Large eddy simulations of nanoparticle synthesis from flame spray pyrolysis
    Rittler, A. and Deng, L. and Wlokas, I. and Kempf, A.M.
    Proceedings of the Combustion Institute 36 1077-1087 (2017)
    Large eddy simulations of the nanoparticle synthesis from flame spray pyrolysis are presented. A standard reactor is investigated, with ethanol/hexamethyldisiloxane (HMDSO) mixture as spray/precursor composition and oxygen as dispersion gas for the production of silica nanoparticles. Spray evaporation, ignition and stabilisation of the flame are achieved by a premixed methane/oxygen pilot flame. The gas, spray and nanoparticle phases are modelled with Eulerian, Lagrangian and Eulerian approaches, respectively. A modified tabulated chemistry model, adapted from the premixed flamelet generated manifold approach (PFGM) with artificial flame thickening (ATF) is proposed, tested and applied for the system. The control variables are the element mass fractions of hydrogen and carbon together with a joint progress variable. The population balance equation of the nanoparticles is modelled in terms of number, volume and surface area concentration, its subfilter distribution is modelled with a delta function. The combustion of HMDSO and formation of silica particle monomers is described by a two-step global mechanism. The nucleation source term is tabulated as a function of the control variables. The submodels for spray and combustion are validated separately to compensate for the shortage in detailed experimental data for nanoparticle spray flames. Subsequently, simulation results for the particles are presented and discussed, in particular the polydisperse particle size distributions resulting from turbulence. © 2016 The Combustion Institute.
    view abstractdoi: 10.1016/j.proci.2016.08.005
  • 2017 • 204 Laser-Induced Functionalization of Organo/Carbon Interfaces for Selective Adsorption of Au Nanoparticles in Microsized Domains
    Schade, M. and Franzka, S. and Hartmann, N.
    Langmuir 33 8686-8692 (2017)
    Laser microprocessing of highly oriented pyrolytic graphite (HOPG) in conjunction with chemical functionalization routines is used to fabricate functional microsized domains. Infrared and Auger electron spectroscopy, contact angle measurements, and electron microscopy are used for characterization of laser-fabricated structures. HOPG samples are coated with alkylsiloxane monolayers. Laser-induced bromination of coated HOPG samples in gaseous bromine is carried out using a microfocused laser beam at a wavelength of 514 nm and 1/e2 laser spot diameter of about 2 μm. Subsequent azidation and amination results in functional domains with sizes in the range of 1.2 to 40 μm and more. At low laser powers and irradiation times fully functionalized circular-shaped structures are formed. At high laser powers and irradiation times laser processing results in decomposition of the organic monolayer and substrate in the center of the structures yielding donut-shaped structures. After laser processing and chemical transformation Au nanoparticles are selectively adsorbed onto the functional domains. This provides an opportunity to build up functional nanoparticle microarrays on carbon-based materials, e.g., for applications in sensing and electrocatalysis. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acs.langmuir.7b00695
  • 2017 • 203 Low temperature growth of gallium oxide thin films via plasma enhanced atomic layer deposition
    O'Donoghue, R. and Rechmann, J. and Aghaee, M. and Rogalla, D. and Becker, H.-W. and Creatore, M. and Wieck, A.D. and Devi, A.
    Dalton Transactions 46 16551-16561 (2017)
    Herein we describe an efficient low temperature (60-160 °C) plasma enhanced atomic layer deposition (PEALD) process for gallium oxide (Ga2O3) thin films using hexakis(dimethylamido)digallium [Ga(NMe2)3]2 with oxygen (O2) plasma on Si(100). The use of O2 plasma was found to have a significant improvement on the growth rate and deposition temperature when compared to former Ga2O3 processes. The process yielded the second highest growth rates (1.5 Å per cycle) in terms of Ga2O3 ALD and the lowest temperature to date for the ALD growth of Ga2O3 and typical ALD characteristics were determined. From in situ quartz crystal microbalance (QCM) studies and ex situ ellipsometry measurements, it was deduced that the process is initially substrate-inhibited. Complementary analytical techniques were employed to investigate the crystallinity (grazing-incidence X-ray diffraction), composition (Rutherford backscattering analysis/nuclear reaction analysis/X-ray photoelectron spectroscopy), morphology (X-ray reflectivity/atomic force microscopy) which revealed the formation of amorphous, homogeneous and nearly stoichiometric Ga2O3 thin films of high purity (carbon and nitrogen &lt;2 at.%) under optimised process conditions. Tauc plots obtained via UV-Vis spectroscopy yielded a band gap of 4.9 eV and the transmittance values were more than 80%. Upon annealing at 1000 °C, the transformation to oxygen rich polycrystalline β-gallium oxide took place, which also resulted in the densification and roughening of the layer, accompanied by a slight reduction in the band gap. This work outlines a fast and efficient method for the low temperature ALD growth of Ga2O3 thin films and provides the means to deposit Ga2O3 upon thermally sensitive polymers like polyethylene terephthalate. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7dt03427j
  • 2017 • 202 Micrometer-sized nano-structured silicon/carbon composites for lithium-ion battery anodes synthesized based on a three-step Hansen solubility parameter (HSP) concept
    Sehlleier, Y.H. and Dobrowolny, S. and Xiao, L. and Heinzel, A. and Schulz, C. and Wiggers, H.
    Journal of Industrial and Engineering Chemistry 52 305-313 (2017)
    The processing towards Si/C composites, components and synthesis parameters were selected based on the concept of Hansen solubility parameters (HSP). Si/polymer composites were generated through modified bulk polymerization and subsequent pyrolysis transformed the polymer into the desired porous carbon matrix. Coulombic efficiencies (CE) in excess of 76% after the first cycle and 99.95% after solid electrolyte interphase (SEI) formation have been achieved. A notably high specific delithiation capacity of around 1600 mAh/g with an extremely stable cycling performance even after 400 cycles is obtained. This scalable and economical synthesis approach is readily applicable to the commercial production of anode materials. © 2017 The Korean Society of Industrial and Engineering Chemistry
    view abstractdoi: 10.1016/j.jiec.2017.04.001
  • 2017 • 201 Modeling binary mixtures of n-alkanes and water using PC-SAFT
    Haarmann, N. and Enders, S. and Sadowski, G.
    Fluid Phase Equilibria (2017)
    Modeling and measuring the mutual solubility in binary n-alkane + water mixtures is very challenging due to their low order of magnitude. Consequently, experimental data regarding mutual solubilities of these systems scatter remarkably. In this work, the PC-SAFT equation of state has been applied to model liquid-liquid and vapor-liquid-liquid equilibria of binary n-alkane + water mixtures. For this purpose, temperature-dependent binary interaction parameters have been fitted to the n-alkane solubility in the aqueous phase for n-alkanes ranging from n-pentane to n-undecane. Furthermore, these binary interaction parameters have been correlated with the carbon number of the n-alkane in order to predict phase equilibria of binary n-alkane + water mixtures for n-alkanes ranging from n-propane to n-pentadecane. Excellent agreement between modeling results and available experimental data has been observed for the liquid-liquid equilibria including the description of the minimum of n-alkane solubility in water as a function of temperature. Even the prediction of the vapor-liquid-liquid equilibria of the respective mixtures showed remarkably good results compared to experimental data. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.fluid.2017.11.015
  • 2017 • 200 MOF-Templated Assembly Approach for Fe3C Nanoparticles Encapsulated in Bamboo-Like N-Doped CNTs: Highly Efficient Oxygen Reduction under Acidic and Basic Conditions
    Aijaz, A. and Masa, J. and Rösler, C. and Antoni, H. and Fischer, R.A. and Schuhmann, W. and Muhler, M.
    Chemistry - A European Journal (2017)
    Developing high-performance non-precious metal catalysts (NPMCs) for the oxygen-reduction reaction (ORR) is of critical importance for sustainable energy conversion. We report a novel NPMC consisting of iron carbide (Fe3C) nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes (b-NCNTs), synthesized by a new metal-organic framework (MOF)-templated assembly approach. The electrocatalyst exhibits excellent ORR activity in 0.1m KOH (0.89V at -1mAcm-2) and in 0.5m H2SO4 (0.73V at -1mAcm-2) with a hydrogen peroxide yield of below 1% in both electrolytes. Due to encapsulation of the Fe3C nanoparticles inside porous b-NCNTs, the reported NPMC retains its high ORR activity after around 70hours in both alkaline and acidic media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201701389
  • 2017 • 199 Nanoparticle atoms pinpointed
    Farle, M.
    Nature 542 35-36 (2017)
    doi: 10.1038/542035a
  • 2017 • 198 Nanoscale x-ray investigation of magnetic metallofullerene peapods
    Fritz, F. and Westerström, R. and Kostanyan, A. and Schlesier, C. and Dreiser, J. and Watts, B. and Houben, L. and Luysberg, M. and Avdoshenko, S.M. and Popov, A.A. and Schneider, C.M. and Meyer, C.
    Nanotechnology 28 (2017)
    Endohedral lanthanide ions packed inside carbon nanotubes (CNTs) in a one-dimensional assembly have been studied with a combination of high resolution transmission electron microscopy (HRTEM), scanning transmission x-ray microscopy (STXM), and x-ray magnetic circular dichroism (XMCD). By correlating HRTEM and STXM images we show that structures down to 30 nm are resolved with chemical contrast and record x-ray absorption spectra from endohedral lanthanide ions embedded in individual nanoscale CNT bundles. XMCD measurements of an Er3N@C80 bulk sample and a macroscopic assembly of filled CNTs indicate that the magnetic properties of the endohedral Er3+ ions are unchanged when encapsulated in CNTs. This study demonstrates the feasibility of local magnetic x-ray characterisation of low concentrations of lanthanide ions embedded in molecular nanostructures. © 2017 IOP Publishing Ltd.
    view abstractdoi: 10.1088/1361-6528/aa8b4c
  • 2017 • 197 NH3 Post-Treatment Induces High Activity of Co-Based Electrocatalysts Supported on Carbon Nanotubes for the Oxygen Evolution Reaction
    Yang, F. and Xia, W. and Maljusch, A. and Masa, J. and Hollmann, D. and Sinev, I. and Cuenya, B.R. and Schuhmann, W. and Muhler, M.
    ChemElectroChem 4 2091-2098 (2017)
    Cobalt oxide nanoparticles were deposited on nitrogen-doped carbon nanotubes (NCNTs) through impregnation by using cobalt nitrate as a precursor and subsequent drying and calcination. Co loadings were prepared in the range from 4 to 40 wt%, and hydrogen and ammonia were applied in the thermal post-treatment of the CoOx/NCNT samples. The Co3O4 spinel structure was detected in all samples, while the thermal treatment in ammonia and hydrogen led to the formation of CoO and metallic Co in addition. Treatment in ammonia resulted in the partial reduction of Co3O4 to CoO and nitrogen doping of the oxides, leading to excellent electrocatalytic activity in the oxygen evolution reaction (OER) and stability despite of the lower Co oxidation states compared with the sample calcined in air. In contrast, the sample reduced in hydrogen showed a lower activity and stability in the OER. The high activity of the ammonia-treated sample can be assigned to improved conductivity, favorable surface properties with surface nitrogen improving the hydrophilicity of the catalysts, and the more facile transformation to the OER-active layered cobalt oxyhydroxide phase under anodic conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/celc.201700109
  • 2017 • 196 Oxygen partial pressure dependence of surface space charge formation in donor-doped SrTiO3
    Andrä, M. and Dvořák, F. and Vorokhta, M. and Nemšák, S. and Matolín, V. and Schneider, C.M. and Dittmann, R. and Gunkel, F. and Mueller, D.N. and Waser, R.
    APL Materials 5 (2017)
    In this study, we investigated the electronic surface structure of donor-doped strontium titanate. Homoepitaxial 0.5 wt. % donor-doped SrTiO3 thin films were analyzed by in situ near ambient pressure X-ray photoelectron spectroscopy at a temperature of 770 K and oxygen pressures up to 5 mbar. Upon exposure to an oxygen atmosphere at elevated temperatures, we observed a rigid binding energy shift of up to 0.6 eV towards lower binding energies with respect to vacuum conditions for all SrTiO3 core level peaks and the valence band maximum with increasing oxygen pressure. The rigid shift is attributed to a relative shift of the Fermi energy towards the valence band concomitant with a negative charge accumulation at the surface, resulting in a compensating electron depletion layer in the near surface region. Charge trapping effects solely based on carbon contaminants are unlikely due to their irreversible desorption under the given experimental conditions. In addition, simple reoxygenation of oxygen vacancies can be ruled out as the high niobium dopant concentration dominates the electronic properties of the material. Instead, the negative surface charge may be provided by the formation of cation vacancies or the formation of charged oxygen adsorbates at the surface. Our results clearly indicate a pO2-dependent surface space charge formation in donor-doped SrTiO3 in oxidizing conditions. © 2017 Author(s).
    view abstractdoi: 10.1063/1.4983618
  • 2017 • 195 Polybenzoxazine-Derived N-doped Carbon as Matrix for Powder-Based Electrocatalysts
    Barwe, S. and Andronescu, C. and Masa, J. and Ventosa, E. and Klink, S. and Genç, A. and Arbiol, J. and Schuhmann, W.
    ChemSusChem 10 2653-2659 (2017)
    In addition to catalytic activity, intrinsic stability, tight immobilization on a suitable electrode surface, and sufficient electronic conductivity are fundamental prerequisites for the long-term operation of particle- and especially powder-based electrocatalysts. We present a novel approach to concurrently address these challenges by using the unique properties of polybenzoxazine (pBO) polymers, namely near-zero shrinkage and high residual-char yield even after pyrolysis at high temperatures. Pyrolysis of a nanocubic prussian blue analogue precursor (KmMnx[Co(CN)6]y⋅n H2O) embedded in a bisphenol A and aniline-based pBO led to the formation of a N-doped carbon matrix modified with MnxCoyOz nanocubes. The obtained electrocatalyst exhibits high efficiency toward the oxygen evolution reaction (OER) and more importantly a stable performance for at least 65 h. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201700593
  • 2017 • 194 Potential of an alumina-supported Ni3Fe catalyst in the methanation of CO2: Impact of alloy formation on activity and stability
    Mutz, B. and Belimov, M. and Wang, W. and Sprenger, P. and Serrer, M.A. and Wang, D. and Pfeifer, P. and Kleist, W. and Grunwaldt, J.-D.
    ACS Catalysis 7 6802-6814 (2017)
    A promising bimetallic 17 wt % Ni3Fe catalyst supported on γ-Al2O3 was prepared via homogeneous deposition-precipitation for the application in the methanation of CO2 to gather more detailed insight into the structure and performance of the catalyst compared to state-of-the-art methanation systems. X-ray diffraction (XRD) analysis, detailed investigations using scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy analysis (EDX) of single particles as well as larger areas, high-resolution transmission electron microscopy (HRTEM) imaging, temperature-programmed reduction (H2-TPR), and in-depth interpretation of Raman bands led to the conclusion that a high fraction of the Ni and Fe formed the desired Ni3Fe alloy resulting in small and well-defined nanoparticles with 4 nm in size and a dispersion of 24%. For comparison, a monometallic catalyst with similar dispersion using the same preparation method and analysis was prepared. Using a fixed-bed reactor, the Ni3Fe catalyst showed better low-temperature performance compared to a monometallic Ni reference catalyst, especially at elevated pressures. Longterm experiments in a microchannel packed bed reactor under industrially relevant reaction conditions in competition with a commercial Ni-based methanation catalyst revealed an improved performance of the Ni3Fe system at 358°C and 6 bar involving enhanced conversion of CO2 to 71%, selectivity to CH4 &gt; 98%, and most notably a high stability. Deactivation occurred only at lower temperatures, which was related to carbon deposition due to an increased CO production. Kinetic measurements were compared with literature models derived for Ni/Al2O3 catalysts, which fit well but underestimate the performance of the Ni3Fe system, emphasizing the synergetic effect of Ni and Fe. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.7b01896
  • 2017 • 193 Preferential Carbon Monoxide Oxidation over Copper-Based Catalysts under In Situ Ball Milling
    Eckert, R. and Felderhoff, M. and Schüth, F.
    Angewandte Chemie - International Edition 56 2445-2448 (2017)
    In situ ball milling of solid catalysts is a promising yet almost unexplored concept for boosting catalytic performance. The continuous preferential oxidation of CO (CO-PROX) under in situ ball milling of Cu-based catalysts such as Cu/Cr2O3 is presented. At temperatures as low as −40 °C, considerable activity and more than 95 % selectivity were achieved. A negative apparent activation energy was observed, which is attributed to the mechanically induced generation and subsequent thermal healing of short-lived surface defects. In situ ball milling at sub-zero temperatures resulted in an increase of the CO oxidation rate by roughly 4 orders of magnitude. This drastic and highly selective enhancement of CO oxidation showcases the potential of in situ ball milling in heterogeneous catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201610501
  • 2017 • 192 Promotional Effect of Fe Impurities in Graphene Precursors on the Activity of MnOX/Graphene Electrocatalysts for the Oxygen Evolution and Oxygen Reduction Reactions
    Morales, D.M. and Masa, J. and Andronescu, C. and Schuhmann, W.
    ChemElectroChem 4 2835-2841 (2017)
    Bifunctional oxygen electrocatalysts were fabricated following a three-step synthesis method, which consisted of i) liquid-phase exfoliation of graphite in the presence of nitrogen-containing manganese macrocyclic complexes, using DMF as the dispersion medium under formation of few-layer graphene sheets. Subsequently, ii) solvent removal by vacuum filtration and drying, and iii) pyrolysis of the resulting composites under an inert gas atmosphere with subsequent mild calcination yielded manganese oxides embedded within a graphitic carbon matrix (MnOX/G). We further demonstrate that traces of Fe impurities in the used graphite result in enhanced electrocatalytic activity of the MnOX/G towards both the oxygen reduction and the oxygen evolution reactions, owing to synergistic interaction of the iron impurities with the species formed upon thermal decomposition of Mn macrocyclic complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201700496
  • 2017 • 191 Reforming results of a novel radial reactor for a solid oxide fuel cell system with anode off-gas recirculation
    Bosch, T. and Carré, M. and Heinzel, A. and Steffen, M. and Lapicque, F.
    Journal of Power Sources 371 197-208 (2017)
    A novel reactor of a natural gas (NG) fueled, 1 kW net power solid oxide fuel cell (SOFC) system with anode off-gas recirculation (AOGR) is experimentally investigated. The reactor operates as pre-reformer, is of the type radial reactor with centrifugal z-flow, has the shape of a hollow cylinder with a volume of approximately 1 L and is equipped with two different precious metal wire-mesh catalyst packages as well as with an internal electric heater. Reforming investigations of the reactor are done stand-alone but as if the reactor would operate within the total SOFC system with AOGR. For the tests presented here it is assumed that the SOFC system runs on pure CH4 instead of NG. The manuscript focuses on the various phases of reactor operation during the startup process of the SOFC system. Startup process reforming experiments cover reactor operation points at which it runs on an oxygen to carbon ratio at the reactor inlet (ϕRI) of 1.2 with air supplied, up to a ϕRI of 2.4 without air supplied. As confirmed by a Monte Carlo simulation, most of the measured outlet gas concentrations are in or close to equilibrium. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.jpowsour.2017.10.025
  • 2017 • 190 Separation and characterization of carbonaceous particulate (soot and char) produced from fast pyrolysis of coal in inert and CO2 atmospheres
    Apicella, B. and Senneca, O. and Russo, C. and Heuer, S. and Cortese, L. and Cerciello, F. and Scherer, V. and Schiemann, M. and Ciajolo, A.
    Fuel 201 118-123 (2017)
    In a previous work [Heuer et al., 2016] a large production of a fluffy carbon-rich material was observed to accompany the char formed during the early stages of a medium rank (bituminous) coal pyrolysis in a drop tube furnace (1573 K, residence times &lt; 130 ms). This peculiar material was found to be much more abundantly formed in CO2 than in N2 flow. SEM analysis showed that it contains a large portion of submicron soot-like particles mixed with particles of tenths of microns in size with the typical char morphology. The present work reports on the separation of the two differently sized fractions produced in CO2 and N2 flow and their subsequent analysis. The separation was performed dispersing the material in ethanol by ultrasonic mixing, followed by settling, and decanting to produce top and bottom products enriched in the fine and coarse particle fractions, respectively. The procedure was repeated several times and the size separation effectiveness was checked by SEM and laser granulometry sizing. Thermogravimetry, elemental and spectroscopic analysis were applied to the coarse and fine fractions to provide insights on their structural features. The fine soot particulate was almost ash-free, suggesting that its formation occurs in the gas phase, as typically soot does, while the coarse fraction presented significant residues of coal inorganic matter typical of char. Both fine and coarse particulate resulted less reactive, and somewhat smaller in size, when produced in CO2 in comparison to N2/Ar pyrolysis conditions. Their lower reactivity is associated with higher aromaticity and structural order as well as with a lower presence of hydrogen and aliphatic functionalities. © 2016 Elsevier Ltd
    view abstractdoi: 10.1016/j.fuel.2016.11.049
  • 2017 • 189 Solvent-Free Mechanochemical Synthesis of Nitrogen-Doped Nanoporous Carbon for Electrochemical Energy Storage
    Schneidermann, C. and Jäckel, N. and Oswald, S. and Giebeler, L. and Presser, V. and Borchardt, L.
    ChemSusChem 10 2416-2424 (2017)
    Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m2 g−1 and large pore volume up to 2 cm3 g−1. The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li2SO4 electrolyte (177 F g−1), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g−1), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g−1). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201700459
  • 2017 • 188 Standardisation of a European measurement method for organic carbon and elemental carbon in ambient air: Results of the field trial campaign and the determination of a measurement uncertainty and working range
    Brown, R.J.C. and Beccaceci, S. and Butterfield, D.M. and Quincey, P.G. and Harris, P.M. and Maggos, T. and Panteliadis, P. and John, A. and Jedynska, A. and Kuhlbusch, T.A.J. and Putaud, J.-P. and Karanasiou, A.
    Environmental Science: Processes and Impacts 19 1249-1259 (2017)
    The European Committee for Standardisation (CEN) Technical Committee 264 'Air Quality' has recently produced a standard method for the measurements of organic carbon and elemental carbon in PM2.5 within its working group 35 in response to the requirements of European Directive 2008/50/EC. It is expected that this method will be used in future by all Member States making measurements of the carbonaceous content of PM2.5. This paper details the results of a laboratory and field measurement campaign and the statistical analysis performed to validate the standard method, assess its uncertainty and define its working range to provide clarity and confidence in the underpinning science for future users of the method. The statistical analysis showed that the expanded combined uncertainty for transmittance protocol measurements of OC, EC and TC is expected to be below 25%, at the 95% level of confidence, above filter loadings of 2 μg cm-2. An estimation of the detection limit of the method for total carbon was 2 μg cm-2. As a result of the laboratory and field measurement campaign the EUSAAR2 transmittance measurement protocol was chosen as the basis of the standard method EN 16909:2017. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7em00261k
  • 2017 • 187 Surface-Casting Synthesis of Mesoporous Zirconia with a CMK-5-Like Structure and High Surface Area
    Gu, D. and Schmidt, W. and Pichler, C.M. and Bongard, H.-J. and Spliethoff, B. and Asahina, S. and Cao, Z. and Terasaki, O. and Schüth, F.
    Angewandte Chemie - International Edition (2017)
    About 15years ago, the Ryoo group described the synthesis of CMK-5, a material consisting of a hexagonal arrangement of carbon nanotubes. Extension of the surface casting synthesis to oxide compositions, however, was not possible so far, in spite of many attempts. Here it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400m2g-1, and in selected cases in the form of CMK-5-like, are indeed accessible via such a surface casting process. The key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-rich mesoporous silica as a hard template. The surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by a factor of two to three. The surface casting process seems to be applicable also to other oxide materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201705042
  • 2017 • 186 Synergistic effect of potassium hydroxide and steam co-treatment on the functionalization of carbon nanotubes applied as basic support in the Pd-catalyzed liquid-phase oxidation of ethanol
    Dong, W. and Xia, W. and Xie, K. and Peng, B. and Muhler, M.
    Carbon 121 452-462 (2017)
    Surface functionalization of carbon nanotubes (CNTs) was achieved by a thermal treatment in the presence of pre-adsorbed potassium hydroxide and steam at 350–550 °C. The generated oxygen-containing functional groups were more basic and thermally stable compared with conventional acid-generated groups. The influence of the KOH-steam co-treatment conditions on the functionalization of CNTs was systematically investigated. Residual K species were found to intercalate in the inner graphene layers of the CNTs providing additional Brønsted basicity. Owing to the favorable basic properties and high thermal stability of the generated functional groups, Pd nanoparticles supported on the co-treated CNTs were found to be strongly anchored leading to a high degree of Pd dispersion and a high resistance to sintering. The Pd nanoparticles on the co-treated CNT support produced at 450 °C and 550 °C showed the highest activity and yields of acetic acid in the aerobic oxidation of aqueous ethanol reaching almost full conversion after 5 h in the absence of additional base. In addition, the KOH-steam co-treatment was found to enhance the recyclability of the Pd/CNT catalysts. © 2017 Elsevier Ltd
    view abstractdoi: 10.1016/j.carbon.2017.06.019
  • 2017 • 185 The Influence of Water on the Performance of Molybdenum Carbide Catalysts in Hydrodeoxygenation Reactions: A Combined Theoretical and Experimental Study
    Engelhardt, J. and Lyu, P. and Nachtigall, P. and Schüth, F. and García, Á.M.
    ChemCatChem 9 1985-1991 (2017)
    Understanding the deactivation of transition-metal carbide catalysts during hydrodeoxygenation (HDO) reactions is of great importance for improving the production of the second generation fuels from biomass. Based on a combined experimental and theoretical study, we present a mechanistic model for the deactivation of molybdenum carbide catalysts during phenol HDO in the presence of water. At increased water pressure, water molecules preferentially bind to the surface, and active sites are no longer accessible for phenol. In line with first principle calculations, experiments reveal that this process is fully reversible because the reduction of the water partial pressure results in a threefold increase in conversion. The direct deoxygenation of phenol was calculated to be the most favorable pathway, which is governed by the structure of the phenol adsorption complex on the surface at high hydrogen coverage. This is consistent with the experimentally observed high benzene selectivity (85 %) for phenol HDO over MoCx/HCS (hollow carbon spheres) catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201700181
  • 2017 • 184 The Space Confinement Approach Using Hollow Graphitic Spheres to Unveil Activity and Stability of Pt-Co Nanocatalysts for PEMFC
    Pizzutilo, E. and Knossalla, J. and Geiger, S. and Grote, J.-P. and Polymeros, G. and Baldizzone, C. and Mezzavilla, S. and Ledendecker, M. and Mingers, A. and Cherevko, S. and Schüth, F. and Mayrhofer, K.J.J.
    Advanced Energy Materials 7 (2017)
    The performance of polymer electrolyte fuel cells is strongly correlated to the electrocatalytic activity and stability. In particular, the latter is the result of an interplay between different degradation mechanisms. The essential high stability, demanded for real applications, requires the synthesis of advanced electrocatalysts that withstand the harsh operation conditions. In the first part of this study, the synthesis of oxygen reduction electrocatalysts consisting of Pt-Co (i.e., Pt5Co, Pt3Co, and PtCo) alloyed nanoparticles encapsulated in the mesoporous shell of hollow graphitic spheres (HGS) is reported. The mass activities of the activated catalysts depend on the initial alloy composition and an activity increase on the order of two to threefold, compared to pure Pt@HGS, is achieved. The key point of the second part is the investigation of the degradation of PtCo@HGS (showing the highest activity). Thanks to pore confinement, the impact of dissolution/dealloying and carbon corrosion can be studied without the interplay of other degradation mechanisms that would induce a substantial change in the particle size distribution. Therefore, impact of the upper potential limit and the scan rates on the dealloying and electrochemical surface area evolution can be examined in detail. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/aenm.201700835
  • 2017 • 183 Thin SnOx films for surface plasmon resonance enhanced ellipsometric gas sensing (SPREE)
    Fischer, D. and Hertwig, A. and Beck, U. and Lohse, V. and Negendank, D. and Kormunda, M. and Esser, N.
    Beilstein Journal of Nanotechnology 8 522-529 (2017)
    Background: Gas sensors are very important in several fields like gas monitoring, safety and environmental applications. In this approach, a new gas sensing concept is investigated which combines the powerful adsorption probability of metal oxide conductive sensors (MOS) with an optical ellipsometric readout. This concept shows promising results to solve the problems of cross sensitivity of the MOS concept.Results: Undoped tin oxide (SnOx) and iron doped tin oxide (Fe:SnOx) thin add-on films were prepared by magnetron sputtering on the top of the actual surface plasmon resonance (SPR) sensing gold layer. The films were tested for their sensitivity to several gas species in the surface plasmon resonance enhanced (SPREE) gas measurement. It was found that the undoped tin oxide (SnOx) shows higher sensitivities to propane (C3H8) then to carbon monoxide (CO). By using Fe:SnOx, this relation is inverted. This behavior was explained by a change of the amount of binding sites for CO in the layer due to this iron doping. For hydrogen (H2) no such relation was found but the sensing ability was identical for both layer materials. This observation was related to a different sensing mechanism for H2 which is driven by the diffusion into the layer instead of adsorption on the surface. Conclusion: The gas sensing selectivity can be enhanced by tuning the properties of the thin film overcoating. A relation of the binding sites in the doped and undoped SnOx films and the gas sensing abilities for CO and C3H8 was found. This could open the path for optimized gas sensing devices with different coated SPREE sensors. © 2017 Fischer et al.; licensee Beilstein-Institut.
    view abstractdoi: 10.3762/bjnano.8.56
  • 2017 • 182 Toward a molecular design of porous carbon materials
    Borchardt, L. and Zhu, Q.-L. and Casco, M.E. and Berger, R. and Zhuang, X. and Kaskel, S. and Feng, X. and Xu, Q.
    Materials Today 20 592-610 (2017)
    The molecular design of porous solids from predefined building blocks, in particular metal-organic and covalent frameworks, has been a tremendous success in the past two decades approaching record porosities and more importantly was an enabler for integrating predefined molecular functionality (enantioselectivity, optical and catalytic properties) into pore walls. Recent efforts indicate that this concept could also be applicable to rationally design porous and nanostructured carbonaceous materials, a class of materials hitherto and especially in the past often considered as “black magic” in terms of pore-wall structure definition and surface functionality. Carbon precursors with structural and compositional information in their molecular backbone, pre-formed covalent bonds, or integrated functional groups enable the design of carbon materials that can be tailored for certain applications. We review this exciting field of synthetic approaches based on molecular building blocks such as ionic liquids, bio molecules, or organic precursor monomers enabling the design of advanced carbonaceous architectures such as porous carbons, porous carbon-rich polymers or graphene nanoribbons. Moreover, our review includes approaches using the reactive and thermal transformation of periodic crystalline structures such as metal-organic frameworks, or carbides into equally defined carbon material. Such molecularly designed carbons are not only ideal model materials for fundamental science but also emerge in applications with until now unattained functionality. © 2017 Elsevier Ltd
    view abstractdoi: 10.1016/j.mattod.2017.06.002
  • 2016 • 181 A Simple Approach towards High-Performance Perovskite-Based Bifunctional Oxygen Electrocatalysts
    Elumeeva, K. and Masa, J. and Tietz, F. and Yang, F. and Xia, W. and Muhler, M. and Schuhmann, W.
    ChemElectroChem 3 138-143 (2016)
    To accelerate the large-scale commercialization of electrochemical energy storage and conversion technologies through water splitting and regeneration in reversible fuel cells, cost-effective, highly efficient, and durable reversible oxygen electrodes are required. We report a comparatively simple approach to modify a group of oxygen-evolving perovskites based on lanthanum cobaltite into effective bifunctional systems through partial atom substitution, which, upon intermixing with nitrogen-doped carbon nanotubes, achieve remarkably low round-trip overvoltage of <850mV in the electrocatalysis of oxygen reduction and oxygen evolution in an alkaline electrolyte, KOH (0.1m). Besides the bifunctional electrocatalytic performance, the composite systems with a low Fe content possessed promising long-term stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201500353
  • 2016 • 180 Adsorption and Desorption of Isoflurane on Carbonaceous Adsorbents and Zeolites at Low Concentrations in Gas Phase
    Ortmann, R. and Pasel, C. and Luckas, M. and Heimböckel, R. and Kraas, S. and Bentgens, J. and Fröba, M. and Bathen, D.
    Journal of Chemical and Engineering Data 61 686-692 (2016)
    This paper presents adsorption isotherms and desorption data of isoflurane from a carrier gas (nitrogen) on different adsorbents at 25°C and 1 bar. As adsorbents activated carbons, newly developed carbon adsorbents and dealuminated zeolites were used. The adsorption of isoflurane was studied in trace level concentrations up to 1200 ppmV. Common isotherm equations were fitted to the measured data. The adsorption isotherms show distinctly different capacities depending on the polarity and the pore structure of the adsorbent. The investigation of desorption reveals weak physical interactions between isoflurane and the surface of most adsorbents. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.jced.5b00844
  • 2016 • 179 Advanced Evaluation of the Long-Term Stability of Oxygen Evolution Electrocatalysts
    Maljusch, A. and Conradi, O. and Hoch, S. and Blug, M. and Schuhmann, W.
    Analytical Chemistry 88 7597-7602 (2016)
    Evaluation of the long-term stability of electrocatalysts is typically performed using galvanostatic polarization at a predefined current density. A stable or insignificant increase in the applied potential is usually interpreted as high long-term stability of the tested catalyst. However, effects such as (i) electrochemical degradation of a catalyst due to its oxidation, (ii) blocking of the catalyst surface by evolved gas bubbles, and (iii) detachment of the catalyst from the electrode surface may lead to a decrease of the catalyst's active surface area being exposed to the electrolyte. In order to separate these effects and to evaluate the true electrochemical degradation of electrocatalysts, an advanced evaluation protocol based on subsequently performed electrochemical impedance, double layer capacitance, cyclic voltammetry, and galvanostatic polarization measurements was developed and used to evaluate the degradation of IrO2 particles drop-coated on glassy carbon rotating disk electrode using Nafion as a binder. A flow-through electrochemical cell was developed enabling circulation of the electrolyte leading to an efficient removal of evolved oxygen bubbles even at high current densities of up to 250 mA/cm2. The degradation rate of IrO2 was evaluated over 225 test cycles (0.733 ± 0.022 mV/h) with a total duration of galvanostatic polarization measurements of over 55 h. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.analchem.6b01289
  • 2016 • 178 Bimetallic nickel complexes for selective CO2 carbon capture and sequestration
    Möller, F. and Merz, K. and Herrmann, C. and Apfel, U.-P.
    Dalton Transactions 45 904-907 (2016)
    Herein we report a dinickel azacryptand complex that enables fast, selective, and tight CO2 binding from air. Exploiting the affinity of the cavitand towards azides, CO2 release was observed. Despite the stability of the azido complex, UV irradiation under atmospheric conditions proved to be a suitable pathway for N3- replacement by CO2. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c5dt04267d
  • 2016 • 177 Bound rubber morphology and loss tangent properties of carbon-black-filled rubber compounds
    Gabriel, D. and Karbach, A. and Drechsler, D. and Gutmann, J. and Graf, K. and Kheirandish, S.
    Colloid and Polymer Science 294 501-511 (2016)
    The bound rubber phenomenon of carbon-black-filled rubber compounds, which is still an intensively discussed subject, is visualized in this research as a stable nanoscale interphase. Using the novel amplitude and phase-modified atomic force microscope technique, a viscoelastic mapping mode, it becomes possible to quantify mechanical loss tangent properties that are defined as the ratio of loss modulus G″ to storage modulus G′. Imaging loss tangent enables the observation of separated energy dissipation of single constituents within a blend system as well as bound rubber dimensions. Determined with the conventional quantification of insoluble rubber, the amount of bound rubber is correlated with values from the analytical evaluation of loss tangent images. Comparing the loss tangent images and histograms to dynamic mechanical analyses allows the characterization of each single component. On the base of the time-temperature superposition principle, bound rubber dimensions and mechanical properties of filled compounds can be optimized. © 2015, Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s00396-015-3802-6
  • 2016 • 176 Characterisation of bifunctional electrocatalysts for oxygen reduction and evolution by means of SECM
    Chen, X. and Botz, A.J.R. and Masa, J. and Schuhmann, W.
    Journal of Solid State Electrochemistry 20 1019-1027 (2016)
    Electrocatalysts that can reversibly reduce oxygen and oxidise water are of prime importance for the advancement of new emerging electrochemical energy storage and conversion systems. We present in this work the application of scanning electrochemical microscopy (SECM) for characterisation of bifunctional catalysts. By using model bifunctional catalysts based on oxides of cobalt (CoxOy) and nickel (NixOy) embedded in nitrogen-doped carbon (NC), we specifically show the unique ability of using SECM to determine a range of the important electrocatalytic parameters including the selectivity of the oxygen reduction reaction (ORR), the initial mechanistic steps during the oxygen evolution reaction (OER), and the onset potential for both ORR and OER in a single experiment. We were able to observe directly that prior to oxygen evolution, local depletion of oxygen occurs at the SECM tip during redox transition accompanying most likely metal oxyhydroxide formation thus enabling direct in situ observation of the initial mechanistic steps of the OER. © 2015, Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s10008-015-3028-z
  • 2016 • 175 Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes
    Gastegger, M. and Kauffmann, C. and Behler, J. and Marquetand, P.
    Journal of Chemical Physics 144 (2016)
    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system's total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference. © 2016 Author(s).
    view abstractdoi: 10.1063/1.4950815
  • 2016 • 174 Degradation of Polymeric Brominated Flame Retardants: Development of an Analytical Approach Using PolyFR and UV Irradiation
    Koch, C. and Dundua, A. and Aragon-Gomez, J. and Nachev, M. and Stephan, S. and Willach, S. and Ulbricht, M. and Schmitz, O. J. and Schmidt, T. C. and Sures, B.
    Environmental Science & Technology 50 12912--12920 (2016)
    Many well-established methods for studying the degradation of brominated flame retardants are not useful when working with polymeric and water insoluble species. An example for this specific class of flame retardants is PoIyFR (polymeric flame retardant; CAS No 1195978-93-8), which is used as a substituent for hexabromocyclododecane. Although it has been on the market for two years now, almost no information is available about its long time behavior in the environment. Within this study, we focus on how to determine a possible degradation of both pure PolyFR as well as PolyFR in the final insulation product, expanded polystyrene foam. Therefore, we chose UV radiation followed by analyses of the total bromine content at different time points via ICP-MS and identified possible degradation products such as 2,4,6-tribromophenol through LC-MS. These results were then linked with measurements of the adsorbable organically bound bromine and total organic carbon in order to estimate their concentrations. With respect to the obtained H-1 NMR, GPC, and contact angle results, the possibility for further degradation was discussed, as UV irradiation can influence the decomposition of molecules in combination with other environmental factors like biodegradation.
    view abstractdoi: 10.1021/acs.est.6b04083
  • 2016 • 173 Demonstrating the steady performance of iron oxide composites over 2000 cycles at fast charge-rates for Li-ion batteries
    Sun, Z. and Madej, E. and Genç, A. and Muhler, M. and Arbiol, J. and Schuhmann, W. and Ventosa, E.
    Chemical Communications 52 7348-7351 (2016)
    The feasibility of using iron oxides as negative electrode materials for safe high-power Li-ion batteries is demonstrated by the carbon-coated FeOx/CNT composite synthesized by controlled pyrolysis of ferrocene, which delivered a specific capacity retention of 84% (445 mA h g-1) after 2000 cycles at 2000 mA g-1 (4C). © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6cc00168h
  • 2016 • 172 Design and operation of an aluminium alloy tank using doped Na3AlH6 in kg scale for hydrogen storage
    Urbanczyk, R. and Peinecke, K. and Meggouh, M. and Minne, P. and Peil, S. and Bathen, D. and Felderhoff, M.
    Journal of Power Sources 324 589-597 (2016)
    In this publication the authors present an aluminium alloy tank for hydrogen storage using 1921 g of Na3AlH6 doped with 4 mol% of TiCl3 and 8 mol% of activated carbon. The tank and the heat exchangers are manufactured by extrusion moulding of Al-Mg-Si based alloys. EN AW 6082 T6 alloy is used for the tank and a specifically developed alloy with a composition similar to EN AW 6060 T6 is used for the heat exchangers. The three heat exchangers have a corrugated profile to enhance the surface area for heat transfer. The doped complex hydride Na3AlH6 is densified to a powder density of 0.62 g cm−3. The hydrogenation experiments are carried out at 2.5 MPa. During one of the dehydrogenation experiments approximately 38 g of hydrogen is released, accounting for gravimetric hydrogen density of 2.0 mass-%. With this tank 15 hydrogenation and 16 dehydrogenation tests are carried out. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.jpowsour.2016.05.102
  • 2016 • 171 Detection of the indentation-size-effect (ISE) and surface hardening by analysis of the loading curvature C
    Pöhl, F. and Huth, S. and Theisen, W.
    International Journal of Solids and Structures 84 160-166 (2016)
    Numerous materials are affected by the Indentation-Size-Effect (ISE). Thus, the interpretation of ISE-influenced indentation data plays an important role. This paper presents a method which allows for the characterization of the ISE using the loading curvature C of a single load-displacement curve (P-h curve) from sharp indentation. The method is based on the analysis of the change of the parameter C as a function of the indentation depth as described by Kick's law (related to the universal hardness or also called Martens hardness HM). The intensity as well as the indentation depth where the ISE is saturated can be detected. Furthermore, it allows for the correction of ISE-affected loading curves with the use of the Vickers macro hardness. For example, this can enable the application of inverse methods for ISE-affected materials or phases. Mechanically polished samples show an additional increase in strength during nanoindentation due to hardened surface layers. The presented method also accounts for this influence and can correct affected loading curves. It was applied to the austenitic stainless steel X2CrNi18-9 (AISI 304L) which is heavily affected and the C45 carbon steel which is slightly affected by the ISE. The influence of hardened surface layers was investigated using electropolished and mechanically polished AISI 304L. © 2016 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.ijsolstr.2016.01.024
  • 2016 • 170 Dy uniform film morphologies on graphene studied with SPA-LEED and STM
    McDougall, D. and Hattab, H. and Hershberger, M.T. and Hupalo, M. and Horn-von Hoegen, M. and Thiel, P.A. and Tringides, M.C.
    Carbon 108 283-290 (2016)
    The use of graphene for microelectronics and spintronic applications requires strategies for metals to wet graphene and to grow layer-by-layer. This is especially important when metals will be used as electrical contacts or as spin filters. Extensive work in the literature so far has shown that this is very challenging, since practically all metals grow 3D, with multi-height islands forming easily. Reasons for the 3D morphology are the much weaker metal carbon bond when compared to the metal cohesive energy and the role of Coulomb repulsion of the poorly screened charges at the metal graphene interface. We employed the complementary techniques of SPA-LEED and STM to study the growth of Dy on graphene. It was found that under kinetic limitations it is possible to fully cover graphene with a bilayer Dy film, by growing well below room temperature in stepwise deposition experiments. The Dy film, however, is amorphous but ways to crystallize it within the 2D morphology are possible, since long range order improves at higher growth temperature. © 2016
    view abstractdoi: 10.1016/j.carbon.2016.06.083
  • 2016 • 169 Effect of pH on the spontaneous synthesis of palladium nanoparticles on reduced graphene oxide
    Zhang, X. and Ooki, W. and Kosaka, Y.R. and Okonogi, A. and Marzun, G. and Wagener, P. and Barcikowski, S. and Kondo, T. and Nakamura, J.
    Applied Surface Science 389 911-915 (2016)
    Palladium (Pd) nanoparticles were spontaneously deposited on reduced graphene oxide (rGO) without any external reducing agents. The prepared Pd/rGO composites were then characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Spontaneous deposition occurred because of a redox reaction between the Pd precursor and rGO, which involved reduction of bivalent Pd to metallic Pd0 and oxidation of the sp2 carbon of rGO to oxygen-containing functional groups. The amount of Pd deposited on rGO varied with pH, and this was attributed to electrostatic interactions between the Pd precursor and rGO based on the results of zeta potential measurements. The importance of the redox reaction in the spontaneous deposition was demonstrated in the experiment with Zn, Ni, Cu, Ag, Pt, Pd, and Au. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.apsusc.2016.08.014
  • 2016 • 168 Effect of Si on the acceleration of bainite transformation by pre-existing martensite
    Toji, Y. and Matsuda, H. and Raabe, D.
    Acta Materialia 116 250-262 (2016)
    Bainite transformation was investigated focusing on the influence of pre-existing martensite on the transformation kinetics, morphology and crystallographic orientation of subsequently formed bainite using EBSD and atom probe tomography. Two 1.1 wt% C-3wt.%Mn steels with and without 2 wt% Si were used to clarify the effect of Si. Steels were rapidly cooled from 900 °C to 300 °C and held at this temperature, or quenched from 900 °C once in water to generate approximately 30 vol% martensite followed by holding at 300 °C. Bainite transformation was clearly accelerated by pre-existing martensite in both Si-containing and Si-free steels. Bainite surrounds the pre-existing martensite in the Si-free steel, whereas it grows to the interior of the austenite grains in the steel containing 2 wt% Si. The major orientation relationship between bainite and adjacent austenite was changed by the presence of martensite from Nishiyama-Wassermann (N-W) to Greninger-Troiano (G-T) regardless of Si content. Clear carbon partitioning from martensite into austenite was observed prior to the bainite transformation in the 2 wt% Si steel, which was not observed in the Si-free steel. We suggest that the dislocations introduced by the martensite transformation act as a primary factor accelerating the bainite transformation when martensite is introduced prior to the bainite transformation. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.06.044
  • 2016 • 167 Estimation of energy of cubic iron-carbon nanoclusters by molecular mechanic method: Berechnung der Energie von kubischen Eisen-Kohlenstoff-Nanoclustern durch molekularmechanische Methoden
    Epple, M. and Prylutskyy, Y. and Nedolya, A.V. and Shapar, D.Y.
    Materialwissenschaft und Werkstofftechnik 47 128-132 (2016)
    The energy of cubic iron-carbon nanoclusters was evaluated using the method of molecular mechanics. The focus was on two types of interstitial sites: octahedral and tetrahedral, in which the carbon atoms can be located. The calculation results showed that in the surface layer of the face-centered cubic nanocluster, all of the tetrahedral interstitial sites were energetically equivalent. If a carbon atom changes position between two tetrahedral interstices in the direction of the 111, it can occupy an energetically preferable position in octahedral interstitial space. The comparison of the nanoclusters energy between the cases of surface and subsurface location of the carbon atoms in the octahedral interstice showed that the system has lower energy in the former case. For body-centered cubic nanocluster, octahedral interstitial sites are more energetically favorable for carbon atoms than the tetrahedral interstice, excluding the surface. However, the octahedral interstitial sites on the surface are more preferable than tetrahedral interstice. Based on the calculations it was found that body-centered cubic and face-centered cubic nanoclusters could be unstable by the volumetric concentration of carbon. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/mawe.201600481
  • 2016 • 166 Experimental Evidence for a Three-Body Interaction between Diffusing CO Molecules
    Zaum, C. and Morgenstern, K.
    Nano Letters 16 3001-3004 (2016)
    The diffusion of carbon monoxide molecules on Cu(111) is investigated in time-lapsed scanning tunneling microscopy in a temperature range from 30 to 38 K. An asymptotic theory of adsorbate diffusion predicted a trio interaction that changes the diffusion barrier of three particles diffusing in close proximity beyond the change induced by the long-range interaction between three pairs of molecules. Distance-dependent variations in the diffusion energy confirm this theoretical prediction. In future, the theory can better assist experiments for a broader exploration, not only for diffusion, but also for nucleation and reaction. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.nanolett.5b05212
  • 2016 • 165 Few-layer graphene modified with nitrogen-rich metallo-macrocyclic complexes as precursor for bifunctional oxygen electrocatalysts
    Morales, D.M. and Masa, J. and Andronescu, C. and Kayran, Y.U. and Sun, Z. and Schuhmann, W.
    Electrochimica Acta 222 1191-1199 (2016)
    We propose a method for the formation of highly active bifunctional oxygen electrocatalysts, by exploiting the unique features of nitrogen-rich metallo-macrocyclic complexes and the structural and electronic properties of few-layer graphene. The precursors of the electrocatalysts were synthesized by sonication of graphite in DMF leading to exfoliation and the formation of few-layer graphene sheets in the presence of a suitable transition metal macrocyclic complex. After pyrolysis and subsequent mild calcination metal oxide nanoparticles as well as metal-nitrogen (MNx) moieties embedded within a N-doped graphitic carbon matrix are obtained. The formation, in-depth characterization and electrochemical performance of two different catalysts derived from Co and Ni containing precursor complexes are demonstrated. © 2016 Elsevier Ltd
    view abstractdoi: 10.1016/j.electacta.2016.11.092
  • 2016 • 164 High-Temperature Stable Ni Nanoparticles for the Dry Reforming of Methane
    Mette, K. and Kühl, S. and Tarasov, A. and Willinger, M.G. and Kröhnert, J. and Wrabetz, S. and Trunschke, A. and Scherzer, M. and Girgsdies, F. and Düdder, H. and Kähler, K. and Ortega, K.F. and Muhler, M. and Schlögl, R. an...
    ACS Catalysis 6 7238-7248 (2016)
    Dry reforming of methane (DRM) has been studied for many years as an attractive option to produce synthesis gas. However, catalyst deactivation by coking over nonprecious-metal catalysts still remains unresolved. Here, we study the influence of structural and compositional properties of nickel catalysts on the catalytic performance and coking propensity in the DRM. A series of bulk catalysts with different Ni contents was synthesized by calcination of hydrotalcite-like precursors NixMg0.67-xAl0.33(OH)2(CO3)0.17·mH2O prepared by constant-pH coprecipitation. The obtained Ni/MgAl oxide catalysts contain Ni nanoparticles with diameters between 7 and 20 nm. High-resolution transmission electron microscopy (HR-TEM) revealed a nickel aluminate overgrowth on the Ni particles, which could be confirmed by Fourier transform infrared (FTIR) spectroscopy. In particular, catalysts with low Ni contents (5 mol %) exhibit predominantly oxidic surfaces dominated by Ni2+ and additionally some isolated Ni0 sites. These properties, which are determined by the overgrowth, effectively diminish the formation of coke during the DRM, while the activity is preserved. A large (TEM) and dynamic (microcalorimetry) metallic Ni surface at high Ni contents (50 mol %) causes significant coke formation during the DRM. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.6b01683
  • 2016 • 163 In Situ EPR Study of the Redox Properties of CuO-CeO2 Catalysts for Preferential CO Oxidation (PROX)
    Wang, F. and Büchel, R. and Savitsky, A. and Zalibera, M. and Widmann, D. and Pratsinis, S.E. and Lubitz, W. and Schüth, F.
    ACS Catalysis 6 3520-3530 (2016)
    Understanding the redox properties of metal oxide based catalysts is a major task in catalysis research. In situ electron paramagnetic resonance (EPR) spectroscopy is capable of monitoring the change of metal ion valences and formation of active sites during redox reactions, allowing for the identification of ongoing redox pathways. Here in situ EPR spectroscopy combined with online gas analysis, supported by ex situ X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), temporal analysis of product (TAP), and mass spectrometry (MS) studies, was utilized to study the redox behavior of CuO-CeO2 catalysts under PROX conditions (preferential oxidation of carbon monoxide in hydrogen). Two redox mechanisms are revealed: (i) a synergetic mechanism that involves the redox pair Ce4+/Ce3+ during oxidation of Cu0/Cu+ species to Cu2+ and (ii) a direct mechanism that bypasses the redox pair Ce4+/Ce3+. In addition, EPR experiments with isotopically enriched 17O2 established the synergetic mechanism as the major redox reaction pathway. The results emphasize the importance of the interactions between Cu and Ce atoms for catalyst performance. With the guidance of these results, an optimized CuO-CeO2 catalyst could be designed. A rather wide temperature operation window of 11 K (from 377 to 388 K), with 99% conversion efficiency and 99% selectivity, was achieved for the preferential oxidation of CO in a H2 feed. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.6b00589
  • 2016 • 162 Interactions between metal species and nitrogen-functionalized carbon nanotubes
    Xia, W.
    Catalysis Science and Technology 6 630-644 (2016)
    Nitrogen-functionalized carbon nanotubes are promising materials in catalysis due to their versatile surface properties involving nitrogen groups, oxygen groups, surface defects and metal impurities. These factors can be used to tune the dispersion, morphology, crystal structure, electronic structure, mobility/stability and finally the catalytic performance of supported metal nanoparticles. This review focuses on selected examples aiming at understanding the interactions between surface groups, defects, and metal species and their impact on the catalytic properties in electrocatalysis and gas-phase redox catalysis. © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5cy01694k
  • 2016 • 161 Intracellular Hydrogen Peroxide Detection with Functionalised Nanoelectrodes
    Marquitan, M. and Clausmeyer, J. and Actis, P. and Córdoba, A.L. and Korchev, Y. and Mark, M.D. and Herlitze, S. and Schuhmann, W.
    ChemElectroChem 3 2125-2129 (2016)
    Hydrogen peroxide (H2O2) is one of the most important reactive oxygen species, and it is involved in a number of cellular processes ranging from signal transduction to immune defence and oxidative stress. It is of great interest to intracellularly quantify H2O2 to improve the understanding of its role in disease processes. In this study, we present an amperometric nanosensor for the quantification of H2O2 at the single-cell level. Deposition of the electrocatalyst Prussian Blue on carbon nanoelectrodes enables selective H2O2 reduction at mild potentials. Owing to their small size and needle-type shape, these nanoelectrodes can penetrate the membrane of single living cells, causing only minimal perturbation. The nanosensors allow for the monitoring of penetration-induced oxidative outbursts as well as the uptake of H2O2 from the extracellular environment in single murine macrophages. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/celc.201600390
  • 2016 • 160 Investigation and optimization of the tribo-mechanical properties of CrAlCN coatings using Design of Experiments
    Tillmann, W. and Stangier, D. and Schröder, P.
    Surface and Coatings Technology 308 147-157 (2016)
    The control of friction as well as its adaption is essential for forming operations. Thin hard coatings have a significant influence on the performance of production processes and the service life of tools, especially for Sheet-Bulk Metal Forming (SBMF) processes with high contact normal stresses and issues concerned with the filling of filigree functional elements. To handle these challenges, the CrAlCN coating system is generated by means of bipolar-pulsed reactive magnetron sputtering, using Design of Experiments. A Central Composite Design is selected to investigate the cathode power, bias voltage, as well as the reactive gas flow composition (nitrogen and acetylene). The aim is to evaluate the correlations and the interaction of the investigated process parameters on the mechanical as well as the tribological behavior of the CrAlCN coating, and to develop models to obtain the desired coating properties. The generated coatings show a clear dependency on the selected process parameters. An increased acetylene flow leads to a reduction of the mechanical properties (hardness and Young's modulus) as well as a decreased adhesion of the CrAlCN coating. In contrast to the influence of the acetylene flow, a higher negative bias voltage leads to improved mechanical properties in the context of wear resistant thin films. The tribological properties revealed that the coefficient of friction is related to the chemical composition of the coating which can, on the one hand, be adjusted by the acetylene flow and, on the other hand, by the cathode power. The optimized CrAlCN coating was deposited onto forming punches and the friction was evaluated using DC04 and DP600 specimens in an adapted ring-compression test. In comparison to polished and heat-treated ASP®2023 steel (62 HRC) and a CrAlN reference coating, the developed coating shows a significant reduction of friction due to the carbon incorporation. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2016.07.110
  • 2016 • 159 Investigation on femto-second laser irradiation assisted shock peening of medium carbon (0.4% C) steel
    Majumdar, J.D. and Gurevich, E.L. and Kumari, R. and Ostendorf, A.
    Applied Surface Science 364 133-140 (2016)
    In the present study, the effect of femtosecond laser irradiation on the peening behavior of 0.4% C steel has been evaluated. Laser irradiation has been conducted with a 100 μJ and 300 fs laser with multiple pulses under varied energy. Followed by laser irradiation, a detailed characterization of the processed zone was undertaken by scanning electron microscopy, and X-ray diffraction technique. Finally, the residual stress distribution, microhardness and wear resistance properties of the processed zone were also evaluated. Laser processing leads to shock peening associated with plasma formation and its expansion, formation of martensite and ferrito-pearlitic phase in the microstructure. Due to laser processing, there is introduction of residual stress on the surface which varies from high tensile (140 MPa) to compressive (-335 MPa) as compared to 152 MPa of the substrate. There is a significant increase in microhardness to 350-500 VHN as compared to 250 VHN of substrate. The fretting wear behavior against hardened steel ball shows a significant reduction in wear depth due to laser processing. Finally, a conclusion of the mechanism of wear has been established. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2015.12.058
  • 2016 • 158 Macro-initiator mediated surface selective functionalization of ultrafiltration membranes with anti-fouling hydrogel layers applicable to ready-to-use capillary membrane modules
    Quilitzsch, M. and Osmond, R. and Krug, M. and Heijnen, M. and Ulbricht, M.
    Journal of Membrane Science 518 328-337 (2016)
    A new process for surface selective graft modification of ultrafiltration (UF) membranes with protective hydrogel layers was developed. The process uses a random copolymer of n-butylmethacrylate and N,N-dimethylaminoethylmethacrylate as a redox co-initiator (“macro-initiator”). Due to its molecular weight, the macro-initiator is completely rejected by the used Multibore® polyethersulfone UF membranes. Zwitterionic [3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl) ammonium hydroxide and bifunctional N,N′-methylenebis(acrylamide) were used as monomers for “macro-initiator”-mediated, surface selective cross-linking polymerization toward anti-fouling hydrogel layers. The functionalization comprises two main steps; i) adsorption of the macro-initiator to the barrier layer surface of the membrane, e.g. during a short ultrafiltration; ii) grafting of the hydrogel layer after bringing the membrane in contact with a solution containing monomer(s) and a dissolved initiator (here ammonium persulfate) which is complementary to the co-initiator for a predetermined reaction time at room temperature. Hydrogel-grafted flat sheet and capillary UF membranes showed dextran sieving curves shifted to lower molecular weight values, increased total organic carbon rejection and improved anti-fouling behaviour in filtration tests with flower soil extract as model foulant. Furthermore, stability tests with sodium hydroxide and hydrogen peroxide solutions showed good chemical stability of graft-functionalized membranes. The obtained results are very promising for future applications, since the presented technique can be applied in ready-to-use membrane modules and capillary membranes easily. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.memsci.2016.07.007
  • 2016 • 157 Mechanism of the Fe3(B,C) and Fe23(C,B)6 solid-state transformation in the hypoeutectic region of the Fe-C-B system
    Lentz, J. and Röttger, A. and Theisen, W.
    Acta Materialia 119 80-91 (2016)
    This study investigates the microstructural mechanisms involved in the solid-state transformation of the Fe3(B,C) → Fe23(C,B)6 phases in the hypoeutectic region of the iron-carbon-boron (Fe-C-B) system. We analyzed the influence of different initial microstructural characteristics on the Fe3(B,C) → Fe23(C,B)6 transformation with regards to the matrix phase, matrix C content, B/(C + B) ratio, and agglomeration of the parental Fe3(B,C) phase. We performed thermodynamic calculations using the CALPHAD method, validated by laboratory melts with varying B/(B + C) ratios. These laboratory melts were then microstructurally characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and wavelength-dispersive X-ray spectroscopy (WDS). We particularly focused on solid-state transformation of borides and carboborides of type M3(C,B) and M23(C,B)6 in the hypoeutectic region of the ternary system Fe-C-B, investigated via both in situ and ex situ XRD measurements. It was found that the solid-state transformations are influenced by enriched B inside the eutectic structure, a result of solidification. This increased B content is not reduced in solid state due to the kinetic limitations of B and C inside the hard-phase structure. Thus phase stability is subject to local equilibria depending on the local C and B concentration of the hard-phase structure. In this process the Fe23(C,B)6 phase also forms a shell-like structure surrounding the Fe3(B,C) and Fe2B phases. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.08.009
  • 2016 • 156 Mesoporous nitrogen containing carbon materials for the simultaneous detection of ascorbic acid, dopamine and uric acid
    Joshi, A. and Schuhmann, W. and Nagaiah, T.C.
    Sensors and Actuators, B: Chemical 230 544-555 (2016)
    Mesoporous nitrogen rich carbonaceous (MNC) materials have been synthesized by pyrolyzing the polymerized ethylenediamine nanocasted into a SBA-15 hard template at 600 and 800 °C and explored for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). The electrocatalytic activity of these materials for the oxidation of analyte molecules was examined by means of redox-competition mode of scanning electrochemical microscopy (SECM), voltammetric, chronoamperometric and rotating disc electrode (RDE) measurements. MNC material exhibits a superior sensitivity towards the oxidation of AA, DA, and UA with a lowest detection limit of 0.01 μM, 0.001 μM and 0.01 μM respectively without any substantial interferences including glucose at physiologically relevant concentrations. © 2016 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.snb.2016.02.050
  • 2016 • 155 Microstructure design of tempered martensite by atomistically informed full-field simulation: From quenching to fracture
    Borukhovich, E. and Du, G. and Stratmann, M. and Boeff, M. and Shchyglo, O. and Hartmaier, A. and Steinbach, I.
    Materials 9 (2016)
    Martensitic steels form a material class with a versatile range of properties that can be selected by varying the processing chain. In order to study and design the desired processing with the minimal experimental effort, modeling tools are required. In this work, a full processing cycle from quenching over tempering to mechanical testing is simulated with a single modeling framework that combines the features of the phase-field method and a coupled chemo-mechanical approach. In order to perform the mechanical testing, the mechanical part is extended to the large deformations case and coupled to crystal plasticity and a linear damage model. The quenching process is governed by the austenite-martensite transformation. In the tempering step, carbon segregation to the grain boundaries and the resulting cementite formation occur. During mechanical testing, the obtained material sample undergoes a large deformation that leads to local failure. The initial formation of the damage zones is observed to happen next to the carbides, while the final damage morphology follows the martensite microstructure. This multi-scale approach can be applied to design optimal microstructures dependent on processing and materials composition. © 2016 by the authors.
    view abstractdoi: 10.3390/ma9080673
  • 2016 • 154 Modeling and Simulation of a Tube Bundle Adsorber for the Capture of CO2 from Flue Gases
    Duarte, G.S. and Schürer, B. and Voss, C. and Bathen, D.
    Chemie-Ingenieur-Technik 88 336-345 (2016)
    Besides absorption and membrane processes, temperature swing adsorption (TSA) processes allow for the removal of impurities from gas streams and the recovery of the adsorbed component with high purity. However, especially in the case of large quantities of impurities (e.g., CO2 in flue gas) the TSA processes suffer from their high energetic demand. To reduce this energy demand tube bundle adsorbers with indirectly heated and cooled adsorbent bed were developed. The influence of several parameters on the performance of these adsorbers in a capturing process for CO2 from a dry flue gas is investigated. A detailed 2D model is derived and several parameter sweeps are conducted. It is observed that the inner thermal resistance plays a dominant role on the performance of the process. Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cite.201500031
  • 2016 • 153 Multiscale description of carbon-supersaturated ferrite in severely drawn pearlitic wires
    Nematollahi, Gh.A. and Grabowski, B. and Raabe, D. and Neugebauer, J.
    Acta Materialia 111 321-334 (2016)
    A multiscale simulation approach based on atomistic calculations and a discrete diffusion model is developed and applied to carbon-supersaturated ferrite, as experimentally observed in severely deformed pearlitic steel. We employ the embedded atom method and the nudged elastic band technique to determine the energetic profile of a carbon atom around a screw dislocation in bcc iron. The results clearly indicate a special region in the proximity of the dislocation core where C atoms are strongly bound, but where they can nevertheless diffuse easily due to low barriers. Our analysis suggests that the previously proposed pipe mechanism for the case of a screw dislocation is unlikely. Instead, our atomistic as well as the diffusion model results support the so-called drag mechanism, by which a mobile screw dislocation is able to transport C atoms along its glide plane. Combining the C-dislocation interaction energies with density-functional-theory calculations of the strain dependent C formation energy allows us to investigate the C supersaturation of the ferrite phase under wire drawing conditions. Corresponding results for local and total C concentrations agree well with previous atom probe tomography measurements indicating that a significant contribution to the supersaturation during wire drawing is due to dislocations. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.03.052
  • 2016 • 152 Nanoelectrodes: Applications in electrocatalysis, single-cell analysis and high-resolution electrochemical imaging
    Clausmeyer, J. and Schuhmann, W.
    TrAC - Trends in Analytical Chemistry 79 46-59 (2016)
    High sensitivity and high spatial resolution in localized electrochemical measurements are the key advantages of electroanalysis using nanometer-sized electrodes. Due to recent progress in nanoelectrode fabrication and electrochemical instrument development, nanoelectrochemical methods are becoming more widespread. We summarize different protocols for the fabrication of needle-type nanoelectrodes and discuss their properties with regard to various applications. We discuss the limits of conventional theory to describe electrochemistry at the nanoscale and point out technical aspects for characterization and handling of nanometric electrodes. Different applications are highlighted: i) Nanoelectrodes are powerful tools for non-ensemble studies of electrocatalysis at single nanoparticles at high mass transport rates. ii) Electrochemical nanosensors are employed for highly localized non-invasive analysis of single living cells and intracellular detection of neurotransmitters and metabolites. iii) Used in scanning electrochemical probe techniques, nanoprobes afford topographical and truly chemical imaging of samples with high spatial resolution. © 2016 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.trac.2016.01.018
  • 2016 • 151 Nitrogen-Doped Hollow Amorphous Carbon Spheres@Graphitic Shells Derived from Pitch: New Structure Leads to Robust Lithium Storage
    Ma, Q. and Wang, L. and Xia, W. and Jia, D. and Zhao, Z.
    Chemistry - A European Journal 22 2339-2344 (2016)
    Nitrogen-doped mesoporous hollow carbon spheres (NHCS) consisting of hybridized amorphous and graphitic carbon were synthesized by chemical vapor deposition with pitch as raw material. Treatment with HNO3 vapor was performed to incorporate oxygen-containing groups on NHCS, and the resulting NHCS-O showed excellent rate capacity, high reversible capacity, and excellent cycling stability when tested as the anode material in lithium-ion batteries. The NHCS-O electrode maintained a reversible specific capacity of 616 mAh g-1 after 250 cycles at a current rate of 500 mA g-1, which is an increase of 113 % compared to the pristine hollow carbon spheres. In addition, the NHCS-O electrode exhibited a reversible capacity of 503 mAh g-1 at a high current density of 1.5 A g-1. The superior electrochemical performance of NHCS-O can be attributed to the hybrid structure, high N and O contents, and rich surface defects. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201503462
  • 2016 • 150 Palladium Nanoparticles Supported on Nitrogen-Doped Carbon Nanotubes as a Release-and-Catch Catalytic System in Aerobic Liquid-Phase Ethanol Oxidation
    Dong, W. and Chen, P. and Xia, W. and Weide, P. and Ruland, H. and Kostka, A. and Köhler, K. and Muhler, M.
    ChemCatChem 8 1269-1273 (2016)
    Pd nanoparticles supported on carbon nanotubes were applied in the selective oxidation of ethanol in the liquid phase. The characterization of the surface and bulk properties combined with the catalytic tests indicated the dissolution and redeposition of Pd under the reaction conditions. A dynamic interplay within the Pd life cycle was identified to be responsible for the overall reactivity. Nitrogen-doped carbon nanotubes were found to act as an excellent support for the Pd catalyst system by efficiently stabilizing and recapturing the Pd species, which resulted in high activity and selectivity to acetic acid. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201501379
  • 2016 • 149 Perovskite-based bifunctional electrocatalysts for oxygen evolution and oxygen reduction in alkaline electrolytes
    Elumeeva, K. and Masa, J. and Sierau, J. and Tietz, F. and Muhler, M. and Schuhmann, W.
    Electrochimica Acta 208 25-32 (2016)
    Due to the high cost of precious metal-based electrocatalysts for oxygen reduction and oxygen evolution, the development of alternative low cost and efficient catalysts is of high importance for energy storage and conversion technologies. Although non-precious catalysts that can efficiently catalyze oxygen reduction and oxygen evolution have been developed, electrocatalysts with high bifunctional activity for both oxygen evolution and reduction are needed. Perovskites based on modified lanthanum cobaltite possess significant activity for the oxygen evolution reaction. We describe the synthesis of a bifunctional oxygen electrode with simultaneous activity for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media by direct growth of nitrogen-doped carbon nanotubes on the surface of a perovskite containing Co and Fe by means of chemical vapor deposition. The difference in the overvoltage between ORR (at 1 mA/cm2) and OER (at 10 mA/cm2) was below 880 mV in 0.1 M KOH. The formation of H2O2 during the ORR was reduced by at least three fold when using the bifunctional catalyst as compared to the non-modified perovskite. Long-term durability tests indicate stable performance for at least 37 h during the OER and 23 h during the ORR. © 2016 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.electacta.2016.05.010
  • 2016 • 148 Phosphine-ligated dinitrosyl iron complexes for redox-controlled NO release
    Wittkamp, F. and Nagel, C. and Lauterjung, P. and Mallick, B. and Schatzschneider, U. and Apfel, U.-P.
    Dalton Transactions 45 10271-10279 (2016)
    Here we present the syntheses and structural, spectroscopic, as well as electrochemical properties of four dinitrosyl iron complexes (DNICs) based on silicon- and carbon-derived di- and tripodal phosphines. Whereas CH3C(CH2PPh2)3 and Ph2Si(CH2PPh2)2 coordinate iron in a η2-binding mode, CH3Si(CH2PPh2)3 undergoes cleavage of one Si-C bond to afford [Fe(NO)2(P(CH3)Ph2)2] at elevated temperatures. The complexes were characterized by IR spectroelectrochemistry as well as UV-vis measurements. The oxidized {Fe(NO)2}9 compounds were obtained by oxidation with (NH4)2[Ce(NO3)6] and their properties evaluated with Mössbauer and IR spectroscopy. Stability experiments on the complexes suggest that they are capable of releasing their NO-ligands in the oxidized {Fe(NO)2}9 but not in the reduced {Fe(NO)2}10 form. A detailed DFT analysis is provided in order to understand the electronic configurations and the complexes' ability to release NO. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c6dt01209d
  • 2016 • 147 Precise synthesis of discrete and dispersible carbon-protected magnetic nanoparticles for efficient magnetic resonance imaging and photothermal therapy
    Lu, A.-H. and Zhang, X.-Q. and Sun, Q. and Zhang, Y. and Song, Q. and Schüth, F. and Chen, C. and Cheng, F.
    Nano Research 9 1460-1469 (2016)
    Carbon-protected magnetic nanoparticles exhibit long-term stability in acid or alkaline medium, good biocompatibility, and high saturation magnetization. As a result, they hold great promise for magnetic resonance imaging, photothermal therapy, etc. However, since pyrolysis, which is often required to convert the carbon precursors to carbon, typically leads to coalescence of the nanoparticles, the obtained carbon-protected magnetic nanoparticles are usually sintered as a non-dispersible aggregation. We have successfully synthesized discrete, dispersible, and uniform carbon-protected magnetic nanoparticles via a precise surface/interface nano-engineering approach. Remarkably, the nanoparticles possess excellent water-dispersibility, biocompatibility, a high T2 relaxivity coefficient (384 mM–1·s–1), and a high photothermal heating effect. Furthermore, they can be used as multifunctional core components suited for future extended investigation in early diagnosis, detection and therapy, catalysis, separation, and magnetism. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s12274-016-1042-9
  • 2016 • 146 Product distribution of CO2 hydrogenation by K- and Mn-promoted Fe catalysts supported on N-functionalized carbon nanotubes
    Kangvansura, P. and Chew, L.M. and Saengsui, W. and Santawaja, P. and Poo-arporn, Y. and Muhler, M. and Schulz, H. and Worayingyong, A.
    Catalysis Today 275 59-65 (2016)
    An iron based catalyst supported on an N-functionalized carbon nanotube (NCNT) was promoted with potassium and manganese as follows: Fe/NCNT, K/Fe/NCNT, Mn/Fe/NCNT, and K/Mn/Fe/NCNT for CO2 hydrogenation. Time-resolved reduction X-ray absorption near edge spectroscopy (XANES) showed mixed phases of Fe, FeO, Fe3O4, and Fe2O3 resulting from K/Fe/NCNT, and of FeO and Fe3O4 resulting from Mn/Fe/NCNT. The product distributions and growth probability of n-alkanes during CO2 hydrogenation indicated that the potassium-promoted iron catalysts performed Fischer-Tropsch (FT) synthesis under steady state at 60 h. 1-Alkenes desorbed from the FT sites with the potassium-promoted catalysts, (K/Fe/NCNT and K/Mn/Fe/NCNT), with low methane formation. Small amounts of 1-alkene, along with high methanation, were produced from the potassium-unpromoted catalysts, (Fe/NCNT and Mn/Fe/NCNT), indicating high local H2:CO ratios on the catalyst surfaces. K/Fe/NCNT and K/Mn/Fe/NCNT catalysts also produced ethanol. Thus, potassium is a key promoter providing active species of the catalysts for alkene and ethanol formation. Reduced surrounding of the NCNT support, potassium as an electronic promoter together with manganese as a structural promoter made the iron-active phase well suitable for CO2 hydrogenation producing mainly alkenes and ethanol. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.cattod.2016.02.045
  • 2016 • 145 Relay-Like Exchange Mechanism through a Spin Radical between TbPc2 Molecules and Graphene/Ni(111) Substrates
    Marocchi, S. and Candini, A. and Klar, D. and Van Den Heuvel, W. and Huang, H. and Troiani, F. and Corradini, V. and Biagi, R. and De Renzi, V. and Klyatskaya, S. and Kummer, K. and Brookes, N.B. and Ruben, M. and Wende, H. and De...
    ACS Nano 10 9353-9360 (2016)
    We investigate the electronic and magnetic properties of TbPc2 single ion magnets adsorbed on a graphene/Ni(111) substrate, by density functional theory (DFT), ab initio complete active space self-consistent field calculations, and X-ray magnetic circular dichroism (XMCD) experiments. Despite the presence of the graphene decoupling layer, a sizable antiferromagnetic coupling between Tb and Ni is observed in the XMCD experiments. The molecule-surface interaction is rationalized by the DFT analysis and is found to follow a relay-like communication pathway, where the radical spin on the organic Pc ligands mediates the interaction between Tb ion and Ni substrate spins. A model Hamiltonian which explicitly takes into account the presence of the spin radical is then developed, and the different magnetic interactions at play are assessed by first-principle calculations and by comparing the calculated magnetization curves with XMCD data. The relay-like mechanism is at the heart of the process through which the spin information contained in the Tb ion is sensed and exploited in carbon-based molecular spintronics devices. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acsnano.6b04107
  • 2016 • 144 Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations
    Álvarez Galván, C. and Schumann, J. and Behrens, M. and Fierro, J.L.G. and Schlögl, R. and Frei, E.
    Applied Catalysis B: Environmental 195 104-111 (2016)
    The physicochemical properties of hydroxycarbonate-based precipitates [zincian malachite (ZM) and aurichalcite precursors], calcined CuO/ZnO precatalysts and finally reduced Cu/ZnO catalysts, with several Cu-Zn ratios, have been investigated by different characterization techniques. Results from isothermal physisorption of N2 (BET), X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), N2O Reactive Frontal Chromatography (N2O-RFC), X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) have been correlated with the catalytic activity for the reverse water-gas shift (rWGS) reaction in order to provide insight into the controversial nature of active species in carbon dioxide activation, respectively the role of Cu and ZnO. Average crystalline domain size of CuO and ZnO show a relationship with the amount of each phase in the calcined sample. This is in agreement with the TPR profiles, which indicate a better dispersion of Cu for the ZnO-rich samples and a shift for the first reduction step to higher temperatures (Tonset for CuII to CuI). XPS measurements point out the surface enrichment of ZnO is less pronounced with higher ZnO/(ZnO + Cu) ratios. Activity results show that catalysts derived from high surface area ex-aurichalcite (Zn content, 50-70% atom) catalysts are more active in rWGS with lower apparent activation energies than ex-ZM catalysts (Zn content, 15-30% atom) with comparable apparent Cu surface area/N2O capacity. Thus, the CO formation rate as function of the apparent Cu surface area indicates that the reaction rate is not dependent on the exposed apparent Cu surface, but from an adjusted interface composition predetermined by the precursor structure and its thermal post-treatment. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.apcatb.2016.05.007
  • 2016 • 143 Sorption measurements for determining surface effects and structure of solid fuels
    Seibel, C. and Wedler, C. and Vorobiev, N. and Schiemann, M. and Scherer, V. and Span, R. and Fieback, T.M.
    Fuel Processing Technology 153 81-86 (2016)
    Novel experimental results on temperature dependent diffusion of CO2 inside porous char particles are provided as well as corresponding data on adsorption of oxygen and carbon dioxide. For this purpose, different chars from a Colombian coal were generated either in a flat flame burner (FFB) under realistic conditions for pulverized coal combustion with heating rates in the order 104–105 K/s or in a thermogravimetric analyser (TGA) at low heating rates and inert conditions (Ar). The chars produced are used for kinetic adsorption measurements with a suspension balance to determine temperature dependent diffusion coefficients for CO2 up to 160 °C. Based on these data the resistance factor for Knudsen diffusion, which describes the influence of the inner particle morphology on gas diffusion, was determined. The results indicate that the diffusion coefficients of the chars converge to the same value with rising temperature, ending in a Knudsen diffusion dominated regime. Furthermore, adsorption measurements for O2 and CO2 were conducted up to temperatures of 150 °C and 450 °C, respectively, on coal chars for the first time. Based on the pure component results, multicomponent adsorption has been predicted based on the well-known multi component IAST model. The results indicate that individual species selectivity changes with temperature. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.fuproc.2016.08.004
  • 2016 • 142 Strong metal-support interaction and alloying in Pd/ZnO catalysts for CO oxidation
    Kast, P. and Friedrich, M. and Girgsdies, F. and Kröhnert, J. and Teschner, D. and Lunkenbein, T. and Behrens, M. and Schlögl, R.
    Catalysis Today 260 21-31 (2016)
    Pd/ZnO catalysts with different Pd content have been synthesized, thoroughly characterized and investigated with regard to their reduction behavior in hydrogen or carbon monoxide containing atmospheres, by applying CO-chemisorption, photoelectron spectroscopy, X-ray diffraction, electron microscopy, TPR and DRIFTS techniques. As a catalytic test reaction, CO-oxidation has been applied. The interaction of the noble metal with the support has been revealed in a way that can distinguish between alloying and other surface spreading/wetting phenomena, induced by strong metal-support interaction (SMSI). It was found that while alloy formation promoted CO-oxidation activity additional ZnOx formation by SMSI had the opposite effect. Zinc enrichment at the surface was detected during reduction of the catalysts, depending on the reducing agent and the Pd particle size. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.cattod.2015.05.021
  • 2016 • 141 Study of biocompatibility effect of nanocarbon particles on various cell types in vitro
    Tolkachov, M. and Sokolova, V. and Loza, K. and Korolovych, V. and Prylutskyy, Y. and Epple, M. and Ritter, U. and Scharff, P.
    Materialwissenschaft und Werkstofftechnik 47 216-221 (2016)
    The viability of primary cells (human mesenchymal stem cells, hMSC, as a model for healthy cells) and a cancer cell line (human transformed cervix epithelial cells, HeLa, as a model for cancer cells) was studied with the MTT assay after the incubation with water-soluble C60 fullerenes and multi-walled carbon nanotubes filled by iron, respectively. The size of the particles was determined by dynamic light scattering. The morphology of the cells incubated with nanocarbon particles was studied by scanning electron microscopy. The effect of C60 fullerenes and Fe-multi-walled carbon nanotubes on the cells is depending on the concentration of applied nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/mawe.201600486
  • 2016 • 140 The effect of sodium on the structure-activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols
    Anton, J. and Nebel, J. and Song, H. and Froese, C. and Weide, P. and Ruland, H. and Muhler, M. and Kaluza, S.
    Journal of Catalysis 335 175-186 (2016)
    A series of Co-modified Cu/ZnO/Al2O3 methanol synthesis catalysts with different Na loadings was prepared and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H2/CO = 1. The bulk and surface properties of the catalysts were characterized after reduction and after 40 h time on stream (TOS) without exposing the catalysts to air during the transfer and the measurements. Increased presence of metallic Co0 after reduction at 350 °C was confirmed by X-ray photoelectron spectroscopy indicating metallic Cu0 to act as a reduction promoter. Catalysts with low Na loadings (≤0.6 wt%) showed strong initial deactivation presumably due to coking of isolated Co0 surface sites favoring hydrocarbon formation. The selectivity to higher alcohols gradually increased during the first 10 h TOS indicating enhanced Cu-Co surface alloy formation considered as active sites for HAS. In contrast, with high Na loadings (≥0.8 wt%) deactivation did not occur and stable performance with constant CO conversion and product distribution was observed indicating significantly altered structural properties. High Na loadings caused the stabilizing amorphous oxide matrix to collapse resulting in strong sintering of the metallic Cu particles, and an increased carbidization of metallic Co0 forming bulk Co2C was observed by X-ray diffraction. Close contact between metallic Co0 and Co2C, which is known to facilitate molecular CO adsorption, is assumed to generate additional active sites for HAS. © 2016 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2015.12.016
  • 2016 • 139 The influence of Si as reactive bonding agent in the electrophoretic coatings of HA–Si–MWCNTs on NiTi alloys
    Khalili, V. and Khalil-Allafi, J. and Maleki-Ghaleh, H. and Paulsen, A. and Frenzel, J. and Eggeler, G.
    Journal of Materials Engineering and Performance 25 390-400 (2016)
    In this study, different composite coatings with 20 wt.% silicon and 1 wt.% multi-walled carbon nanotubes of hydroxyapatite were developed on NiTi substrate using a combination of electrophoretic deposition and reactive bonding during the sintering. Silicon was used as reactive bonding agent. During electrophoretic deposition, the constant voltage of 30 V was applied for 60 s. After deposition, samples were dried and then sintered at 850 °C for 1 h in a vacuum furnace. SEM, XRD and EDX were used to characterize the microstructure, phase and elemental identification of coatings, respectively. The SEM images of the coatings reveal a uniform and compact structure for HA–Si and HA–Si–MWCNTs. The presence of silicon as a reactive bonding agent as well as formation of new phases such as SiO2, CaSiO3 and Ca3SiO5 during the sintering process results in compact coatings and consumes produced phases from HA decomposition. Formation of the mentioned phases was confirmed using XRD analysis. The EDX elemental maps show a homogeneous distribution of silicon all over the composite coatings. Also, the bonding strength of HA–Si–MWCNTs coating is found to be 27.47 ± 1 MPa. © 2015, ASM International.
    view abstractdoi: 10.1007/s11665-015-1824-3
  • 2016 • 138 TiO2 quantum dots embedded in bamboo-like porous carbon nanotubes as ultra high power and long life anodes for lithium ion batteries
    Tang, Y. and Liu, L. and Wang, X. and Jia, D. and Xia, W. and Zhao, Z. and Qiu, J.
    Journal of Power Sources 319 227-234 (2016)
    TiO2 quantum dots embedded in bamboo-like porous carbon nanotubes have been constructed through the pyrolysis of sulfonated polymer nanotubes and TiO2 hybrids. The TiO2 quantum dots are formed during the pyrolysis, due to the space confinement within the highly cross-linked copolymer networks. The sulfonation degree of the polymer nanotubes is a critical factor to ensure the formation of the unique interpenetrating structure. The nanocomposites exhibit high reversible capacity of 523 mAh g-1 at 100 mA g-1 after 200 cycles, excellent rate capability and superior long-term cycling stability at high current density, which could attain a high discharge capacity of 189 mAh g-1 at 2000 mA g-1 for up to 2000 cycles. The enhanced electrochemical performance of the nanocomposites benefit from the uniform distribution of TiO2 quantum dots, high electronic conductivity of porous carbons and unique interpenetrating structure, which simultaneously solved the major problems of TiO2 anode facing the pulverization, loss of electrical contact and particle aggregation. © 2016 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jpowsour.2016.04.033
  • 2015 • 137 3D structural and atomic-scale analysis of lath martensite: Effect of the transformation sequence
    Morsdorf, L. and Tasan, C.C. and Ponge, D. and Raabe, D.
    Acta Materialia 95 366-377 (2015)
    To improve the fundamental understanding of the multi-scale characteristics of martensitic microstructures and their micro-mechanical properties, a multi-probe methodology is developed and applied to low-carbon lath martensitic model alloys. The approach is based on the joint employment of electron channeling contrast imaging (ECCI), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), atom probe tomography (APT) and nanoindentation, in conjunction with high precision and large field-of-view 3D serial sectioning. This methodology enabled us to resolve (i) size variations of martensite sub-units, (ii) associated dislocation sub-structures, (iii) chemical heterogeneities, and (iv) the resulting local mechanical properties. The identified interrelated microstructure heterogeneity is discussed and related to the martensitic transformation sequence, which is proposed to intrinsically lead to formation of a nano-composite structure in low-carbon martensitic steels. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2015.05.023
  • 2015 • 136 A novel approach for the characterization of liquid phase adsorption on activated carbons
    Treese, J. and Pasel, C. and Luckas, M. and Bathen, D.
    Chemie-Ingenieur-Technik 87 563-570 (2015)
    Abstract Activated carbons are widely applicable in industrial adsorption processes. However, characterization of their surface properties is problematic due to the number of different source materials and variations in production processes. Here, a model of the carbon surface derived that is based on the knowledge of fundamental molecular interactions on carbon surfaces. Adsorption isotherms of selected probe molecules are measured on different activated carbons and discussed how the model can be applied in the characterization of the surface properties of activated carbons. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cite.201400085
  • 2015 • 135 A Review of the Properties and Processes Determining the Fate of Engineered Nanomaterials in the Aquatic Environment
    Peijnenburg, W.J.G.M. and Baalousha, M. and Chen, J. and Chaudry, Q. and Von Der Kammer, F. and Kuhlbusch, T.A.J. and Lead, J. and Nickel, C. and Quik, J.T.K. and Renker, M. and Wang, Z. and Koelmans, A.A.
    Critical Reviews in Environmental Science and Technology 45 2084-2134 (2015)
    Proper understanding of the basic processes and specific properties of engineered nanomaterials (NMs) that modify the fate and effects of NMs is crucial for NM-tailored risk assessment. This in turn requires developers of NMs and for regulators to consider the most important parameters governing the properties, behavior and toxicity of NMs. As fate and effect studies are commonly performed in laboratory settings, mimicking to a varying extent realistic exposure conditions, it is important to be able to extrapolate results of fate and effect studies in synthetic media to realistic environmental conditions. This requires detailed understanding of the processes controlling the fate and behavior of NMs in terrestrial and aquatic media, as dependent on the composition of the medium. It is the aim of this contribution to provide background reading to the NM and media specific properties and processes that affect the fate and behavior of NMs in aquatic environments, focusing on the specific properties of NMs that modulate the interactions in the aquatic environment. A general introduction on the dominant fate determining processes of NMs is supplemented by case studies on specific classes of NMs: metal NMs, stable oxides, iron oxides, and carbon nanotubes. Based on the synthesis of the current knowledge base toward essential data and information needs, the review provides a description of the particle specific properties and the water characteristics that need monitoring in order to allow for future quantification and extrapolation of fate and behavior properties of NMs in freshwater compartments of varying composition. © 2015 Copyright Taylor & Francis Group, LLC.
    view abstractdoi: 10.1080/10643389.2015.1010430
  • 2015 • 134 Activation of carbon-supported catalysts by ozonized acidic solutions for the direct implementation in (electro-)chemical reactors
    Baldizzone, C. and Mezzavilla, S. and Hodnik, N. and Zeradjanin, A.R. and Kostka, A. and Schüth, F. and Mayrhofer, K.J.J.
    Chemical Communications 51 1226-1229 (2015)
    This work introduces a practical and scalable post-synthesis treatment for carbon-supported catalysts designed to achieve complete activation and, if necessary, simultaneously surface dealloying. The core concept behind the method is to control the potential without utilizing any electrochemical equipment, but rather by applying an appropriate gas mixture to a catalyst suspension. © 2015 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c4cc08480b
  • 2015 • 133 Alloying effects on microstructure formation of dual phase steels
    Schemmann, L. and Zaefferer, S. and Raabe, D. and Friedel, F. and Mattissen, D.
    Acta Materialia 95 386-398 (2015)
    In dual-phase (DP) steels, inherited microstructures and elemental distributions affect the kinetics and morphology of phase transformation phenomena and the mechanical properties of the final material. In order to study the inheritance process, we selected two model materials with the same average DP steel composition but with different initial microstructures, created by coiling at different temperatures after hot rolling. These samples were submitted to a DP-steel heat treatment consisting of a short isothermal annealing in the pure austenite region and a quenching process. The evolution of microstructure, chemical composition and mechanical properties (hardness) during this treatment was investigated. The initial samples had a bainitic-martensitic (B + M) microstructure for the material coiled at lower temperature and a ferritic-pearlitic (P + F) microstructure for that coiled at higher temperature. The P + F microstructure had a much more inhomogeneous distribution of substitutional elements (in particular of Mn) and of carbon. After complete heat treatment, both materials showed a typical DP microstructure (martensite islands embedded in ferrite) but the P + F material showed lower hardness compared to the B + M material. It was found that the inhomogeneous elemental distribution prevailed in the P + F material. The inheritance process was studied by combining measurements of the elemental distribution by Wavelength-Dispersive X-ray spectroscopy (WDX), simulations of the evolution of the elemental composition via the DICTRA (diffusion-controlled reactions) computer programme, dilatometry to observe the kinetics of phase transformation, and observation and quantification of the microstructures by Electron Backscatter Diffraction (EBSD) measurements. For the P + F material it was found that the α-γ transformation during annealing is slowed down in regions of lower Mn content and is therefore not completed. During the subsequent cooling the incompletely autenitized material does not require ferrite nucleation and the γ-α transformation starts at relative high temperatures. For B + M, in contrast, nucleation of ferrite is needed and the transformation starts at lower temperatures. As a result the B + M material develops a higher martensite content as well as a higher density of geometrically necessary dislocations (GNDs). It is speculated that for the B + M material the γ-α transformation occurs through a bainitic (i.e. partly displacive) process while the transformation at higher temperatures in the P + F material proceeds exclusively in a diffusive way. © 2015 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2015.05.005
  • 2015 • 132 Ammonia decomposition over iron phthalocyanine-based materials
    Tüysüz, H. and Schüth, F. and Zhi, L. and Müllen, K. and Comotti, M.
    ChemCatChem 7 1453-1459 (2015)
    Iron phthalocyanine-based materials have been used herein as efficient catalysts for the ammonia decomposition reaction. These materials showed high activity, even superior to that showed by the commercial nickel-based catalyst and iron-doped carbon nanotubes, which were used as benchmarks in this study. Catalyst stability under reaction conditions appeared satisfactory, because no deactivation phenomena were observed. The type of the phthalocyanine precursor did not affect the catalytic performance; however, the preparation method had a strong effect. If the resulting material was exposed to the reaction conditions, some structural modification occurred. No clear correlation between phase composition and activity could be established because similar nitrogen content and similar crystalline domains in the sample led to different behaviors. However, the results of extensive characterization suggested that catalytic activities and conversion profiles were most likely dependent on material textural properties and thus on the preparation method used. The accessibility of iron species seems to be limited for catalysts prepared under vacuum. These phenomena are most likely responsible for the activation profile and for the low catalytic activity typical of these materials. In contrast, higher accessibility of iron species, typical of materials prepared under argon, would lead to improved and stable catalytic performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201500024
  • 2015 • 131 An approach for transparent and electrically conducting coatings: A transparent plastic varnish with nanoparticulate magnetic additives
    Beck, G. and Barcikowski, S. and Chakravadhanula, V.S.K. and Comesaña-Hermo, M. and Deng, M. and Farle, M. and Hilgendorff, M. and Jakobi, J. and Janek, J. and Kienle, L. and Mogwitz, B. and Schubert, T. and Stiemke, F.
    Thin Solid Films 595 96-107 (2015)
    For the purpose of preparing TCCs (= transparent and electrical conducting coatings), metallic and ferromagnetic nano-additives were dispersed into a transparent varnish and the obtained dispersions were coated on transparent plastic substrates. During hardening of the dispersion the magnetic nano-additives were aligned by a magnetic field. The resulting coatings have electrical pathways along lines of nano-additive chains and are highly transparent in the areas between the lines. Therefore, the electrical conductivity is anisotropic, and it depends on the alignment of the nano-additives (i.e. on the distance between the nano-additives within the chains and the length of the lines) as well as on the thickness of an oxide and/or solvent shell around the nano-additives. The transparency depends also on the alignment and here especially on the thickness and the distance between the formed lines. The quality of the alignment in turn, depends on the magnetic properties and on the size of the particles. We used commercial plastic varnishes, which form electrically isolating (≥ 10− 12 S/m) and transparent (about 90% transparency) coatings, and the following magnetic additives: Co-, Fe-, CoPt3, CoPt3@Au- and Fe@Au-nanoparticles as well as CoNi-nanowires. Coatings with Fe@Au-nanoparticles show the best results in terms of the electrical conductivity (10− 5 S/m–10− 6 S/m) at transparencies above 70%. Furthermore, in addition to the magnetic nano-additives, transparent additives (Al2O3-particles) and non-magnetic, but better conducting additives (carbon-nanotubes) were added to the varnish to increase the transparency and the electrical conductivity, respectively. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2015.10.059
  • 2015 • 130 Assembling Paramagnetic Ceruloplasmin at Electrode Surfaces Covered with Ferromagnetic Nanoparticles. Scanning Electrochemical Microscopy in the Presence of a Magnetic Field
    Matysiak, E. and Botz, A.J.R. and Clausmeyer, J. and Wagner, B. and Schuhmann, W. and Stojek, Z. and Nowicka, A.M.
    Langmuir 31 8176-8183 (2015)
    Adsorption of ceruloplasmin (Cp) at a gold electrode modified with ferromagnetic iron nanoparticles encapsulated in carbon (Fe@C Nps) leads to a successful immobilization of the enzyme in its electroactive form. The proper placement of Cp at the electrode surface on top of the nanocapsules containing an iron core allowed a preorientation of the enzyme, hence allowing direct electron transfer between the electrode and the enzyme. Laser ablation coupled with inductively coupled plasma mass spectrometry indicated that Cp was predominantly located at the paramagnetic nanoparticles. Scanning electrochemical microscopy measurements in the sample-generation/tip-collection mode proved that Cp was ferrooxidative inactive if it was immobilized on the bare gold surface and reached the highest activity if it was adsorbed on Fe@C Nps in the presence of a magnetic field. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.langmuir.5b01155
  • 2015 • 129 Bifunctional redox tagging of carbon nanoparticles
    Poon, J. and Batchelor-McAuley, C. and Tschulik, K. and Palgrave, R.G. and Compton, R.G.
    Nanoscale 7 2069-2075 (2015)
    Despite extensive work on the controlled surface modification of carbon with redox moieties, to date almost all available methodologies involve complex chemistry and are prone to the formation of polymerized multi-layer surface structures. Herein, the facile bifunctional redox tagging of carbon nanoparticles (diameter 27 nm) and its characterization is undertaken using the industrial dye Reactive Blue 2. The modification route is demonstrated to be via exceptionally strong physisorption. The modified carbon is found to exhibit both well-defined oxidative and reductive voltammetric redox features which are quantitatively interpreted. The method provides a generic approach to monolayer modifications of carbon and carbon nanoparticle surfaces. © The Royal Society of Chemistry 2015.
    view abstractdoi: 10.1039/c4nr06058j
  • 2015 • 128 Biopolymer foaming with supercritical CO2 - Thermodynamics, foaming behaviour and mechanical characteristics
    Frerich, S.C.
    Journal of Supercritical Fluids 96 349-358 (2015)
    Polymer foams, especially those based on biodegradable polymers, are in high demand for energy saving applications, for example as thermal insulations or packaging materials. To understand and predict the quality and material properties of polymer foams, concise knowledge of the factors influencing the foaming behaviour, especially pressure and temperature, is required. Therefore, three biodegradable polyesters, namely poly (lactide) (PLA), poly (butylene succinate) (PBS) and a blend of poly (lactide) and poly (hydroxy butyrate) (PLA-PHB), have been subjected to a direct foaming procedure using compressed carbon dioxide as blowing agent, studying the influence of saturation temperature (ranging from 95 °C to 175°C) and applied pressure (ranging from atmospheric pressure to 30 MPa) on the resulting foam material. As these results are strongly depending on the melting behaviour of the polymers, all three polymers were subjected to calorimetric analysis in a scanning transitiometer that allows for applying pressure levels of up to 45 MPa. The created porous materials were characterized by determining their density, porosity and morphology, using SEM analysis. Their mechanical behaviour was investigated by using compressive strength tests. It is shown that the quality of the produced foam structures and its properties is strongly depending on the foaming conditions. In order to obtain foams with a high quality, the saturation temperature and pressure have to be adapted to the phase transition liquid-solid of the polymer-gas system. The results obtained via scanning transitiometer represent the SLG-line of the binary systems polymer and CO2, and their influence on the foaming behaviour enabled the identification of ideal foaming conditions for the three polymers regarded in this study. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.supflu.2014.09.043
  • 2015 • 127 Carbon Monoxide-Induced Stability and Atomic Segregation Phenomena in Shape-Selected Octahedral PtNi Nanoparticles
    Ahmadi, M. and Cui, C. and Mistry, H. and Strasser, P. and Roldan Cuenya, B.
    ACS Nano 9 10686-10694 (2015)
    The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsnano.5b01807
  • 2015 • 126 Carbon partitioning during quenching and partitioning heat treatment accompanied by carbide precipitation
    Toji, Y. and Miyamoto, G. and Raabe, D.
    Acta Materialia 86 137-147 (2015)
    Carbon partitioning from martensite into austenite in the quenching and partitioning (Q&P) process has been suggested to be controlled by the constrained carbon equilibrium (CCE) criterion. It defines an approach for predicting the carbon concentration in austenite under the condition that competing reactions such as carbide formation and bainite transformation are suppressed. Carbide precipitation in martensite is, however, often observed during the partitioning step, even in low-carbon steels as well as in high-carbon steels, even when containing a high amount of Si. Therefore, carbon partitioning from martensite into austenite is studied here, considering carbide precipitation in martensite. Carbon partitioning was investigated by means of a field-emission electron probe micro analysis (FE-EPMA) and atom probe tomography (APT), using 1.07 wt.% and 0.59 wt.% carbon steels with various martensite volume fractions. Carbon partitioning from martensite to austenite was clearly observed in all specimens, even though a considerable amount of carbide precipitated inside the martensite. The austenite carbon concentration after the partitioning step was not influenced by either the martensite volume fraction or the bulk carbon content. A modified model for predicting the austenite carbon concentration after the partitioning step was proposed to explain the experimental results by assuming carbon equilibria between austenite, ferrite and cementite under a constrained condition. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2014.11.049
  • 2015 • 125 Chemical vapor deposition of Si/SiC nano-multilayer thin films
    Weber, A. and Remfort, R. and Wöhrl, N. and Assenmacher, W. and Schulz, S.
    Thin Solid Films 593 44-52 (2015)
    Stoichiometric SiC films were deposited with the commercially available single source precursor Et3SiH by classical thermal chemical vapor deposition (CVD) as well as plasma-enhanced CVD at low temperatures in the absence of any other reactive gases. Temperature-variable deposition studies revealed that polycrystalline films containing different SiC polytypes with a Si to carbon ratio of close to 1:1 are formed at 1000°C in thermal CVD process and below 100°C in the plasma-enhanced CVD process. The plasma enhanced CVD process enables the reduction of residual stress in the deposited films and offers the deposition on temperature sensitive substrates in the future. In both deposition processes the film thickness can be controlled by variation of the process parameters such as the substrate temperature and the deposition time. The resulting material films were characterized with respect to their chemical composition and their crystallinity using scanning electron microscope, energy dispersive X-ray spectroscopy (XRD), atomic force microscopy, X-ray diffraction, grazing incidence X-ray diffraction, secondary ion mass spectrometry and Raman spectroscopy. Finally, Si/SiC multilayers of up to 10 individual layers of equal thickness (about 450 nm) were deposited at 1000°C using Et3SiH and SiH4. The resulting multilayers features amorphous SiC films alternating with Si films, which feature larger crystals up to 300 nm size as measured by transmission electron microscopy as well as by XRD. XRD features three distinct peaks for Si(111), Si(220) and Si(311). © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2015.08.042
  • 2015 • 124 Co3O4-MnO2-CNT Hybrids Synthesized by HNO3 Vapor Oxidation of Catalytically Grown CNTs as OER Electrocatalysts
    Xie, K. and Masa, J. and Madej, E. and Yang, F. and Weide, P. and Dong, W. and Muhler, M. and Schuhmann, W. and Xia, W.
    ChemCatChem 7 3027-3035 (2015)
    An efficient two-step gas-phase method was developed for the synthesis of Co<inf>3</inf>O<inf>4</inf>-MnO<inf>2</inf>-CNT hybrids used as electrocatalysts in the oxygen evolution reaction (OER). Spinel Co-Mn oxide was used for the catalytic growth of multiwalled carbon nanotubes (CNTs) and the amount of metal species remaining in the CNTs was adjusted by varying the growth time. Gas-phase treatment in HNO<inf>3</inf> vapor at 200 °C was performed to 1)open the CNTs, 2)oxidize encapsulated Co nanoparticles to Co<inf>3</inf>O<inf>4</inf> as well as MnO nanoparticles to MnO<inf>2</inf>, and 3)to create oxygen functional groups on carbon. The hybrid demonstrated excellent OER activity and stability up to 37.5h under alkaline conditions, with longer exposure to HNO<inf>3</inf> vapor up to 72h beneficial for improved electrocatalytic properties. The excellent OER performance can be assigned to the high oxidation states of the oxide nanoparticles, the strong electrical coupling between these oxides and the CNTs as well as favorable surface properties rendering the hybrids a promising alternative to noble metal based OER catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201500469
  • 2015 • 123 Combined AFM/SECM Investigation of the Solid Electrolyte Interphase in Li-Ion Batteries
    Zampardi, G. and Klink, S. and Kuznetsov, V. and Erichsen, T. and Maljusch, A. and LaMantia, F. and Schuhmann, W. and Ventosa, E.
    ChemElectroChem 2 1607-1611 (2015)
    The solid electrolyte interphase (SEI) is an electronically insulating film formed from the decomposition of the organic electrolyte at the surface of the negative electrodes in Li-ion batteries (LIBs). This film is of vital importance in the performance and safety of LIBs. Atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) are combined in one platform for the consecutive insitu investigation of surface reactions in LIBs inside an Ar-filled glovebox. As proof of concept, the formation and the electrochemical properties of the SEI formed on glassy carbon electrodes are investigated. Changes in topography during film formation of the SEI are studied via AFM. The AFM tip is then used to partially remove a small area (50×50μm2) of the SEI, which is subsequently probed using SECM in feedback mode. The AFM-scratched spot is clearly visualized in the SECM image, demonstrating the strength of the AFM/SECM combination for the investigation in the field of LIBs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201500085
  • 2015 • 122 Continuous delivery of rhBMP2 and rhVEGF165 at a certain ratio enhances bone formation in mandibular defects over the delivery of rhBMP2 alone - An experimental study in rats
    Lohse, N. and Moser, N. and Backhaus, S. and Annen, T. and Epple, M. and Schliephake, H.
    Journal of Controlled Release 220 201-209 (2015)
    The aim of the present study was to test the hypothesis that different amounts of vascular endothelial growth factor and bone morphogenic protein differentially affect bone formation when applied for repair of non-healing defects in the rat mandible. Porous composite PDLLA/CaCO3 carriers were fabricated as slow release carriers and loaded with rhBMP2 and rhVEGF165 in 10 different dosage combinations using gas foaming with supercritical carbon dioxide. They were implanted in non-healing defects of the mandibles of 132 adult Wistar rats with additional lateral augmentation. Bone formation was assessed both radiographically (bone volume) and by histomorphometry (bone density). The use of carriers with a ratio of delivery of VEGF/BMP between 0.7 and 1.2 was significantly related to the occurrence of significant increases in radiographic bone volume and/or histologic bone density compared to the use of carriers with a ratio of delivery of ≤ 0.5 when all intervals and all outcome parameters were considered. Moreover, simultaneous delivery at this ratio helped to "save" rhBMP2 as both bone volume and bone density after 13 weeks were reached/surpassed using half the dosage required for rhBMP2 alone. It is concluded, that the combined delivery of rhVEGF165 and rhBMP2 for repair of critical size mandibular defects can significantly enhance volume and density of bone formation over delivery of rhBMP2 alone. It appears from the present results that continuous simultaneous delivery of rhVEGF165 and rhBMP2 at a ratio of approximately 1 is favourable for the enhancement of bone formation. © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.jconrel.2015.10.032
  • 2015 • 121 Controllable Synthesis of Mesoporous Peapod-like Co3O4@Carbon Nanotube Arrays for High-Performance Lithium-Ion Batteries
    Gu, D. and Li, W. and Wang, F. and Bongard, H. and Spliethoff, B. and Schmidt, W. and Weidenthaler, C. and Xia, Y. and Zhao, D. and Schüth, F.
    Angewandte Chemie - International Edition 54 7060-7064 (2015)
    Abstract Transition metal oxides are regarded as promising anode materials for lithium-ion batteries because of their high theoretical capacities compared with commercial graphite. Unfortunately, the implementation of such novel anodes is hampered by their large volume changes during the Li+ insertion and extraction process and their low electric conductivities. Herein, we report a specifically designed anode architecture to overcome such problems, that is, mesoporous peapod-like Co<inf>3</inf>O<inf>4</inf>@carbon nanotube arrays, which are constructed through a controllable nanocasting process. Co<inf>3</inf>O<inf>4</inf> nanoparticles are confined exclusively in the intratubular pores of the nanotube arrays. The pores between the nanotubes are open, and thus render the Co<inf>3</inf>O<inf>4</inf> nanoparticles accessible for effective electrolyte diffusion. Moreover, the carbon nanotubes act as a conductive network. As a result, the peapod-like Co<inf>3</inf>O<inf>4</inf>@carbon nanotube electrode shows a high specific capacity, excellent rate capacity, and very good cycling performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201501475
  • 2015 • 120 Determination of the formation and range of stability of the SEI on glassy carbon by local electrochemistry
    Zampardi, G. and La Mantia, F. and Schuhmann, W.
    RSC Advances 5 31166-31171 (2015)
    The solid electrolyte interphase (SEI) is an electronic insulating and ionic conducting layer that is of main importance in lithium-ions batteries, since it critically affects the final performance of the battery system. The formation of this electronic insulating layer was determined in operando on a glassy carbon electrode by means of a microelectrode positioned in close proximity to its surface using scanning electrochemical microscopy (SECM). Glassy carbon was chosen as an ideal model system for carbonaceous materials, since it forms a SEI similar in composition to the one on graphite but concomitantly shows negligible intercalation of lithium ions. Moreover, the stability of the SEI was analysed depending on different potential ranges and the role of the cations on the insulating character of the SEI was investigated. © 2015 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5ra02940f
  • 2015 • 119 Edge magnetotransport in graphene: A combined analytical and numerical study
    Stegmann, T. and Lorke, A.
    Annalen der Physik 527 723-736 (2015)
    The current flow along the boundary of graphene stripes in a perpendicular magnetic field is studied theoretically by the nonequilibrium Green's function method. In the case of specular reflections at the boundary, the Hall resistance shows equidistant peaks, which are due to classical cyclotron motion. When the strength of the magnetic field is increased, anomalous resistance oscillations are observed, similar to those found in a nonrelativistic 2D electron gas [New. J. Phys. 15:113047 (2013)]. Using a simplified model, which allows to solve the Dirac equation analytically, the oscillations are explained by the interference between the occupied edge states causing beatings in the Hall resistance. A rule of thumb is given for the experimental observability. Furthermore, the local current flow in graphene is affected significantly by the boundary geometry. A finite edge current flows on armchair edges, while the current on zigzag edges vanishes completely. The quantum Hall staircase can be observed in the case of diffusive boundary scattering. The number of spatially separated edge channels in the local current equals the number of occupied Landau levels. The edge channels in the local density of states are smeared out but can be made visible if only a subset of the carbon atoms is taken into account. © 2015 by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/andp.201500124
  • 2015 • 118 Effects of retained austenite volume fraction, morphology, and carbon content on strength and ductility of nanostructured TRIP-assisted steels
    Shen, Y.F. and Qiu, L.N. and Sun, X. and Zuo, L. and Liaw, P.K. and Raabe, D.
    Materials Science and Engineering A 636 551-564 (2015)
    With a suite of multi-modal and multi-scale characterization techniques, the present study unambiguously proves that a substantially-improved combination of ultrahigh strength and good ductility can be achieved by tailoring the volume fraction, morphology, and carbon content of the retained austenite (RA) in a transformation-induced-plasticity (TRIP) steel with the nominal chemical composition of 0.19C-0.30Si-1.76Mn-1.52Al (weight percent, wt%). After intercritical annealing and bainitic holding, a combination of ultimate tensile strength (UTS) of 1100. MPa and true strain of 50% has been obtained, as a result of the ultrafine RA lamellae, which are alternately arranged in the bainitic ferrite around junction regions of ferrite grains. For reference, specimens with a blocky RA, prepared without the bainitic holding, yield a low ductility (35%) and a low UTS (800. MPa). The volume fraction, morphology, and carbon content of RA have been characterized using various techniques, including the magnetic probing, scanning electron microscopy (SEM), electron-backscatter-diffraction (EBSD), and transmission electron microscopy (TEM). Interrupted tensile tests, mapped using EBSD in conjunction with the kernel average misorientation (KAM) analysis, reveal that the lamellar RA is the governing microstructure component responsible for the higher mechanical stability, compared to the blocky one. By coupling these various techniques, we quantitatively demonstrate that in addition to the RA volume fraction, its morphology and carbon content are equally important in optimizing the strength and ductility of TRIP-assisted steels. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.msea.2015.04.030
  • 2015 • 117 Electrochemical detection of single E. coli bacteria labeled with silver nanoparticles
    Sepunaru, L. and Tschulik, K. and Batchelor-McAuley, C. and Gavish, R. and Compton, R.G.
    Biomaterials Science 3 816-820 (2015)
    A proof-of-concept for the electrochemical detection of single Escherichia coli bacteria decorated with silver nanoparticles is reported. Impacts of bacteria with an electrode - held at a suitably oxidizing potential - lead to an accompanying burst of current with each collision event. The frequency of impacts scales with the concentration of bacteria and the charge indicates the extent of decoration. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5bm00114e
  • 2015 • 116 Film Stress of Amorphous Hydrogenated Carbon on Biaxially Oriented Polyethylene Terephthalate
    Bahre, H. and Behm, H. and Grochla, D. and Böke, M., and Dahlmann, R., and Hopmann, C., and Ludwig, Al., and Winter, J.
    Plasma Processes and Polymers 12 896-904 (2015)
    Amorphous hydrogenated carbon (a-C:H) deposited on steel with plasma enhanced chemical vapor deposition can be used as elongation tolerant oxygen barrier. However, the elongation tolerance of the a-C:H film is lost if deposited on a poly(ethylene terephthalate) (PET) for reasons unknown. To assess this phenomenon, a-C:H was deposited on PET, silicon substrates, and silicon micro-cantilevers, and the stress was determined by measuring the radius of curvature. a-C:H deposited on PET showed lower compressive stress than on silicon. This difference is not due to the formation of a gradient layer or plastic deformation of PET. Instead, the most probable explanation is that energetic ions cause a partial release of biaxial orientation within the PET, thereby reducing the compressive stress. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/ppap.201500045
  • 2015 • 115 High-precision deformation and damage development assessment of composite materials by high-speed camera, high-frequency impulse and digital image correlation techniques
    Myslicki, S. and Ortlieb, M. and Frieling, G. and Walther, F.
    Materialpruefung/Materials Testing 57 933-941 (2015)
    Although composite materials like wood, vulcanized fiber and carbon reinforced plastic (CFRP) are already investigated by means of their mechanical properties, the abrupt fracture mechanism as well as the deformation behavior right before and after fracture has not been investigated. However, it is marginally investigated for CFRP because of the quite high fracture speed. The knowledge about the damage evolution as the crack start and propagation can help to improve the strength and sensitivity to fracture by improving the materials structure and to utilize these materials for structural applications. For the investigated materials, fracture happens abruptly as it is the nature of composites and the detailed fracture mechanisms could not be detected by conventional measurement techniques. Therefore, an innovative combination of testing devices is presented which is able to fill this gap. Tensile tests were performed to receive conventional stress-strain curves. At the fracture stage, a high-speed camera recorded the fracture process. This information could be combined with digital image correlation (DIC) to visualize the deformation behavior. At the same time acoustic emission (AE) was used to detect the spectrum of mechanical vibrations which gives information about the released energy due to fracture. The challenging triggering of the high-speed camera was solved for each material individually. By using improved light sources, the recording speed could be set up to 2 million frames per second (Mfps). The investigations show different fracture mechanisms for each composite. Wood and vulcanized fiber were also investigated in different directions due to their anisotropy. © Carl Hanser Verlag, München.
    view abstractdoi: 10.3139/120.110813
  • 2015 • 114 Highly Ordered Mesoporous Cobalt-Containing Oxides: Structure, Catalytic Properties, and Active Sites in Oxidation of Carbon Monoxide
    Gu, D. and Jia, C.-J. and Weidenthaler, C. and Bongard, H.-J. and Spliethoff, B. and Schmidt, W. and Schüth, F.
    Journal of the American Chemical Society 137 11407-11418 (2015)
    Co<inf>3</inf>O<inf>4</inf> with a spinel structure is a very active oxide catalyst for the oxidation of CO. In such catalysts, octahedrally coordinated Co3+ is considered to be the active site, while tetrahedrally coordinated Co2+ is assumed to be basically inactive. In this study, a highly ordered mesoporous CoO has been prepared by H<inf>2</inf> reduction of nanocast Co<inf>3</inf>O<inf>4</inf> at low temperature (250 °C). The as-prepared CoO material, which has a rock-salt structure with a single Co2+ octahedrally coordinated by lattice oxygen in Fm3¯m symmetry, exhibited unexpectedly high activity for CO oxidation. Careful investigation of the catalytic behavior of mesoporous CoO catalyst led to the conclusion that the oxidation of surface Co2+ to Co3+ causes the high activity. Other mesoporous spinels (CuCo<inf>2</inf>O<inf>4</inf>, CoCr<inf>2</inf>O<inf>4</inf>, and CoFe<inf>2</inf>O<inf>4</inf>) with different Co species substituted with non/low-active metal ions were also synthesized to investigate the catalytically active site of cobalt-based catalysts. The results show that not only is the octahedrally coordinated Co3+ highly active but also the octahedrally coordinated Co2+ species in CoFe<inf>2</inf>O<inf>4</inf> with an inverse spinel structure shows some activity. These results suggest that the octahedrally coordinated Co2+ species is easily oxidized and shows high catalytic activity for CO oxidation. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/jacs.5b06336
  • 2015 • 113 Influence of carbon content, particle size, and partial manganese substitution on the electrochemical performance of LiFexMn1-xPO4/carbon composites
    Hamid, N.A. and Wennig, S. and Heinzel, A. and Schulz, C. and Wiggers, H.
    Ionics 21 1857-1866 (2015)
    LiFePO<inf>4</inf>/C and LiFe<inf>x</inf>Mn<inf>1-x</inf>PO<inf>4</inf>/C (x = 0.7) nanocomposites were successfully synthesized via scalable spray-flame synthesis followed by solid-state reaction. A solution of iron (III) acetylacetonate and tributyl phosphate in toluene was used to produce amorphous, nanosized FePO<inf>4</inf>⋅H<inf>2</inf>O in a spray-flame reactor which was then milled with Li<inf>2</inf>CO<inf>3</inf> and glucose to produce a LiFePO<inf>4</inf>/C composite material in a solid-state reaction. The influence of calcination temperature and carbon content on the properties of the resulting material was investigated using specific surface area measurements (BET), X-ray diffraction (XRD), electron microscopy, and electrochemical characterization. The impact of manganese addition on the electrochemical behavior was analyzed using cyclic voltammetry (CV) and constant-current (CC) measurements. XRD shows that the combination of gas-phase synthesis and subsequent solid-state reaction yields highly pure LiFePO<inf>4</inf>/C. BET measurement revealed that the particle size of LiFePO<inf>4</inf> in the composite depends on the amount of glucose. A discharge capacity of more than 140 mAh/g at C/20 is achieved for LiFePO<inf>4</inf>/C with a carbon content of 6 wt%. This material supports high charge as well as discharge rates delivering more than 60 mAh/g at 16 C and sustains good cycle stability providing 115 mAh/g at 1 C. The energy density of the olivine increases about 10 % by substituting 30 mol% of iron by manganese while preserving the electrochemical performance of pure LiFePO<inf>4</inf>/C. © 2015, Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s11581-015-1366-6
  • 2015 • 112 Mechanisms of subgrain coarsening and its effect on the mechanical properties of carbon-supersaturated nanocrystalline hypereutectoid steel
    Li, Y.J. and Kostka, A. and Choi, P. and Goto, S. and Ponge, D. and Kirchheim, R. and Raabe, D.
    Acta Materialia 84 110-123 (2015)
    Carbon-supersaturated nanocrystalline hypereutectoid steels with a tensile strength of 6.35 GPa were produced from severely cold-drawn pearlite. The nanocrystalline material undergoes softening upon annealing at temperatures between 200 and 450°C. The ductility in terms of elongation to failure exhibits a non-monotonic dependence on temperature. Here, the microstructural mechanisms responsible for changes in the mechanical properties were studied using transmission electron microscopy (TEM), TEM-based automated scanning nanobeam diffraction and atom probe tomography (APT). TEM and APT investigations of the nanocrystalline hypereutectoid steel show subgrain coarsening upon annealing, which leads to strength reduction following a Hall-Petch law. APT analyzes of the Mn distribution near subgrain boundaries and in the cementite give strong evidence of capillary-driven subgrain coarsening occurring through subgrain boundary migration. The pronounced deterioration of ductility after annealing at temperatures above 350°C is attributed to the formation of cementite at subgrain boundaries. The overall segregation of carbon atoms at ferrite subgrain boundaries gives the nanocrystalline material excellent thermal stability upon annealing. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2014.10.027
  • 2015 • 111 Methanation of CO2: Structural response of a Ni-based catalyst under fluctuating reaction conditions unraveled by operando spectroscopy
    Mutz, B. and Carvalho, H.W.P. and Mangold, S. and Kleist, W. and Grunwaldt, J.-D.
    Journal of Catalysis 327 48-53 (2015)
    The methanation of CO<inf>2</inf> as a relevant strategy for energy storage has been studied by operando X-ray absorption spectroscopy under dynamic H<inf>2</inf>/CO<inf>2</inf> and CO<inf>2</inf> reaction atmospheres. A typical CO<inf>2</inf> conversion of 81% was reached at 400 °C with a 23 wt.-% Ni/CaO-Al<inf>2</inf>O<inf>3</inf> catalyst, yielding 80% of CH<inf>4</inf>. The operando XAS experiment under working conditions revealed pronounced structural changes, e.g., a fast bulk oxidation of the Ni particles after removal of H<inf>2</inf> from the H<inf>2</inf>/CO<inf>2</inf> (4:1) gas stream. A lower performance of the catalyst was observed in the subsequent methanation cycle due to the presence of a residual oxidized fraction of Ni. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2015.04.006
  • 2015 • 110 Non-aqueous semi-solid flow battery based on Na-ion chemistry. P2-type NaxNi0.22Co0.11Mn0.66O2-NaTi2(PO4)3
    Ventosa, E. and Buchholz, D. and Klink, S. and Flox, C. and Chagas, L.G. and Vaalma, C. and Schuhmann, W. and Passerini, S. and Morante, J.R.
    Chemical Communications 51 7298-7301 (2015)
    We report the first proof of concept for a non-aqueous semi-solid flow battery (SSFB) based on Na-ion chemistry using P2-type Na<inf>x</inf>Ni<inf>0.22</inf>Co<inf>0.11</inf>Mn<inf>0.66</inf>O<inf>2</inf> and NaTi<inf>2</inf>(PO<inf>4</inf>)<inf>3</inf> as positive and negative electrodes, respectively. This concept opens the door for developing a new low-cost type of non-aqueous semi-solid flow batteries based on the rich chemistry of Na-ion intercalating compounds. © The Royal Society of Chemistry 2015.
    view abstractdoi: 10.1039/c4cc09597a
  • 2015 • 109 Non-destructive Patterning of Carbon Electrodes by Using the Direct Mode of Scanning Electrochemical Microscopy
    Stratmann, L. and Clausmeyer, J. and Schuhmann, W.
    ChemPhysChem 16 3477-3482 (2015)
    Patterning of glassy carbon surfaces grafted with a layer of nitrophenyl moieties was achieved by using the direct mode of scanning electrochemical microscopy (SECM) to locally reduce the nitro groups to hydroxylamine and amino functionalities. SECM and atomic force microscopy (AFM) revealed that potentiostatic pulses applied to the working electrode lead to local destruction of the glassy carbon surface, most likely caused by etchants generated at the positioned SECM tip used as the counter electrode. By applying galvanostatic pulses, and thus, limiting the current during structuring, corrosion of the carbon surface was substantially suppressed. After galvanostatic patterning, unambiguous proof of the formation of the anticipated amino moieties was possible by modulation of the pH value during the feedback mode of SECM imaging. This patterning strategy is suitable for the further bio-modification of microstructured surfaces. Alkaline phosphatase, as a model enzyme, was locally bound to the modified areas, thus showing that the technique can be used for the development of protein microarrays. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cphc.201500585
  • 2015 • 108 Noncovalent grafting of carbon nanotubes with triblock terpolymers: Toward patchy 1D hybrids
    Gegenhuber, T. and Gröschel, A.H. and Löbling, T.I. and Drechsler, M. and Ehlert, S. and Förster, S. and Schmalz, H.
    Macromolecules 48 1767-1776 (2015)
    The chemical structure and high aspect ratio of carbon nanotubes (CNTs) give rise to numerous exceptional physical properties but are also the origin for their intrinsic tendency to agglomerate. Since the full potential of CNTs is harnessed in homogeneous dispersions, e.g. in a polymer matrix, bundling of CNTs must be suppressed by compatibilizing unfavorable interfaces. We present a robust, noncovalent functionalization of multiwalled CNTs via physical grafting of polystyrene-block-polyethylene-block-poly(methyl methacrylate) (SEM) triblock terpolymers to the CNT surface in organic media. In an ultrasound-assisted approach at ambient temperature, the polyethylene (PE) middle block of SEM strongly adsorbs to the CNTs surface, yielding long-term stable dispersions of well-separated 1D hybrids with up to 3 wt % CNT content. Importantly, the strong affinity of PE toward CNTs prevents polymer desorption irrespective of the solvent conditions. The incompatible polystyrene (PS) and poly(methyl methacrylate) (PMMA) end blocks of SEM self-assemble into alternating PS/PMMA corona patches and provide excellent steric stabilization for the CNTs. Shorter PS and PMMA blocks give access to dispersions with higher CNT concentration and are more efficient in stabilizing longer CNTs. Unlike covalent functionalization methods, our approach preserves the conjugated sp2-structure of the CNTs and provides an efficient, simple and time-saving method for the preparation of polymer stabilized CNTs. The patchy PS/PMMA corona of the 1D hybrids is able to adapt to the surrounding environment as demonstrated on efficient high-content blending of PMMA with 5 wt % of well-dispersed CNT/SEM hybrids. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/ma5023378
  • 2015 • 107 Novel silica-based adsorbents with activated carbon structure
    Curdts, B. and Pflitsch, C. and Pasel, C. and Helmich, M. and Bathen, D. and Atakan, B.
    Microporous and Mesoporous Materials 210 202-205 (2015)
    The preparation of silica adsorbances from chemical vapor infiltration of activated carbon with tetramethylsilane (TMS) is shown. The method bases on a two step process. In a first step, activated carbons are infiltrated at 943 K in a nitrogen-TMS-vapor atmosphere of 200 mbar. At these conditions, the carbon skeleton is covered with silicon. The resulting material is highly porous and well adapting the surface structure of the carbon templates. It is already partly oxidized at room temperature when coming into contact with air. In a second step, the infiltrated carbons are completely oxidized in air at 853 K. At these conditions, the supporting carbon skeleton is completely burned and the silicon becomes silicon oxide. The resulting materials are highly porous with extremely large surface areas around 835 m2/g. Overall, the novel material seems to well adapt the original macro- and microstructure of the activated carbon used. © 2015 The Authors. Published by Elsevier Inc.
    view abstractdoi: 10.1016/j.micromeso.2015.02.007
  • 2015 • 106 NOx conversion properties of a novel material: Iron nanoparticles stabilized in carbon
    Busch, M. and Kompch, A. and Suleiman, S. and Notthoff, C. and Bergmann, U. and Theissmann, R. and Atakan, B. and Winterer, M.
    Applied Catalysis B: Environmental 166-167 211-216 (2015)
    Nitrogen oxides (NOx) belong to the most common pollutants from combustion processes and are a major threat to human health. Carbon-based catalysts exhibit strong advantages for NOx removal like low-toxic application and easy handling. However, gasification of the carbon matrix at elevated temperatures is still one of the greatest concerns. Hence, we have directed our focus on especially low temperature NOx-removal using a novel material, iron nanoparticles stabilized in a carbon matrix (nano-Fe/C). The investigations included NO2 uptake properties and catalytic conversion of NO2 in recycle flow at 425K and 328K, scanning transmission electron microscopy and 77K-N2-adsorption. Nano-Fe/C exhibits superior NOx-removal properties compared with untreated or iron-infiltrated activated carbon or magnetite reference catalysts. No severe catalyst deactivation or catalyst aging at 425K is observed. Even at 328K nano-Fe/C still exhibits NO2-conversion, although without converting the product NO. NO2 adsorption at 297K is suggested to occur in three stages with different kinetics: (1) NO2 adsorption and reduction to NO, (2) physisorption on the oxidized catalyst surface and (3) saturation of the catalyst and diffusion into the substrate matrix. At 425K, NO2 is quickly reduced to NO and the resulting NO is further converted to N2O. After complete consumption of NO, the residual NO2 is also converted to N2O. A possible reaction mechanism is suggested based on the conversion kinetics. © 2014 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.apcatb.2014.11.013
  • 2015 • 105 On the Role of Metals in Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction
    Masa, J. and Xia, W. and Muhler, M. and Schuhmann, W.
    Angewandte Chemie - International Edition 54 10102-10120 (2015)
    The notion of metal-free catalysts is used to refer to carbon materials modified with nonmetallic elements. However, some claimed metal-free catalysts are prepared using metal-containing precursors. It is highly contested that metal residues in nitrogen-doped carbon (NC) catalysts play a crucial role in the oxygen reduction reaction (ORR). In an attempt to reconcile divergent views, a definition for truly metal-free catalysts is proposed and the differences between NC and M-N<inf>x</inf>/C catalysts are discussed. Metal impurities at levels usually undetectable by techniques such as XPS, XRD, and EDX significantly promote the ORR. Poisoning tests to mask the metal ions reveal the involvement of metal residues as active sites or as modifiers of the electronic structure of the active sites in NC. The unique merits of both M-N<inf>x</inf>/C and NC catalysts are discussed to inspire the development of more advanced nonprecious-metal catalysts for the ORR. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201500569
  • 2015 • 104 Particle-induced cell migration assay (PICMA): A new in vitro assay for inflammatory particle effects based on permanent cell lines
    Westphal, G.A. and Schremmer, I. and Rostek, A. and Loza, K. and Rosenkranz, N. and Brüning, T. and Epple, M. and Bünger, J.
    Toxicology in Vitro 29 997-1005 (2015)
    Inflammation is a decisive pathophysiologic mechanism of particle toxicity and accumulation of neutrophils in the lung is believed to be a crucial step in this process. This study describes an in vitro model for investigations of the chemotactic attraction of neutrophils in response to particles using permanent cell lines. We challenged NR8383 rat macrophages with particles that were characterized concerning chemical nature, crystallinity, and size distribution in the dry state and in the culture medium. The cell supernatants were used to investigate migration of differentiated human leukemia cells (dHL-60 cells). The dose range for the tests was determined using an impedance-based Real-Time Cell Analyzer. The challenge of NR8383 cells with 32-96μgcm-2 coarse and nanosized particles resulted in cell supernatants which induced strong and dose-dependent migration of dHL-60 cells. Quartz caused the strongest effects - exceeding the positive control "fetal calf serum" (FCS) several-fold, followed by silica, rutile, carbon black, and anatase. BaSO<inf>4</inf> served as inert control and induced no cell migration. Particles caused NR8383 cells to secrete chemotactic compounds. The assay clearly distinguished between the particles of different inflammatory potential in a highly reproducible way. Specificity of the test is suggested by negative results with BaSO<inf>4</inf>. © 2015 The Authors.
    view abstractdoi: 10.1016/j.tiv.2015.04.005
  • 2015 • 103 Phase Equilibria in Systems of Morpholine, Acetonitrile, and n -Alkanes
    Riechert, O. and Zeiner, T. and Sadowski, G.
    Journal of Chemical and Engineering Data 60 2098-2103 (2015)
    This work presents investigations on the liquid-liquid equilibria (LLE) of ternary systems composed of morpholine, acetonitrile, and an n-alkane at 298.15 K and atmospheric pressure. The investigated n-alkanes were n-hexane, n-heptane, and n-octane. The experimental data were compared to predictions using the perturbed chain-statistical associating fluid theory (PC-SAFT). The predictions are based on pure-component parameters fitted to vapor pressures and liquid densities as well as on binary parameters fitted to binary systems' phase equilibria. For that purpose, the vapor-liquid equilibrium of the morpholine/acetonitrile system was measured at 100 mbar and modeled with PC-SAFT. Binary interaction parameters for acetonitrile/n-alkane systems were obtained from a correlation as a function of the n-alkane carbon number. This correlation, together with the other pure-component and binary parameters, was used to make predictions on ternary systems with n-alkanes longer than n-octane, for which data were taken from literature. All ternary LLE predictions were in satisfactory agreement with experimental data. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.jced.5b00175
  • 2015 • 102 Photothermally induced bromination of carbon/polymer bipolar plate materials for fuel cell applications
    Schade, M. and Franzka, S. and Cappuccio, F. and Peinecke, V. and Heinzel, A. and Hartmann, N.
    Applied Surface Science 336 85-88 (2015)
    A facile photothermal procedure for direct functionalization of carbon/polymer bipolar plate materials is demonstrated. Through irradiation with a microfocused beam of an Ar+-laser at λ = 514 nm in gaseous bromine and distinct laser powers and pulse lengths local bromination of the carbon/polymer material takes place. At a 1/e spot diameter of 2.1 μm, functionalized surface areas with diameters down to 5 μm are fabricated. In complementary experiments large-area bromination is investigated using an ordinary tungsten lamp. For characterization contact angle goniometry, X-ray photoelectron spectroscopy and electron microscopy in conjunction with labeling techniques are employed. After irradiation bromine groups can easily be substituted by other chemical functionalities, e.g. azide and amine groups. This provides a facile approach in order to fabricate surface patterns and gradient structures with varying wetting characteristics. Mechanistic aspects and prospects of photothermal routines in micropatterning of carbon/polymer materials are discussed. © 2014 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.apsusc.2014.09.161
  • 2015 • 101 Si-CNT/rGO Nanoheterostructures as High-Performance Lithium-Ion-Battery Anodes
    Xiao, L. and Sehlleier, Y.H. and Dobrowolny, S. and Orthner, H. and Mahlendorf, F. and Heinzel, A. and Schulz, C. and Wiggers, H.
    ChemElectroChem 2 1983-1990 (2015)
    A robust and electrochemically stable 3D nanoheterostructure consisting of Si nanoparticles (NPs), carbon nanotubes (CNTs) and reduced graphene oxide (rGO) is developed as an anode material (Si-CNT/rGO) for lithium-ion batteries (LIBs). It integrates the benefits from its three building blocks of Si NPs, CNTs, and rGO; Si NPs offer high capacity, CNTs act as a mechanical, electrically conductive support to connect Si NPs, and highly electrically conductive and flexible rGO provides a robust matrix with enough void space to accommodate the volume changes of Si NPs upon lithiation/delithiation and to simultaneously assure good electric contact. The composite material shows a high reversible capacity of 1665mAhg-1 with good capacity retention of 88.6% over 500 cycles when cycled at 0.5C, that is, a 0.02% capacity decay per cycle. The high-power capability is demonstrated at 10C (16.2Ag-1) where 755mAhg-1 are delivered, thus indicating promising characteristics of this material for high-performance LIBs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201500323
  • 2015 • 100 Simulations of the Eutectic Transformations in the Platinum–Carbon System
    Monas, A. and Bloembergen, P. and Dong, W. and Shchyglo, O. and Steinbach, I.
    International Journal of Thermophysics 36 3366-3383 (2015)
    In this paper, we present the simulation of the eutectic phase transitions in the Pt–C system, in terms of both freezing and melting, using the multi-phase-field model. The experimentally obtained heat-extraction and -injection rates associated with the induction of freezing and melting are converted into the corresponding rates for microstructure-scale simulations. In spite of the extreme differences in the volume fractions of the FCC–Pt-rich phase on the one hand and graphite (C) on the other, satisfactory results for the kinetics of solidification and melting have been obtained, involving reasonable offsets in temperature, inducing freezing and melting, with respect to the equilibrium eutectic temperature. For freezing in the simulations, the needle/rod-like morphology, as experimentally observed, was reproduced for different heat extraction rates. The seemingly anomalous peak characterizing the simulated freezing curves is ascribed to the speed up of the solidification process due to the curvature effect. Similarly, a peak is observed in the experimental freezing curves, also showing up more clearly with increasing freezing rates. Melting was simulated starting from a frozen structure produced by a freezing simulation. The simulations reproduce the experimental melting curves and, together with the simulated freezing curves, help to understand the phase transition of the Pt–C eutectic. Finally, the effect of metallic impurities was studied. As shown for Au, impurities affect the morphology of the eutectic structure, their impact increasing with the impurity content, i.e., they can act as modifiers of the structure, as earlier reported for irregular eutectics. © 2015, Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s10765-015-1999-8
  • 2015 • 99 Stability of Dealloyed Porous Pt/Ni Nanoparticles
    Baldizzone, C. and Gan, L. and Hodnik, N. and Keeley, G.P. and Kostka, A. and Heggen, M. and Strasser, P. and Mayrhofer, K.J.J.
    ACS Catalysis 5 5000-5007 (2015)
    We provide a comprehensive durability assessment dedicated to a promising class of electrocatalysts for the oxygen reduction reaction (i.e., porous platinum nanoparticles). The stability of these nanoengineered open structures is tested under two accelerated degradation test conditions (ADT), particularly selected to mimic the potential regimes experienced by the catalyst during the operative life of a fuel cell (i.e., load cycles (up to 1.0 V<inf>RHE</inf>) and start-up cycles (up to 1.4 V<inf>RHE</inf>)). To understand the evolution of the electrochemical performance, the catalyst properties are investigated by means of fundamental rotating disc electrode studies, identical location-transmission electron microscopy (IL-TEM) coupled with electron energy loss spectroscopy chemical mapping (IL-EELS), and post-use chemical analysis and online highly sensitive potential resolved dissolution concentration monitoring by scanning flow cell inductively coupled plasma-mass spectrometry (SFC-ICP-MS). The experimental results on the nanoporous Pt revealed distinctive degradation mechanisms that could potentially affect a wide range of other nanoengineered open structures. The study concludes that, although providing promising activity performance, under the relevant operational conditions of fuel cells, the nanoporosity is only metastable and subjected to a progressive reorganization toward the minimization of the nanoscale curvature. The rate and pathways of this specific degradation mechanism together with other well-known degradation mechanisms like carbon corrosion and platinum dissolution are strongly dependent on the selected upper limit potential, leading to distinctly different durability performance. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.5b01151
  • 2015 • 98 Synthesis and X-ray Crystal Structure of Diimidosulfinate Transition Metal Complexes
    Bayram, M. and Bläser, D. and Wölper, C. and Schulz, S.
    Organometallics 34 3421-3427 (2015)
    Bis(trimethylsilyl)sulfurdiimide S(NSiMe3)2 reacts with equimolar amounts of Me2Zn and Cp∗2Zn either with insertion into the metal-carbon bond and formation of the expected S-methyl diimidosulfinate complex [MeZnN(SiMe3)S(Me)NSiMe3]2 1 or the unexpected complex {Me3SiNS[N(SiMe3)SNSiMe3]N(SiMe3)Zn}2 2. Insertion reactions were also observed with Cp∗MMe3 (M = Ti, Zr, Hf), yielding Cp∗(Me)2M[Me3SiNS(Me)NSiMe3] (M = Ti 3, Zr 4, Hf 5), whereas the corresponding Cl-substituted derivatives Cp∗(Cl)2M[(Me3SiNS(Me)NSiMe3] (M = Ti 6, Zr 7, Hf 8) were obtained from salt elimination reactions of Li S-methyl diimidosulfinate (Me3SiN)2S(Me)Li(thf)]2 9 with Cp∗MCl3. Compounds 1-8 were characterized by heteronuclear NMR (1H and 13C) and IR spectroscopy, and the solid state structures of 1-5 and 9 were determined by single crystal X-ray diffraction. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.organomet.5b00407
  • 2015 • 97 Synthesis of Heterobimetallic Group 13 Compounds via Oxidative Addition Reaction of Gallanediyl LGa and InEt3
    Ganesamoorthy, C. and Blaser, D. and Wolper, C. and Schulz, S.
    Organometallics 34 2991--2996 (2015)
    Equimolar amounts of LGa (L = [(2,6-i-Pr-2-C6H3)NC(Me)](2)CH) and InEt3 were found to react with insertion into the Incarbon bond and formation of LGa(Et)InEt2 (1), while in the presence of the N-heterocyclic carbene It-Bu [C(Nt-Bu2CH)(2)], the base-stabilized compound LGa(Et)Et2In <- It-Bu (2) was formed, which shows an abnormal binding mode of the NHC group. In addition, the reaction of InEt3 with two equivalents of LGa occurred with double insertion and formation of [LGa(Et)](2)InEt (3). 1-3 were characterized by heteronuclear NMR (H-1, C-13) and IR spectroscopy, their solid-state structures were determined by single-crystal X-ray analyses, and their thermal stability was investigated by in situ NMR spectroscopy.
    view abstractdoi: 10.1021/acs.organomet.5b00302
  • 2015 • 96 The effect of contact load on CoCrMo wear and the formation and retention of tribofilms
    Wimmer, M.A. and Laurent, M.P. and Mathew, M.T. and Nagelli, C. and Liao, Y. and Marks, L.D. and Jacobs, J.J. and Fischer, A.
    Wear 332-333 643-649 (2015)
    Tribochemical reactions in a protein lubricated metal-on-metal (MoM) sliding contact may play a significant role for its wear performance. Such reactions lead to the formation of a carbonaceous 'tribofilm', which can act as a protective layer against corrosion and wear. The purpose of this study was to determine the effect of contact load on wear and the formation and retention of tribofilms. Wear tests were performed in a custom-made ball-on-flat testing apparatus that incorporated an electrochemical cell. A ceramic ball was used to articulate against low-carbon wrought CoCrMo alloy pins in bovine serum. Using a range of contact loads at a single potentiostatic condition (close to free potential), weight loss and changes in surface properties were evaluated. We determined that wear was influenced by the loading condition. As expected, wear increased with load, but the association between applied load and measured weight loss was not linear. In the intermediate load region, in the range of 32-48 N (~58-80 MPa), there was more than an order of magnitude drop in the wear per unit load, and the wear versus load data suggested an inflexion point at 49N. Regression analyses yielded a cubic model (R2=0.991; p=0.0002), where the cubic term, which represents the inflexion, was highly significant (p=0.0021). This model is supported by the observations that the minimum in the friction versus load curve is at 52 N and the highest relative increase in polarization resistance occurred at 49 N. Scanning electron microscopy and Raman spectroscopy indicated the absence of a tribofilm for the low and within the contact area of the high load cases. Synergistic interactions of wear and corrosion seem to play an important role. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.wear.2015.02.013
  • 2015 • 95 Thin-film composite membranes for organophilic nanofiltration based on photo-cross-linkable polyimide
    Behnke, S. and Ulbricht, M.
    Reactive and Functional Polymers 86 233-242 (2015)
    This work demonstrates that it is possible to prepare new, competitive thin-film composite (TFC) membranes with a polyolefin ultrafiltration membrane as support and with a non-porous photo-cross-linked polyimide as separation layer for organic solvent nanofiltration. The commercial polyimide Lenzing P84® was modified by a polymer-analogous reaction to introduce side groups with carbon-carbon double bonds to increase its photo-reactivity with respect to cross-linking. Polymer characterization revealed that this was successfully achieved at acceptable level of main chain scission. The higher reactivity of the photo-cross-linkable polyimide had been confirmed by comparison with the original polymer; i.e., shorter gelation times upon UV irradiation, higher suppression of swelling by solvents and complete stability in strong solvents for not cross-linked polyimide such as dimethylformamide (DMF) had been obtained. For films from unmodified and modified polyimide, the degree of swelling in various solvents could be adjusted by UV irradiation time. Photo-cross-linking of the original polyimide did not lead to stability in DMF. TFC membranes had been prepared by polymer solution casting on a polyethylene ultrafiltration membrane, UV irradiation of the liquid film and subsequent solvent evaporation. Polyimide barrier film thicknesses between 10 and 1 μm were obtained by variation of cast film thickness. Performance in organic solvent nanofiltration was analyzed by using hexane, toluene, isopropanol and DMF as well as two dyes with molar masses of ∼300 and ∼1000 g/mol. Permeances of TFC membranes from unmodified polyimide were low (< 0.1 L/hm2 bar) while rejections of up to 100% for the dye with ∼1000 g/mol could be achieved. TFC membranes from modified and photo-cross-linked polyimide had adjustable separation performance in DMF with a trade-off between permeance and selectivity, in the same range (e.g.: 0.3 L/hm2 bar and 97% rejection for the dye with ∼1000 g/mol) as a commercial conventional polyimide membrane tested in parallel. The established membrane preparation method is promising because by tuning the degree of cross-linking of the polymeric barrier layer, the membrane separation performance could be tailored within the same manufacturing process. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.reactfunctpolym.2014.09.027
  • 2015 • 94 Three-Dimensional, Fibrous Lithium Iron Phosphate Structures Deposited by Magnetron Sputtering
    Bünting, A. and Uhlenbruck, S. and Sebold, D. and Buchkremer, H.P. and Vaßen, R.
    ACS Applied Materials and Interfaces 7 22594-22600 (2015)
    Crystalline, three-dimensional (3D) structured lithium iron phosphate (LiFePO4) thin films with additional carbon are fabricated by a radio frequency (RF) magnetron-sputtering process in a single step. The 3D structured thin films are obtained at deposition temperatures of 600 °C and deposition times longer than 60 min by using a conventional sputtering setup. In contrast to glancing angle deposition (GLAD) techniques, no tilting of the substrate is required. Thin films are characterized by X-ray diffraction (XRD), Raman spectrospcopy, scanning electron microscopy (SEM), cyclic voltammetry (CV), and galvanostatic charging and discharging. The structured LiFePO4 + C thin films consist of fibers that grow perpendicular to the substrate surface. The fibers have diameters up to 500 nm and crystallize in the desired olivine structure. The 3D structured thin films have superior electrochemical properties compared with dense two-dimensional (2D) LiFePO4 thin films and are, hence, very promising for application in 3D microbatteries. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsami.5b07090
  • 2015 • 93 Trimodal hierarchical carbide-derived carbon monoliths from steam- and CO2-activated wood templates for high rate lithium sulfur batteries
    Adam, M. and Strubel, P. and Borchardt, L. and Althues, H. and Dörfler, S. and Kaskel, S.
    Journal of Materials Chemistry A 3 24103-24111 (2015)
    Hierarchically structured biomorphic carbide-derived carbon (CDC) materials are obtained by applying a combined activation- and CDC approach on abundantly available, renewable and cheap raw materials. For the synthesis of these materials we mimic nature by using wood structures as templates which are already optimized for mass transport during their long-term evolutional process. The impregnation of steam- or carbon dioxide-pre-activated wood templates with a polycarbosilane precursor and the subsequent halogen treatment yields a hierarchical material that exhibits longitudinally orientated macropores from the wood structure as well as well-defined and narrowly distributed micro- and meso-pores derived from the activation and CDC approach. These materials offer specific surface areas up to 1750 m2 g-1, micro-/meso-pore volumes up to 1.0 cm3 g-1 and macropore volumes of 1.2 cm3 g-1. This sophisticated hierarchical pore system ensures both efficient mass transfer and high specific surface area, ideal for mass transport limited applications, such as the lithium sulfur battery. Testing steam activated wood-CDCs as cathode materials for Li-S batteries reveals excellent performance, especially a highly stable discharge capacity and sulfur utilization. Stable capacities of over 580 mA h gsulfur-1 at current densities exceeding 20 mA cm-2 (2C) are possible using only very low amounts of electrolyte of 6.8 μL mgsulfur-1. © 2015 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5ta06782k
  • 2014 • 92 A carbon-coated TiO2(B) nanosheet composite for lithium ion batteries
    Sun, Z. and Huang, X. and Muhler, M. and Schuhmann, W. and Ventosa, E.
    Chemical Communications 50 5506-5509 (2014)
    The carbon-coated TiO2(B) nanosheet composite synthesized by one-step hydrolysis of TiCl3 followed by vacuum annealing and air annealing delivers outstanding electrochemical performance as a negative electrode for Li-ion batteries, i.e. reversible capacity above 150 mA h g -1 at 30 C (10 A g-1). This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cc01888e
  • 2014 • 91 Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe-Nx/C groups
    Rincón, R.A. and Masa, J. and Mehrpour, S. and Tietz, F. and Schuhmann, W.
    Chemical Communications 50 14760-14762 (2014)
    The incorporation of Fe-Nx/C moieties into perovskites remarkably activates them for the oxygen reduction reaction (ORR) and also leads to notable improvement of their activity towards the oxygen evolution reaction (OER) thus presenting a new route for realizing high performance, low cost bifunctional catalysts for reversible oxygen electrodes. This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cc06446a
  • 2014 • 90 Atomic imaging of carbon-supported Pt, Pt/Co, and Ir@Pt nanocatalysts by atom-probe tomography
    Li, T. and Bagot, P.A.J. and Christian, E. and Theobald, B.R.C. and Sharman, J.D.B. and Ozkaya, D. and Moody, M.P. and Tsang, S.C.E. and Smith, G.D.W.
    ACS Catalysis 4 695-702 (2014)
    Atom probe tomography (APT) has been used to characterize commercially prepared Pt, Pt/Co alloy, and Ir@Pt core-shell nanoparticles supported on high-surface-area carbon black. Concentration profiles and 3D atom maps revealing the detailed internal structures and compositions of Pt, Pt/Co alloy, and Ir@Pt core-shell particles have been generated, and the distribution of trace impurity elements, including Na and Cl, has been examined. The observation of retained Na on the support, especially in the Pt nanoparticle system, indicates a more rigorous washing procedure is required. In the Pt/Co alloyed carbon-supported nanoparticle system, a marked variation in both compositions and particle sizes is observed. In the case of Ir@Pt, significant intermixing of the Ir core and Pt shell atoms takes place, which would be very difficult to measure by other techniques. All such observations will likely impact the catalytic performance of these materials. We envisage that the single nanoparticle analysis capability of APT, providing atomic-scale structures and chemical mapping, can also act as a means of quality control, identifying differences in the final product compared with the intended specification. Although the catalytic activity of these nanoparticles was not part of current study, the detailed information offered by such studies will permit knowledge-based improvements in nanoscale catalyst preparation methods and will also provide new ways of investigating structure and activity relationships at the nanometer scale. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/cs401117e
  • 2014 • 89 Atomic-scale analysis of carbon partitioning between martensite and austenite by atom probe tomography and correlative transmission electron microscopy
    Toji, Y. and Matsuda, H. and Herbig, M. and Choi, P.-P. and Raabe, D.
    Acta Materialia 65 215-228 (2014)
    Carbon partitioning between ferritic and austenitic phases is essential for austenite stabilization in the most advanced steels such as those produced by the quenching and partitioning (Q&P) process. The atomistic analysis of the carbon partitioning in Q&P alloys is, however, difficult owing to the simultaneous occurrence of bainite transformation, which can also contribute to carbon enrichment into remaining austenite and hence overlap with the carbon partitioning from martensite into austenite. Therefore, we provide here a direct atomic-scale evidence of carbon partitioning from martensite into austenite without the presence of bainite transformation. Carbon partitioning is investigated by means of atom probe tomography and correlative transmission electron microscopy. A model steel (Fe-0.59 wt.% C (2.7 at.% C)-2.0 wt.% Si-2.9 wt.% Mn) with martensite finish temperature below room temperature was designed and used in order to clearly separate the carbon partitioning between martensite and austenite from the bainite transformation. The steel was austenitized at 900°C, then water-quenched and tempered at 400°C. Approximately 8 vol.% retained austenite existed in the asquenched state. We confirmed by X-ray diffraction and dilatometry that austenite decomposition via bainite transformation did not occur during tempering. No carbon enrichment in austenite was observed in the as-quenched specimen. On the other hand, clear carbon enrichment in austenite was observed in the 400°C tempered specimens with a carbon concentration inside the austenite of 5-8 at.%. The results hence quantitatively revealed carbon partitioning from martensite to austenite, excluding bainite transformation during the Q&P heat treatment. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.10.064
  • 2014 • 88 Atomic-scale quantification of grain boundary segregation in nanocrystalline material
    Herbig, M. and Raabe, D. and Li, Y.J. and Choi, P. and Zaefferer, S. and Goto, S.
    Physical Review Letters 112 (2014)
    Grain boundary segregation leads to nanoscale chemical variations that can alter a material's performance by orders of magnitude (e.g., embrittlement). To understand this phenomenon, a large number of grain boundaries must be characterized in terms of both their five crystallographic interface parameters and their atomic-scale chemical composition. We demonstrate how this can be achieved using an approach that combines the accuracy of structural characterization in transmission electron microscopy with the 3D chemical sensitivity of atom probe tomography. We find a linear trend between carbon segregation and the misorientation angle ω for low-angle grain boundaries in ferrite, which indicates that ω is the most influential crystallographic parameter in this regime. However, there are significant deviations from this linear trend indicating an additional strong influence of other crystallographic parameters (grain boundary plane, rotation axis). For high-angle grain boundaries, no general trend between carbon excess and ω is observed; i.e., the grain boundary plane and rotation axis have an even higher influence on the segregation behavior in this regime. Slight deviations from special grain boundary configurations are shown to lead to unexpectedly high levels of segregation. © 2014 American Physical Society.
    view abstractdoi: 10.1103/PhysRevLett.112.126103
  • 2014 • 87 Carbon-based micro-ball and micro-crystal deposition using filamentary pulsed atmospheric pressure plasma
    Pothiraja, R. and Bibinov, N. and Awakowicz, P.
    Journal of Physics D: Applied Physics 47 (2014)
    Thin plasma filaments are produced by the propagation of ionization waves from a spiked driven electrode in a quartz tube in an argon/methane gas mixture (2400sccm/2sccm) at atmospheric pressure. The position of the touch point of filaments on the substrate surface is controlled in our experiment by applying various suitable substrate configurations and geometries of the grounded electrode. The gas conditions at the touch point are varied from argon to ambient air. Based on microphotography and discharge current waveforms, the duration of the filament touching the substrate is estimated to be about one microsecond. Carbon-based materials are deposited during this time at the touch points on the substrate surface. Micro-balls are produced if the filament touch points are saved from ambient air by the argon flow. Under an air admixture, micro-crystals are formed. The dimension of both materials is approximately one micrometre (0.5-2m) and corresponds to about 1010-1012 carbon atoms. Neither the diffusion of neutral species nor drift of ions can be reason for the formation of such a big micro-material during this short period of filament-substrate interaction. It is possible that charged carbon-based materials are formed in the plasma channel and transported to the surface of the substrate. The mechanism of this transport and characterization of micro-materials, which are formed under different gas conditions in our experiment, will be studied in the future. © 2014 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0022-3727/47/31/315203
  • 2014 • 86 Carbon-based yolk-shell materials for fuel cell applications
    Galeano, C. and Baldizzone, C. and Bongard, H. and Spliethoff, B. and Weidenthaler, C. and Meier, J.C. and Mayrhofer, K.J.J. and Schüth, F.
    Advanced Functional Materials 24 220-232 (2014)
    The synthesis of yolk-shell catalysts, consisting of platinum or gold-platinum cores and graphitic carbon shells, and their electrocatalytic stabilities are described. Different encapsulation pathways for the metal nanoparticles are explored and optimized. Electrochemical studies of the optimized AuPt, @C catalyst revealed a high stability of the encapsulated metal particles. However, in order to reach full activity, several thousand potential cycles are required. After the electrochemical surface area is fully developed, the catalysts show exceptionally high stability, with almost no degradation over approximately 30 000 potential cycles between 0.4 and 1.4 VRHE. Encapsulation of noble metals in graphitic hollow shells by hard templating is explored as a means for stabilizing fuel cell catalysts. Small platinum particles can be encapsulated, but the achievable loading is too small. Encapsulation of Au-Pt yolk-shell particles allows higher loading, and with such cores, stable catalysts could be produced. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adfm.201302239
  • 2014 • 85 Chemical vapor infiltration of activated carbon with tetramethylsilane
    Pflitsch, C. and Curdts, B. and Helmich, M. and Pasel, C. and Notthoff, C. and Bathen, D. and Atakan, B.
    Carbon 79 28-35 (2014)
    Chemical vapor infiltration of activated carbon with tetramethylsilane (TMS) at 200 hPa total pressure and a gas phase concentration of 15 (mol-)% TMS in nitrogen is studied. The influence of temperature on the infiltration process is discussed in detail. Up to 873 K, the infiltration is performed in the kinetically controlled regime resulting in high loadings up to around 42 (wt.-)%. The modified materials show high values for BET-surface and pore volume indicating a sufficient adoption of the infiltrated silicon layer to the surface morphology of the carbon substrates. Low oxidation resistance of the infiltrated material and EDX measurements give rise to the assumption that the infiltrated material is silicon. At higher infiltration temperatures above 873 K, particles are formed which have the shape of cylindrical nanostructures. EDX measurements reveal that silicon carbide is produced at these temperatures. © 2014 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2014.07.018
  • 2014 • 84 Coupled atomistic-continuum study of the effects of C atoms at α-Fe dislocation cores
    Chockalingam, K. and Janisch, R. and Hartmaier, A.
    Modelling and Simulation in Materials Science and Engineering 22 (2014)
    The influence of carbon at dislocation cores in α-Fe is studied to determine the Peierls stress, i.e. the critical stress required to move the dislocation at 0 K. The effect of carbon on both edge and screw dislocations is investigated. A coupled molecular statics (MS) and extended finite element method (XFEM) is employed for this study, where the dislocation core is modeled atomistically. The results on pure Fe are found to be in good agreement with a fully atomistic study. The coupled approach captures the right core behavior and significantly reduces the size of the atomistic region, while describing the behavior of a single dislocation in an infinite anisotropic elastic medium. Furthermore, mechanical boundary conditions can be applied consistently. It was found that the influence of carbon on edge dislocations is much stronger than that on screw dislocations, and that carbon causes a directionally dependent Peierls stress in the case of a screw dislocation. Even though the increase of the Peierls stress is much more pronounced for edge dislocations, the total value does not reach the level of the Peierls stress for screw dislocations, either with or without carbon at the core. Hence, we conclude that the motion of screw dislocations remains the rate limiting factor for plastic deformation of α-Fe. © 2014 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0965-0393/22/7/075007
  • 2014 • 83 Electrochemical nanoprobes for single-cell analysis
    Actis, P. and Tokar, S. and Clausmeyer, J. and Babakinejad, B. and Mikhaleva, S. and Cornut, R. and Takahashi, Y. and López Córdoba, A. and Novak, P. and Shevchuck, A.I. and Dougan, J.A. and Kazarian, S.G. and Gorelkin, P.V. and...
    ACS Nano 8 875-884 (2014)
    The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5-200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microscopy probes, which should allow high resolution electrochemical mapping of species on or in living cells. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/nn405612q
  • 2014 • 82 Encapsulation strategies in energy conversion materials
    Schüth, F.
    Chemistry of Materials 26 423-434 (2014)
    Many energy conversion materials show increased performance, if the materials are used in nanostructured form. However, this could be detrimental for stability of the materials, since during cycling the nanostructuring tends to be lost because of particle growth. This problem may be solved by encapsulation of the active material in different types of matrices or coatings, which beyond the stabilization may also provide additional functionality, such as conductivity or mechanical reinforcement. This Perspective covers the general features of encapsulation strategies, and desribes selected examples for different types of energy conversion materials. At the end, promising development lines will be discussed, together with the need for a more systematic study of the effects of encapsulation. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/cm402791v
  • 2014 • 81 Ex-situ preparation of high-conductive polymer/SWNTs nanocomposites for structure fabrication
    Guo, Q. and Ghadiri, R. and Weigel, T. and Aumann, A. and Gurevich, E.L. and Esen, C. and Li, Y. and Cheng, W. and Chichkov, B. and Ostendorf, A.
    Proceedings of SPIE - The International Society for Optical Engineering 9277 (2014)
    This paper reports ex-situ preparation of conductive polymer/single-walled carbon nanotubes (SWNTs) nanocomposites by adding high conductive SWNTs to the polymer matrix. Sonication methods were used to disperse the SWNTs in the polymer. The conductivity of the nanocomposites is tuned by increasing the concentration of SWNTs. Furthermore, we present two-photon polymerization (2PP) method to fabricate structures on the basis of conductive photosensitive composites. The conductive structures were successfully generated by means of 2PP effect induced by a femtosecond laser. © 2014 SPIE.
    view abstractdoi: 10.1117/12.2071870
  • 2014 • 80 Heterogeneous Catalysis of CO2 Conversion to Methanol on Copper Surfaces
    Behrens, M.
    Angewandte Chemie - International Edition 53 12022-12024 (2014)
    Combined experimental and theoretical approaches resulted in a better understanding of the hydrogenation of CO2 to methanol on copper-based catalysts. These results highlight the important role of the reducible oxide promoter for CO2 activation. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201409282
  • 2014 • 79 Hierarchical carbide-derived carbon foams with advanced mesostructure as a versatile electrochemical energy-storage material
    Oschatz, M. and Borchardt, L. and Pinkert, K. and Thieme, S. and Lohe, M.R. and Hoffmann, C. and Benusch, M. and Wisser, F.M. and Ziegler, C. and Giebeler, L. and Rümmeli, M.H. and Eckert, J. and Eychmüller, A. and Kaskel, S.
    Advanced Energy Materials 4 (2014)
    Highly porous carbide-derived carbon (CDC) mesofoams (DUT-70) are prepared by nanocasting of mesocellular silica foams with a polycarbosilane precursor. Ceramic conversion followed by silica removal and high-temperature chlorine treatment yields CDCs with a hierarchical micro-mesopore arrangement. This new type of polymer-based CDC is characterized by specific surface areas as high as 2700 m2 g-1, coupled with ultrahigh micro- and mesopore volumes up to 2.6 cm3 g-1. The relationship between synthesis conditions and the properties of the resulting carbon materials is described in detail, allowing precise control of the properties of DUT-70. Since the hierarchical pore system ensures both efficient mass transfer and high capacities, the novel CDC shows outstanding performance as an electrode material in electrochemical double-layer capacitors (EDLCs) with specific capacities above 240 F g-1 when measured in a symmetrical two-electrode configuration. Remarkable capacities of 175 F g-1 can be retained even at high current densities of 20 A g-1 as a result of the enhanced ion-transport pathways provided by the cellular mesostructure. Moreover, DUT-70 can be infiltrated with sulfur and host the active material in lithium-sulfur battery cathodes. Reversible capacities of 790 mAh g-1 are achieved at a current rate of C/10 after 100 cycles, which renders DUT-70 an ideal support material for electrochemical energy-storage applications. Hierarchical carbide-derived carbon (CDC) mesofoams (DUT-70) with extremely high specific surface areas and nanopore volumes are presented. DUT-70 shows outstanding specific capacities as electrode materials in electrochemical double-layer capacitors and as sulfur host in lithium-sulfur battery cathodes. This CDC is an advanced material for electrochemical energy storage, combining high capacities with efficient mass-transfer behavior. © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/aenm.201300645
  • 2014 • 78 History effects in lithium-oxygen batteries: How initial seeding influences the discharge capacity
    Rinaldi, A. and Wijaya, O. and Hoster, H.E. and Yu, D.Y.W.
    ChemSusChem 7 1283-1288 (2014)
    In laboratory experiments, Li-O2 systems show "sudden death" at capacities far below the theoretical value. Identifying how discharge products limit the total capacity is crucial in Li-O2 system. We investigated the effect of Li2O2 seed layer deposited on carbon cathode under potentiostatic conditions at increasing overpotentials to the subsequent slow discharge at galvanostatic condition. The discharge capacity attainable in the second step is found to vary by more than a factor of 3 depending on the history, i.e., the seed layer. These results provide evidence that the battery history is decisive for the total discharge capacities. History lesson: The discharge product will at some point form the surface of the ongoing electrochemical reaction in Li-O2 battery. The nature of Li2O2 deposits are crucial for a battery's capacity performance. The discharge profiles of carbon cathodes that are precovered by Li2O2 seed layers are compared. The layers are Coulometrically equal but are deposited at varying deposition rates, and demonstrate how faster initial seeding leads to lower total discharge capacities. © 2014 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201300986
  • 2014 • 77 Impact of nanodiffusion on the stacking fault energy in high-strength steels
    Hickel, T. and Sandlöbes, S. and Marceau, R.K.W. and Dick, A. and Bleskov, I. and Neugebauer, J. and Raabe, D.
    Acta Materialia 75 147-155 (2014)
    A key requirement of modern steels - the combination of high strength and high deformability - can best be achieved by enabling a local adaptation of the microstructure during deformation. A local hardening is most efficiently obtained by a modification of the stacking sequence of atomic layers, resulting in the formation of twins or martensite. Combining ab initio calculations with in situ transmission electron microscopy, we show that the ability of a material to incorporate such stacking faults depends on its overall chemical composition and, importantly, the local composition near the defect, which is controlled by nanodiffusion. Specifically, the role of carbon for the stacking fault energy in high-Mn steels is investigated. Consequences for the long-term mechanical properties and the characterisation of these materials are discussed. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2014.04.062
  • 2014 • 76 In vitro and in vivo interactions of selected nanoparticles with rodent serum proteins and their consequences in biokinetics
    Kreyling, W.G. and Fertsch-Gapp, S. and Schäffler, M. and Johnston, B.D. and Haberl, N. and Pfeiffer, C. and Diendorf, J. and Schleh, C. and Hirn, S. and Semmler-Behnke, M. and Epple, M. and Parak, W.J.
    Beilstein Journal of Nanotechnology 5 1699-1711 (2014)
    When particles incorporated within a mammalian organism come into contact with body fluids they will bind to soluble proteins or those within cellular membranes forming what is called a protein corona. This binding process is very complex and highly dynamic due to the plethora of proteins with different affinities and fractions in different body fluids and the large variation of compounds and structures of the particle surface. Interestingly, in the case of nanoparticles (NP) this protein corona is well suited to provide a guiding vehicle of translocation within body fluids and across membranes. This NP translocation may subsequently lead to accumulation in various organs and tissues and their respective cell types that are not expected to accumulate such tiny foreign bodies. Because of this unprecedented NP accumulation, potentially adverse biological responses in tissues and cells cannot be neglected a priori but require thorough investigations. Therefore, we studied the interactions and protein binding kinetics of blood serum proteins with a number of engineered NP as a function of their physicochemical properties. Here we show by in vitro incubation tests that the binding capacity of different engineered NP (polystyrene, elemental carbon) for selected serum proteins depends strongly on the NP size and the properties of engineered surface modifications. In the following attempt, we studied systematically the effect of the size (5, 15, 80 nm) of gold spheres (AuNP), surface-modified with the same ionic ligand; as well as 5 nm AuNP with five different surface modifications on the binding to serum proteins by using proteomics analyses. We found that the binding of numerous serum proteins depended strongly on the physicochemical properties of the AuNP. These in vitro results helped us substantially in the interpretation of our numerous in vivo biokinetics studies performed in rodents using the same NP. These had shown that not only the physicochemical properties determined the AuNP translocation from the organ of intake towards blood circulation and subsequent accumulation in secondary organs and tissues but also the the transport across organ membranes depended on the route of AuNP application. Our in vitro protein binding studies support the notion that the observed differences in in vivo biokinetics are mediated by the NP protein corona and its dynamical change during AuNP translocation in fluids and across membranes within the organism. © 2014 Kreyling et al.
    view abstractdoi: 10.3762/bjnano.5.180
  • 2014 • 75 Influence of molecular hydrogen on acetylene pyrolysis: Experiment and modeling
    Aghsaee, M. and Dürrstein, S.H. and Herzler, J. and Böhm, H. and Fikri, M. and Schulz, C.
    Combustion and Flame 161 2263-2269 (2014)
    The effect of molecular hydrogen on the formation of molecular carbonaceous species important for soot formation is studied through a combination of shock-tube experiments with high-repetition-rate time-of-flight mass spectrometry and detailed chemistry modeling. The experiment allows to simultaneously measure the concentration-time profiles for various species with a time resolution of 10μs. Concentration histories of reactants and polyacetylene intermediates (C2xH2, x=1-4) are measured during the pyrolysis of acetylene with and without H2 added to the gas mixture for a wide range of conditions. In the 1760-2565K temperature range, reasonable agreement between the experiment and the model predictions for C2H2, C4H2, C6H2, and C8H2 is achieved. H2 addition leads to the depletion of important building blocks for particle formation, namely of polyacetylenes due to an enhanced consumption of important radicals by H2, which are required for the fast build-up of carbonaceous material. © 2014 The Combustion Institute.
    view abstractdoi: 10.1016/j.combustflame.2014.03.012
  • 2014 • 74 Influence of solution nitriding of supersolidus-sintered cold work tool steels on their hardenability
    Blüm, M. and Conrads, J. and Weber, S. and Theisen, W.
    HTM - Journal of Heat Treatment and Materials 69 273-281 (2014)
    Powder metallurgical steel grades offer higher quality and performance compared to cast and forged steel grades due to their finer microstructure without segregations or textures. Because high-alloyed, cold work tool steels cannot be compacted by solid-state sintering, hot isostatic pressing is state of the art. This process, however, is comparatively expensive and there is thus a high demand for alternative densification processes. Supersolidus liquid-phase sintering represents an alternative to hot isostatic pressing for densification of these steels to theoretical density. During sintering, the steel powder interacts with the sintering atmosphere, which can be a vacuum, hydrogen, hydrogen plus nitrogen, or nitrogen. In a nitrogen atmosphere, there may be nitrogen uptake by the sintered material, which changes the chemical composition of the steel and thus results in a decrease in the sintering temperature. The aim of this work is to investigate the influence of nitrogen uptake on the hardenability of a high-alloyed and supersolidus-sintered cold work tool steel. Computational thermodynamics using the Calphad method were applied to calculate the optimal parameters for direct quenching from the sintering temperature. In addition, the tempering response was investigated as a function of the heat-treatment parameters. It was found that nitriding exerts a significant influence on the hardenability, which is also dependent on the cooling rate from the sintering temperature to the quenching temperature. Hardenability was predicted qualitatively on the basis of equilibrium carbon concentrations of the austenitic matrix calculated with the Calphad method. © 2014 Carl Hanser Verlag GmbH & Co. KG.
    view abstractdoi: 10.3139/105.110234
  • 2014 • 73 Interface effects in NaAlH4-carbon nanocomposites for hydrogen storage
    Gao, J. and Ngene, P. and Herrich, M. and Xia, W. and Gutfleisch, O. and Muhler, M. and De Jong, K.P. and De Jongh, P.E.
    International Journal of Hydrogen Energy 39 10175-10183 (2014)
    For practical solid-state hydrogen storage, reversibility under mild conditions is crucial. Complex metal hydrides such as NaAlH4 and LiBH4 have attractive hydrogen contents. However, hydrogen release and especially uptake after desorption are sluggish and require high temperatures and pressures. Kinetics can be greatly enhanced by nanostructuring, for instance by confining metal hydrides in a porous carbon scaffold. We present for a detailed study of the impact of the nature of the carbon-metal hydride interface on the hydrogen storage properties. Nanostructures were prepared by melt infiltration of either NaAlH4 or LiBH4 into a carbon scaffold, of which the surface had been modified, varying from H-terminated to oxidized (up to 4.4 O/nm2). It has been suggested that the chemical and electronic properties of the carbon/metal hydride interface can have a large influence on hydrogen storage properties. However, no significant impact on the first H2 release temperatures was found. In contrast, the surface properties of the carbon played a major role in determining the reversible hydrogen storage capacity. Only a part of the oxygen-containing groups reacted with hydrides during melt infiltration, but further reaction during cycling led to significant losses, with reversible hydrogen storage capacity loss up to 40% for surface oxidized carbon. However, if the carbon surface had been hydrogen terminated, ∼6 wt% with respect to the NaAlH4 weight was released in the second cycle, corresponding to 95% reversibility. This clearly shows that control over the nature and amount of surface groups offers a strategy to achieve fully reversible hydrogen storage in complex metal hydride-carbon nanocomposites. © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.ijhydene.2014.03.188
  • 2014 • 72 Investigation of coking during dry reforming of methane by means of thermogravimetry
    Tarasov, A. and Düdder, H. and Mette, K. and Kühl, S. and Kähler, K. and Schlögl, R. and Muhler, M. and Behrens, M.
    Chemie-Ingenieur-Technik 86 1916-1924 (2014)
    Coking dynamics of Ni-based and Ni-free catalysts were studied in a magnetic suspension thermobalance under methane dry reforming conditions. Ni-rich catalysts undergo strong coking featured with a surface saturation point where the coking rate is drastically reduced. Catalyst resistance towards coking may be enhanced by using noble-metal-based Ni-free precursors or decreasing the Ni content in the catalytic system. The post reaction performed temperature-programmed oxidation experiment of the coked catalyst is diffusion-limited due to large amounts of formed carbon. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/cite.201400092
  • 2014 • 71 Iron oxide/polymer-based nanocomposite material for hydrogen sulfide adsorption applications
    Blatt, O. and Helmich, M. and Steuten, B. and Hardt, S. and Bathen, D. and Wiggers, H.
    Chemical Engineering and Technology 37 1938-1944 (2014)
    The processing of iron oxide nanoparticles derived from spray flame synthesis for specific adsorption applications is described. After the as-prepared particles proved the ability for H2S removal in pure gas treatment, two different nanoparticle- based composite materials were prepared. While impregnation of activated carbon with the as-prepared nanoparticles showed the expected increase in H2S adsorption capacities, a significant enhancement in desulfurization performance was observed for a novel iron oxide nanoparticle composite material. H2S adsorption was tested in fixed-bed breakthrough curve measurements. The H2S removal efficiency of the novel material under ambient conditions indicates highly promising properties for potential use in industrial and air pollution control applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/ceat.201400303
  • 2014 • 70 Kroll-carbons based on silica and alumina templates as high-rate electrode materials in electrochemical double-layer capacitors
    Oschatz, M. and Boukhalfa, S. and Nickel, W. and Lee, J.T. and Klosz, S. and Borchardt, L. and Eychmüller, A. and Yushin, G. and Kaskel, S.
    Journal of Materials Chemistry A 2 5131-5139 (2014)
    Hierarchical Kroll-carbons (KCs) with combined micro- and mesopore systems are prepared from silica and alumina templates by a reductive carbochlorination reaction of fumed silica and alumina nanoparticles inside a dense carbon matrix. The resulting KCs offer specific surface areas close to 2000 m2 g-1 and total pore volumes exceeding 3 cm3 g-1, resulting from their hierarchical pore structure. High micropore volumes of 0.39 cm3 g-1 are achieved in alumina-based KCs due to the enhanced carbon etching reaction being mainly responsible for the evolution of porosity. Mesopore sizes are uniform and precisely controllable over a wide range by the template particle dimensions. The possibility of directly recycling the process exhaust gases for the template synthesis and the use of renewable carbohydrates as the carbon source lead to a scalable and efficient alternative to classical hard- and soft templating approaches for the production of mesoporous and hierarchical carbon materials. Silica- and alumina-based Kroll-carbons are versatile electrode materials in electrochemical double-layer capacitors (EDLCs). Specific capacitances of up to 135 F g-1 in an aqueous electrolyte (1 M sulfuric acid) and 174 F g-1 in ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) are achieved when measured in a symmetric cell configuration up to voltages of 0.6 and 2.5 V, respectively. 90% of the capacitance can be utilized at high current densities (20 A g -1) and room temperature rendering Kroll-carbons as attractive materials for EDLC electrodes resulting in high capacities and high rate performance due to the combined presence of micro- and mesopores. This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c3ta14815g
  • 2014 • 69 Metal-free catalysts for oxygen reduction in alkaline electrolytes: Influence of the presence of Co, Fe, Mn and Ni inclusions
    Masa, J. and Zhao, A. and Wei, X. and Muhler, M. and Schuhmann, W.
    Electrochimica Acta 128 271-278 (2014)
    Metal-free nitrogen modified carbon catalysts (NC) are very closely related to MNC catalysts which contain a transition metal(s) (M), usually Fe or Co as an essential constituent. We investigated the influence of metal inclusions on the activity of nitrogen-doped carbon black in the electrocatalysis of the oxygen reduction reaction (ORR). A reference metal-free NC catalyst was prepared by pyrolysis of a polypyrrole/Vulcan XC72 composite at 800 °C for 2 h under helium. Controlled amounts of Co, Fe, Mn and Ni in low concentrations were then introduced into NC by impregnating it with the corresponding meso-tetra(4-pyridyl) porphyrin metal complex followed by further pyrolysis at 650 °C for 2 h under helium. The resulting catalysts were investigated for ORR using rotating disk electrode and rotating-ring disk electrode voltammetry in 0.1 M KOH. Additionally, the rate of decomposition of hydrogen peroxide by the different catalysts was determined in order to probe the influence of the metal inclusions on the mechanism and selectivity of the ORR. The results show that Fe, Co and Mn inclusions cause a substantial decrease of the overpotential of the reaction and enhance the catalytic current, whereas the presence of Ni has a poisoning effect on ORR. In the presence of Fe, the catalysts apparently reduce oxygen selectively to OH- in a direct four electron transfer process as opposed to the two-step, two electron pathway involving hydrogen peroxide as an intermediate for the case of the NC catalyst. © 2013 Elsevier Ltd.
    view abstractdoi: 10.1016/j.electacta.2013.11.026
  • 2014 • 68 MnxOy/NC and CoxOy/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes
    Masa, J. and Xia, W. and Sinev, I. and Zhao, A. and Sun, Z. and Grützke, S. and Weide, P. and Muhler, M. and Schuhmann, W.
    Angewandte Chemie - International Edition 53 8508-8512 (2014)
    Reversible interconversion of water into H2 and O2, and the recombination of H2 and O2 to H2O thereby harnessing the energy of the reaction provides a completely green cycle for sustainable energy conversion and storage. The realization of this goal is however hampered by the lack of efficient catalysts for water splitting and oxygen reduction. We report exceptionally active bifunctional catalysts for oxygen electrodes comprising Mn3O4 and Co 3O4 nanoparticles embedded in nitrogen-doped carbon, obtained by selective pyrolysis and subsequent mild calcination of manganese and cobalt N4 macrocyclic complexes. Intimate interaction was observed between the metals and nitrogen suggesting residual M-Nx coordination in the catalysts. The catalysts afford remarkably lower reversible overpotentials in KOH (0.1M) than those for RuO2, IrO2, Pt, NiO, Mn3O4, and Co3O4, thus placing them among the best non-precious-metal catalysts for reversible oxygen electrodes reported to date. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201402710
  • 2014 • 67 Nanoparticle-Impact Experiments are Highly Sensitive to the Presence of Adsorbed Species on Electrode Surfaces
    Kätelhön, E. and Cheng, W. and Batchelor-Mcauley, C. and Tschulik, K. and Compton, R.G.
    ChemElectroChem 1 1057-1062 (2014)
    We theoretically and experimentally investigate the influence of partial surface blocking on the electrochemistry of nanoparticles impacting at an electrode. To this end, we introduce an analytical model for the adsorption of single blocking molecules on the electrode and calculate the resulting fractional electrode coverage. We find that even small amounts of adsorbed molecules can fully suppress detection of impacts of nanoparticles while the electrode characteristics in the detection of electroactive molecules hardly change. Our findings are supported by experimental data on the indigo nanoparticle electroreduction at a carbon microelectrode (radius 5.5μm) in aqueous solution. We find that nanoimpacts are fully suppressed in the presence of acetone at concentrations of 250nm, which have a negligible effect on the electrode kinetics of the Fe(CN)3-/4- 6 couple. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201402014
  • 2014 • 66 New insights into the austenitization process of low-alloyed hypereutectoid steels: Nucleation analysis of strain-induced austenite formation
    Zhang, H. and Pradeep, K.G. and Mandal, S. and Ponge, D. and Raabe, D.
    Acta Materialia 80 296-308 (2014)
    Austenite formation, which originated from a fined-grained ferrite plus carbide microstructure, was observed during tensile testing at 973 K (60 K below Ae1, the equilibrium austenite-pearlite transformation temperature). Scanning electron microscopy, electron backscatter diffraction and atom probe tomography results reveal the mechanism of austenitic transformation below Ae1. The initial fine-grained microstructure, in combination with the warm deformation process, determines the occurrence of strain-induced austenite formation below Ae1. The initial fine-grained microstructure essentially contains a higher dislocation density to facilitate the formation of Cottrell atmospheres and a larger area fraction of ferrite/carbide interfaces which serve as austenite nucleation sites. The warm deformation promotes the Ostwald ripening process and the increase in dislocation density, and hence promotes the accumulation of local high carbon concentrations in the form of Cottrell atmospheres to reach a sufficiently high thermodynamic driving force for austenite nucleation. The critical carbon concentration required for the nucleation of austenite was calculated using classical nucleation theory, which correlated well with the experimental observations. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2014.07.073
  • 2014 • 65 On the spheroidized carbide dissolution and elemental partitioning in high carbon bearing steel 100Cr6
    Song, W. and Choi, P.-P. and Inden, G. and Prahl, U. and Raabe, D. and Bleck, W.
    Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 45 595-606 (2014)
    We report on the characterization of high carbon bearing steel 100Cr6 using electron microscopy and atom probe tomography in combination with multi-component diffusion simulations. Scanning electron micrographs show that around 14 vol pct spheroidized carbides are formed during soft annealing and only 3 vol pct remain after dissolution into the austenitic matrix through austenitization at 1123 K (850 °C) for 300 seconds. The spheroidized particles are identified as (Fe, Cr)3C by transmission electron microscopy. Atom probe analysis reveals the redistribution and partitioning of the elements involved, i.e., C, Si, Mn, Cr, Fe, in both, the spheroidized carbides and the bainitic matrix in the sample isothermally heat-treated at 773 K (500 °C) after austenitization. Homogeneous distribution of C and a Cr gradient were detected within the spheroidized carbides. Due to its limited diffusivity in (Fe, Cr) 3C, Cr exhibits a maximum concentration at the surface of spheroidized carbides (16 at. pct) and decreases gradually from the surface towards the core down to about 2 at. pct. The atom probe results also indicate that the partially dissolved spheroidized carbides during austenitization may serve as nucleation sites for intermediate temperature cementite within bainite, which results in a relatively softer surface and harder core in spheroidized particles. This microstructure may contribute to the good wear resistance and fatigue properties of the steel. Good agreement between DICTRA simulations and experimental composition profiles is obtained by an increase of mobility of the substitutional elements in cementite by a factor of five, compared to the mobility in the database MOBFE2. © The Minerals, Metals & Materials Society and ASM International 2013.
    view abstractdoi: 10.1007/s11661-013-2048-5
  • 2014 • 64 Parameterized electronic description of carbon cohesion in iron grain boundaries
    Hatcher, N. and Madsen, G.K.H. and Drautz, R.
    Journal of Physics Condensed Matter 26 (2014)
    We employ a recently developed iron-carbon orthogonal tight-binding model in calculations of carbon in iron grain boundaries. We use the model to evaluate the properties of carbon near and on the Σ5 (3 1 0)[0 0 1] symmetric tilt grain boundary (GB) in iron, and calculations show that a carbon atom lowers the GB energy by 0.29 eV/atom in accordance with DFT. Carbon segregation to the GB is analyzed, and we find an energy barrier of 0.92 eV for carbon to segregate to the carbon-free interface while segregation to a fully filled interface is disfavored. Local volume (via Voronoi tessellation), magnetic, and electronic effects are correlated with atomic energy changes, and we isolate two different mechanisms governing carbon's behavior in iron: a volumetric strain which increases the energy of carbon in interstitial α iron and a non-strained local bonding which stabilizes carbon at the GB. © 2014 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0953-8984/26/14/145502
  • 2014 • 63 Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural
    Wang, G.-H. and Hilgert, J. and Richter, F.H. and Wang, F. and Bongard, H.-J. and Spliethoff, B. and Weidenthaler, C. and Schüth, F.
    Nature Materials 13 293-300 (2014)
    The synthesis of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) is a highly attractive route to a renewable fuel. However, achieving high yields in this reaction is a substantial challenge. Here it is described how PtCo bimetallic nanoparticles with diameters of 3.6 ± 0.7 nm can solve this problem. Over PtCo catalysts the conversion of HMF was 100% within 10 min and the yield to DMF reached 98% after 2 h, which substantially exceeds the best results reported in the literature. Moreover, the synthetic method can be generalized to other bimetallic nanoparticles encapsulated in hollow carbon spheres. © 2014 Macmillan Publishers Limited.
    view abstractdoi: 10.1038/nmat3872
  • 2014 • 62 Plutonium sorption to nanocast mesoporous carbon
    Parsons-Moss, T. and Tüysüz, H. and Wang, D. and Jones, S. and Olive, D. and Nitsche, H.
    Radiochimica Acta 102 489-504 (2014)
    Nanocast ordered mesoporous carbons are attractive as sorbents because of their extremely high surface areas and large pore volumes. This paper compares Pu uptake, added as Pu(VI), to both untreated and chemically oxidized CMK-(carbon molecular sieves from KAIST) type mesoporous carbon with that to a commercial amorphous activated carbon. The CMK was synthesized via nanocasting by using cubic ordered mesoporous silica KIT-6 as a hard template, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption. A portion of the CMK was oxidized by treatment with nitric acid, and will be called OX CMK. The three carbon powders have similar particle morphology, and high BET surface areas. The activated carbon is disordered, while the CMK materials show large domains of ordered cubic mesostructure. The CMK material seems to have more oxygen-containing functional groups than the activated carbon, and the oxidation of the CMK increased the density of these groups, especially - COOH, thus lowering the point of zero charge (PZC) of the material. Batch studies of all 3 materials with plutonium solutions, in a 0.1M NaClO4 matrix were performed to investigate pH dependence, sorption kinetics, Pu uptake capacities, competition with ethylenediaminetetraacetic acid (EDTA) in solution, and Pu desorption. Both CMKmaterials demonstrated high Pu sorption from solutions of pH 3 or greater, and the oxidized CMK also showed high sorption from pH 2 solutions. The activated carbon bound less Pu, and at a much slower rate than CMK. All other batch experiments were carried out in pH 4 solutions. The Pu uptake from low-concentration solutions was faster for the oxidized CMKthan for untreated CMK, but inmore concentrated samples (~250 μMPu), the Pu uptake kinetics and apparent capacity were the same for oxidized and untreated CMK. The 23-h Pu uptake capacity of the CMK materials was measured to be at least 58 ± 5mg 239Pu per g CMK carbon, compared to 12 ± 5mg 239Pu per g activated carbon. The presence of EDTA in solution decreased the Pu sorption to CMK. Desorption from all samples occurred in 1M HClO4, usually within 24 h. The Pu interaction with the carbon surface was also probed via X-ray absorption spectroscopy (XAS) on the Pu LIII absorption edge. Spectral fits of the X-ray absorption near-edge structure (XANES) data collected on both types of CMK samples showed that Pu(VI) was reduced to Pu(IV) at the carbon surface. The high affinity of mesoporous carbon for Pu, and the spontaneous reduction of Pu(VI) or Pu(V) to Pu(IV) at these carbon surfaces could be valuable for a variety of applications.
    view abstractdoi: 10.1515/ract-2014-2138
  • 2014 • 61 PQQ-sGDH bioelectrodes based on os-complex modified electrodeposition polymers and carbon nanotubes
    Chen, X. and Shao, M. and Pöller, S. and Guschin, D. and Pinyou, P. and Schuhmann, W.
    Journal of the Electrochemical Society 161 H3058-H3063 (2014)
    Graphite electrodes were modified with specifically designed Os-complex modified electrodeposition polymers exhibiting a formal potential of the polymer-bound complex of about 0 to 20 mV (vs. Ag/AgCl/3MKCl) which is only about 100 mV anodic of the formal potential of pyrroloquinoline quinone (PQQ) in PQQ-dependent glucose dehydrogenase (PQQ-GDH). The efficiency of wiring the polymer-entrapped PQQ-GDH was dependent on the nature of the polymer backbone, the crosslinking with bifunctional crosslinkers and the co-entrapment of multi-walled carbon nanotubes. Due to the limited long-term stability a new polymer synthesis strategy was adapted using the same Os-complex but providing enhanced crosslinking capabilities by introducing epoxide functions at the polymer backbone. Related bioelectrodes showed enhanced glucose-dependent current and a stability of at least 3 days of continuous operation. © The Author(s) 2014.
    view abstractdoi: 10.1149/2.0111413jes
  • 2014 • 60 Reactivity of mesoporous carbon against water - An in-situ XPS study
    Reiche, S. and Blume, R. and Zhao, X.C. and Su, D. and Kunkes, E. and Behrens, M. and Schlögl, R.
    Carbon 77 175-183 (2014)
    Functionalized mesoporous carbon catalysts can be used in the acid catalyzed dehydration of fructose to 5-hydroxymethyl furfural (HMF). However, strong deactivation can be observed after preconditioning of the material in the reaction solvent 2-butanol. Surface changes caused by the pretreatment have been studied by XPS. The comparison of the pristine sample and the pretreated carbon sample showed similar distribution of oxygen functional groups by ex-situ XPS, as well as similar behavior during heating in vacuum. However, the addition of water (0.1 mbar vapor pressure) and subsequent heating to 130 °C exhibited prominent differences in the evolution of the O1s, as well as for the C1s spectra of the two samples. Changes in the surface termination and hydrophobicity of the materials are discussed under the aspect of possible reactions of surface functional groups with the alcoholic solvent and water. © 2014 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2014.05.019
  • 2014 • 59 Redox dynamics of Ni catalysts in CO2 reforming of methane
    Mette, K. and Kühl, S. and Tarasov, A. and Düdder, H. and Kähler, K. and Muhler, M. and Schlögl, R. and Behrens, M.
    Catalysis Today 101-110 (2014)
    The influence of redox dynamics of a Ni/MgAl oxide catalyst for dry reforming of methane (DRM) at high temperature was studied to correlate structural stability with catalytic activity and coking propensity. Structural aging of the catalyst was simulated by repeated temperature-programmed reduction/oxidation (TPR/TPO) cycles. Despite a very high Ni loading of 55.4 wt.%, small Ni nanoparticles of 11 nm were obtained from a hydrotalcite-like precursor with a homogeneous distribution. Redox cycling gradually changed the interaction of the active Ni phase with the oxide support resulting in a crystalline Ni/MgAl<inf>2</inf>O<inf>4</inf>-type catalyst. After cycling the average particle size increased from 11 to 21 nm - while still a large fraction of small particles was present - bringing about a decrease in Ni surface area of 72%. Interestingly, the redox dynamics and its strong structural and chemical consequences were found to have only a moderate influence on the activity in DRM at 900 °C, but lead to a stable attenuation of carbon formation due to a lower fraction of graphitic carbon after DRM in a fixed-bed reactor. Supplementary DRM experiments in a thermobalance revealed that coke formation as a continuous process until a carbon limit is reached and confirmed a higher coking rate for the cycled catalyst. © 2014 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.cattod.2014.06.011
  • 2014 • 58 Role of surface functional groups in ordered mesoporous carbide-derived carbon/ionic liquid electrolyte double-layer capacitor interfaces
    Pinkert, K. and Oschatz, M. and Borchardt, L. and Klose, M. and Zier, M. and Nickel, W. and Giebeler, L. and Oswald, S. and Kaskel, S. and Eckert, J.
    ACS Applied Materials and Interfaces 6 2922-2928 (2014)
    Ordered mesoporous carbide-derived carbon (OM-CDC) with a specific surface area as high as 2900 m2 g-1 was used as a model system in a supercapacitor setup based on an ionic liquid (IL; 1-ethyl-3-methylimidazolium tetrafluoroborate) electrolyte. Our study systematically investigates the effect of surface functional groups on IL-based carbon supercapacitors. Oxygen and chlorine functionalization was achieved by air oxidation and chlorine treatment, respectively, to introduce well-defined levels of polarity. The latter was analyzed by means of water physisorption isotherms at 298 K, and the functionalization level was quantified with X-ray photoelectron spectroscopy. While oxygen functionalization leads to a decreased capacitance at higher power densities, surface chlorination significantly improves the rate capability. A high specific capacitance of up to 203 F g-1 was observed for a chlorinated OM-CDC sample with a drastically increased rate capability in a voltage range of ±3.4 V. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/am4055029
  • 2014 • 57 Segregation stabilizes nanocrystalline bulk steel with near theoretical strength
    Li, Y. and Raabe, D. and Herbig, M. and Choi, P.-P. and Goto, S. and Kostka, A. and Yarita, H. and Borchers, C. and Kirchheim, R.
    Physical Review Letters 113 (2014)
    Grain refinement through severe plastic deformation enables synthesis of ultrahigh-strength nanostructured materials. Two challenges exist in that context: First, deformation-driven grain refinement is limited by dynamic dislocation recovery and crystal coarsening due to capillary driving forces; second, grain boundary sliding and hence softening occur when the grain size approaches several nanometers. Here, both challenges have been overcome by severe drawing of a pearlitic steel wire (pearlite: lamellar structure of alternating iron and iron carbide layers). First, at large strains the carbide phase dissolves via mechanical alloying, rendering the initially two-phase pearlite structure into a carbon-supersaturated iron phase. This carbon-rich iron phase evolves into a columnar nanoscaled subgrain structure which topologically prevents grain boundary sliding. Second, Gibbs segregation of the supersaturated carbon to the iron subgrain boundaries reduces their interface energy, hence reducing the driving force for dynamic recovery and crystal coarsening. Thus, a stable cross-sectional subgrain size <10nm is achieved. These two effects lead to a stable columnar nanosized grain structure that impedes dislocation motion and enables an extreme tensile strength of 7 GPa, making this alloy the strongest ductile bulk material known. © 2014 American Physical Society.
    view abstractdoi: 10.1103/PhysRevLett.113.106104
  • 2014 • 56 Sequential Bi-C bond activation reactions of BiEt3via insertion reactions of RE {R = HC[C(Me)N(2,6-i-Pr2C6H3)]2; E = Al, Ga, In}
    Ganesamoorthy, C. and Bläser, D. and Wölper, C. and Schulz, S.
    Chemical Communications 50 12382-12384 (2014)
    Two of the Bi-C bonds of BiEt3 are sequentially activated by mono-valent RM {R = HC[C(Me)N(2,6-i-Pr2C6H3)]2; M = Al, Ga, In}. The first Bi-C bond activation leads to the formation of insertion complexes, [RMEt(BiEt2)] (M = Al 1; Ga 2; In 3), whereas the consecutive second activation proceeds through a reductive elimination of RMEt2 (M = Al 4, Ga 5), elemental Bi and BiEt3. © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cc05028b
  • 2014 • 55 Strongly coupled carbon nanofiber-metal oxide coaxial nanocables with enhanced lithium storage properties
    Zhang, G. and Wu, H.B. and Hoster, H.E. and Lou, X.W.
    Energy and Environmental Science 7 302-305 (2014)
    A facile two-step strategy involving a polyol method and subsequent thermal annealing treatment is successfully developed for the general synthesis of metal oxide/carbon coaxial nanocables. Benefitting from the strong coupling effect, these hybrid nanocables exhibit remarkable lithium storage properties with high capacity, long cycle life and excellent rate capability. © 2014 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3ee43123a
  • 2014 • 54 Structural characterization of micro- and mesoporous carbon materials using in situ high pressure 129Xe NMR spectroscopy
    Oschatz, M. and Hoffmann, H.C. and Pallmann, J. and Schaber, J. and Borchardt, L. and Nickel, W. and Senkovska, I. and Rico-Francés, S. and Silvestre-Albero, J. and Kaskel, S. and Brunner, E.
    Chemistry of Materials 26 3280-3288 (2014)
    In situ high pressure 129Xe NMR spectroscopy in combination with volumetric adsorption measurements were used for the textural characterization of different carbon materials with well-defined porosity including microporous carbide-derived carbons, ordered mesoporous carbide-derived carbon, and ordered mesoporous CMK-3. Adsorption/desorption isotherms were measured also by NMR up to relative pressures close to p/p0 = 1 at 237 K. The 129Xe NMR chemical shift of xenon adsorbed in porous carbons is found to be correlated with the pore size in analogy to other materials such as zeolites. In addition, these measurements were performed loading the samples with n-nonane. Nonane molecules preferentially block the micropores. However, 129Xe NMR spectroscopy proves that the nonane also influences the mesopores, thus providing information about the pore system in hierarchically structured materials. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/cm501102y
  • 2014 • 53 The role of carbonaceous deposits in the activity and stability of Ni-based catalysts applied in the dry reforming of methane
    Düdder, H. and Kähler, K. and Krause, B. and Mette, K. and Kühl, S. and Behrens, M. and Scherer, V. and Muhler, M.
    Catalysis Science and Technology 4 3317-3328 (2014)
    Highly stable Ni catalysts with varying Ni contents up to 50 mol% originating from hydrotalcite-like precursors were applied in the dry reforming of methane at 800 and 900 °C. The integral specific rate of methane conversion determined after 10 h on stream was 3.8 mmol s-1 g cat -1 at 900 °C. Due to the outstanding high activity, a catalyst mass of just 10 mg had to be used to avoid operating the reaction in thermodynamic equilibrium. The resulting WHSV was as high as 1.44 × 106 ml gcat -1 h-1. The observed axial temperature distribution with a pronounced cold spot was analyzed by computational fluid dynamics simulations to verify the strong influence of this highly endothermic reaction. Transmission electron microscopy and temperature-programmed oxidation experiments were used to probe the formation of different carbon species, which was found to depend on the catalyst composition and the reaction temperature. Among the formed carbon species, multi-walled carbon nanofibers were detrimental to the long-term stability at 800 °C, whereas their formation was suppressed at 900 °C. The formation of graphitic carbon at 900 °C originating from methane pyrolysis played a minor role. The methane conversion after 100 h of dry reforming at 900 °C compared to the initial one amounted to 98% for the 25 mol% Ni catalyst. The oxidative regeneration of the catalyst was achieved in the isothermal mode using only carbon dioxide in the feed. © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cy00409d
  • 2014 • 52 Tribolayer formation in a metal-on-metal (MoM) hip joint: An electrochemical investigation
    Mathew, M.T. and Nagelli, C. and Pourzal, R. and Fischer, A. and Laurent, M.P. and Jacobs, J.J. and Wimmer, M.A.
    Journal of the Mechanical Behavior of Biomedical Materials 29 199-212 (2014)
    The demand for total hip replacement (THR) surgery is increasing in the younger population due to faster rehabilitation and more complete restoration of function. Up to 2009, metal-on-metal (MoM) hip joint bearings were a popular choice due to their design flexibility, post-operative stability and relatively low wear rates. The main wear mechanisms that occur along the bearing surface of MoM joints are tribochemical reactions that deposit a mixture of wear debris, metal ions and organic matrix of decomposed proteins known as a tribolayer. No in-depth electrochemical studies have been reported on the structure and characteristics of this tribolayer or about the parameters involved in its formation.In this study, we conducted an electrochemical investigation of different surfaces (bulk-like: control, nano-crystalline: new implant and tribolayer surface: retrieved implant) made out of two commonly used hip CoCrMo alloys (high-carbon and low-carbon). As per ASTM standard, cyclic polarization tests and electrochemical impedance spectroscopy tests were conducted. The results obtained from electrochemical parameters for different surfaces clearly indicated a reduction in corrosion for the tribolayer surface (Icorr: 0.76μA/cm2). Further, polarization resistance (Rp:2.39±0.60MΩ/cm2) and capacitance (Cdl:15.20±0.75μF/cm2) indicated variation in corrosion kinetics for the tribolayer surface, that attributed to its structure and stability in a simulated body environment. © 2013 Elsevier Ltd.
    view abstractdoi: 10.1016/j.jmbbm.2013.08.018
  • 2013 • 51 'Sticky electrodes' for the detection of silver nanoparticles
    Tschulik, K. and Palgrave, R.G. and Batchelor-Mcauley, C. and Compton, R.G.
    Nanotechnology 24 (2013)
    Detection and quantification of nanoparticles in environmental systems is a task that requires reliable and affordable analytical methods. Here an approach using a cysteine-modified 'sticky' glassy carbon electrode is presented. The electrode is immersed in a silver nanoparticle containing electrolyte and left in this suspension without an applied potential, i.e. under open circuit condition, for a variable amount of time. The amount of silver nanoparticles immobilized on the electrode within this sticking time is then determined by oxidative stripping, yielding the anodic charge and thus the amount of Ag nanoparticles sticking to the electrode surface. When using a cysteine-modified glassy carbon electrode, significant and reproducible amounts of silver nanoparticles stick to the surface, which is not the case for unmodified glassy carbon surfaces. Additionally, proof-of-concept experiments are performed on real seawater samples. These demonstrate that also under simulated environmental conditions an increased immobilization and hence improved detection of silver nanoparticles on cysteine-modified glassy carbon electrodes is achieved, while no inhibitive interference with this complex matrix is observed. © 2013 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0957-4484/24/29/295502
  • 2013 • 50 A new route for the preparation of mesoporous carbon materials with high performance in lithium–sulphur battery cathodes
    Oschatz, M. and Thieme, S. and Borchardt, L. and Lohe, M.R. and Biemelt, T. and Brückner, J. and Althues, H. and Kaskel, S.
    Chemical Communications 49 5832-5834 (2013)
    A novel method for the preparation of highly mesoporous carbon materials (Kroll-Carbons; KCs) is described based on reactive carbochlorination etching of titania nanoparticles inside a dense carbon matrix leading to mesoporous carbons with precisely controllable porosity and high performance as cathode materials for lithium–sulphur (Li–S) batteries. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3cc42841a
  • 2013 • 49 Ab initio prediction of the critical thickness of a precipitate
    Sampath, S. and Janisch, R.
    Journal of Physics Condensed Matter 25 (2013)
    Segregation and precipitation of second phases in metals and metallic alloys is an important phenomenon that has a strong influence on the mechanical properties of the material. Models exist that describe the growth of coherent, semi-coherent and incoherent precipitates. One important parameter of these models is the energy of the interface between matrix and precipitate. In this work we apply ab initio density functional theory calculations to obtain this parameter and to understand how it depends on chemical composition and mechanical strain at the interface. Our example is a metastable Mo-C phase, the body-centred tetragonal structure, which exists as a semi-coherent precipitate in body-centred cubic molybdenum. The interface of this precipitate is supposed to change from coherent to semi-coherent during the growth of the precipitate. We predict the critical thickness of the precipitate by calculating the different contributions to a semi-coherent interface energy by means of ab initio density functional theory calculations. The parameters in our model include the elastic strain energy stored in the precipitate, as well as a misfit dislocation energy that depends on the dislocation core width and the dislocation spacing. Our predicted critical thickness agrees well with experimental observations. © 2013 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0953-8984/25/35/355005
  • 2013 • 48 Carbon dioxide activated carbide-derived carbon monoliths as high performance adsorbents
    Oschatz, M. and Borchardt, L. and Senkovska, I. and Klein, N. and Leistner, M. and Kaskel, S.
    Carbon 56 139-145 (2013)
    Carbide-derived carbon (CDC) monoliths (DUT-38) with a distinctive macropore network are physically activated using carbon dioxide as oxidizing agent. This procedure is carried out in a temperature range between 850 and 975 °C with durations ranging from 2 to 6 h. Resulting materials show significantly increased specific surface areas as high as 3100 m2/g and total (micro/meso) pore volumes of more than 1.9 cm3/g. The methane (214 mg/g at 80 bar/25 °C), hydrogen (55.6 mg/g at 40 bar/-196 °C), and n-butane (860 mg/g at 77 vol.%/25 °C) storage capacities of the activated CDCs are significantly higher as compared to the non-activated reference material. Moreover, carbon dioxide activation is a suitable method for the removal of metal chlorides and chlorine residuals adsorbed in the pores of CDC after high temperature chlorination. The activation does not influence the hydrophobic surface properties of the CDCs as determined by water adsorption experiments. The macropore network and the monolithic shape of the starting materials can be fully preserved during the activation procedure. n-Butane breakthrough studies demonstrate the materials applicability as an efficient hydrophobic filter material by combining excellent materials transport with some of the highest capacity values that have ever been reported for CDCs. © 2013 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2012.12.084
  • 2013 • 47 Direct methane oxidation over Pt-modified nitrogen-doped carbons
    Soorholtz, M. and White, R.J. and Zimmermann, T. and Titirici, M.-M. and Antonietti, M. and Palkovits, R. and Schüth, F.
    Chemical Communications 49 240-242 (2013)
    Nitrogen-doped carbons derived from biomass precursors were modified with Pt2+ and successfully tested as solid catalysts in the direct oxidation of methane in fuming sulfuric acid. Remarkably, the catalytic performance was found to be substantially better than the Pt-modified Covalent Triazine Framework (CTF) system previously reported, although deactivation is more pronounced for the biomass derived catalyst supports. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2cc36232e
  • 2013 • 46 Element-resolved corrosion analysis of stainless-type glass-forming steels
    Duarte, M.J. and Klemm, J. and Klemm, S.O. and Mayrhofer, K.J.J. and Stratmann, M. and Borodin, S. and Romero, A.H. and Madinehei, M. and Crespo, D. and Serrano, J. and Gerstl, S.S.A. and Choi, P.P. and Raabe, D. and Renner, F.U.
    Science 341 372-376 (2013)
    Ultrathin passive films effectively prevent the chemical attack of stainless steel grades in corrosive environments; their stability depends on the interplay between structure and chemistry of the constituents iron, chromium, and molybdenum (Fe-Cr-Mo). Carbon (C), and eventually boron (B), are also important constituents of steels, although in small quantities. In particular, nanoscale inhomogeneities along the surface can have an impact on material failure but are still poorly understood. Addressing a stainless-type glass-forming Fe50Cr15Mo14C15B 6 alloy and using a combination of complementary high-resolution analytical techniques, we relate near-atomistic insights into increasingly inhomogeneous nanostructures with time- and element-resolved dissolution behavior. The progressive elemental partitioning on the nanoscale determines the degree of passivation. A detrimental transition from Cr-controlled passivity to Mo-controlled breakdown is dissected atom by atom, demonstrating the importance of nanoscale knowledge for understanding corrosion.
    view abstractdoi: 10.1126/science.1230081
  • 2013 • 45 Formation of carbon nanofilms on single crystal quartz
    Samsonau, S.V. and Dzedzits, E. and Shvarkov, S.D. and Meinerzhagen, F. and Wieck, A.D. and Zaitsev, A.M.
    Sensors and Actuators, B: Chemical 186 610-613 (2013)
    In this work formation of the very first layers of carbon nanofilms on single crystal quartz substrates is studied. Films where grown by molecular beam growth, and have been characterized by Raman spectroscopy and atomic force microscopy. Formation of a non-conductive carbon layer of low crystallinity on the initial stage of the growth process is reported. Ab-initio calculations with an atom-by-atom approach have been performed to explain the experimental data. © 2013 Elsevier B.V.
    view abstractdoi: 10.1016/j.snb.2013.06.023
  • 2013 • 44 Functionalised porous nanocomposites: A multidisciplinary approach to investigate designed structures for supercapacitor applications
    Pinkert, K. and Giebeler, L. and Herklotz, M. and Oswald, S. and Thomas, J. and Meier, A. and Borchardt, L. and Kaskel, S. and Ehrenberg, H. and Eckert, J.
    Journal of Materials Chemistry A 1 4904-4910 (2013)
    The rational design of nanocomposite structures with specific functions in energy storage applications is a key requisite to increase energy and power density in electrical storage systems. Nanoscale characterisation tools are essential to achieve controlled syntheses of such well-defined interface structures in order to reveal structure-property relationships in functional nanocomposites. In the following, we report on the synthesis of iron (hydr)oxide nanoparticles homogeneously embedded into the walls of the three dimensional carbon network of mesoporous carbon CMK-3 via a mild one-step redox functionalisation. Depth profile Auger electron spectroscopy (DP-AES) and energy filtered transmission electron microscopy (EF-TEM) are applied to analyse elemental distribution profiles and location of the active components. The combination of the two analytical techniques provides a highly resolved spatial distribution of transition metal (hydr)oxide nanoparticles inside the carbon network. Functionalised porous carbon nanocomposites were tested for supercapacitor applications and the highest energy density of an iron oxide carbon composite is demonstrated. The iron (hydr)oxide contributes with a pseudocapacitance of 357 F g-1 to the porous nanocomposite in a 6 M KOH electrolyte. An overall doubling of the specific capacitance of the active electrode material compared to the pristine CMK-3 is achieved. © The Royal Society of Chemistry 2013.
    view abstractdoi: 10.1039/c3ta00118k
  • 2013 • 43 Influence of recombination center interaction on the photoluminescence of AlGaAs/GaAs heterostructures
    Schuster, J. and Kim, T.Y. and Batke, E. and Reuter, D. and Wieck, A.D.
    Semiconductor Science and Technology 28 (2013)
    The photoluminescence of an electron inversion layer with a monolayer of carbon acceptors in GaAs was investigated at liquid helium temperatures. In the limit of high laser illumination the luminescence line approaches a hat shape, the expected form if the recombination center is a single isolated acceptor. At medium illumination the line takes on a trapezoidal form, and in the small illumination limit a triangular shape emerges. The line shape variations could be traced back to the interaction of the carbon acceptors which is ruled by the illumination strength. Acceptor-acceptor interactions spread the distribution of transition energies and initiate a transfer of oscillator strength. The triangular line shape at low illumination is a clear signature of an impurity band formed in the carbon monolayer. © 2013 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0268-1242/28/8/085012
  • 2013 • 42 Influence of supersaturated carbon on the diffusion of Ni in ferrite determined by atom probe tomography
    Kresse, T. and Li, Y.J. and Boll, T. and Borchers, C. and Choi, P. and Al-Kassab, T. and Raabe, D. and Kirchheim, R.
    Scripta Materialia 69 424-427 (2013)
    In patented and cold-drawn pearlitic steel wires dissociation of cementite occurs during mechanical deformation. In this study the influence of the carbon decomposition on the diffusion of nickel in ferrite is investigated by means of atom probe tomography. In the temperature range 423-523 K we observed a much smaller activation energy of Ni diffusion than for self-diffusion in body-centered cubic iron, indicating an increased vacancy density owing to enhanced formation of vacancy-carbon complexes. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.scriptamat.2013.05.039
  • 2013 • 41 Interaction of electrolyte molecules with carbon materials of well-defined porosity: Characterization by solid-state NMR spectroscopy
    Borchardt, L. and Oschatz, M. and Paasch, S. and Kaskel, S. and Brunner, E.
    Physical Chemistry Chemical Physics 15 15177-15184 (2013)
    Electrochemical double-layer capacitors (EDLCs or supercapacitors) are of special potential interest with respect to energy storage. Nearly all EDLCs make use of porous carbons as electrode materials. Further tuning of their performance in EDLC applications requires a better understanding of their properties. In particular, the understanding of the interactions between carbon-based materials and electrolyte solutions is of fundamental interest with respect to future applications. Since the capacitance of carbon-based electrode materials is known to depend on the pore size, we have studied different porous carbon materials of well-defined, variable pore size loaded with 1 M TEABF 4 in acetonitrile or with pure acetonitrile using solid-state magic angle spinning (MAS) 1H, 11B, and 13C NMR spectroscopy. © the Owner Societies 2013.
    view abstractdoi: 10.1039/c3cp52283k
  • 2013 • 40 Mo(VI)-melamine hybrid as single-source precursor to pure-phase β-Mo2C for the selective hydrogenation of naphthalene to tetralin
    Pang, M. and Wang, X. and Xia, W. and Muhler, M. and Liang, C.
    Industrial and Engineering Chemistry Research 52 4564-4571 (2013)
    A white Mo(VI)-melamine hybrid solid precipitated immediately when aqueous solutions of (NH4)6Mo7O24 and melamine were mixed. This hybrid proved to be an efficient single-source precursor for single-phase β-Mo2C. Treating the precursor at 650 C in either Ar or H2 resulted in molybdenum carbides, with H 2 being the optimal choice from the perspective of achieving a high-purity carbide. This single-source route successfully inverted the direction of carbon diffusion, thus alleviating the polymerization of carbon species on the carbide surface, which will provide several advantages in catalytic applications. As in the hydrogenation of naphthalene, an ultrahigh selectivity to tetralin was achieved over the resultant β-Mo2C, and its highly purified surface facilitated a steady state with high conversion. With the characteristics of low cost and nontoxicity, the Mo(VI)-melamine hybrid could serve as a green starting material for obtaining highly crystallized β-Mo2C with high purity. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/ie400119d
  • 2013 • 39 Preparation of graphene with graphane areas of controlled hydrogen isotope composition on opposite sides
    Balgar, T. and Kim, H. and Hasselbrink, E.
    Journal of Physical Chemistry Letters 4 2094-2098 (2013)
    Monolayer graphene was prepared on an Ir(111) substrate where it exhibits a 25 × 25 Å2 moiré pattern. Molecular hydrogen was dosed first, allowing it to dissociate on open areas of the Ir substrate. The generated H atoms formed an intercalated reservoir that can bind to the graphene subsequently. Next, atomic hydrogen was dosed, which binds to the graphene sheet and also initiates the transfer of H from the Ir substrate to the graphene sheet. The opposite sides of the sheet can be hydrogenated with isotope selectivity, as a sequence of difference isotopes, H or D, can be chosen at will in the preparation procedure. Sum-frequency generation spectra prove that as consequence of the dosing sequence, C-H bonds are predominantly pointing toward the Ir substrate side when H2 is dosed first and alternatively toward the vacuum side when D2 is dosed first. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/jz400690w
  • 2013 • 38 Separating the initial growth rate from the rate of deactivation in the growth kinetics of multi-walled carbon nanotubes from ethene over a cobalt-based bulk catalyst in a fixed-bed reactor
    Becker, M.J. and Xia, W. and Xie, K. and Dittmer, A. and Voelskow, K. and Turek, T. and Muhler, M.
    Carbon 58 107-115 (2013)
    The initial growth kinetics of multi-walled carbon nanotubes (CNTs) was investigated using a highly active Co-based mixed-oxide catalyst in a tubular fixed-bed reactor under plug-flow conditions with ethene as carbon source. The growth temperature and the ethene concentration were systematically varied in the range from 758 to 923 K and from 5 to 45 vol.%, respectively. The carbon mass accumulation was derived from the ethene conversion and analyzed by a kinetic model, from which the initial CNT growth rate and the mean lifetime of the active sites were derived permitting the prediction of the maximum theoretical CNT yield. With increasing growth temperatures up to 923 K both the initial growth rate and the mean lifetime of active sites increased strongly with a significantly prolonged lifetime above 848 K. The initial growth rate was slow at lower ethene concentrations, but the mean life time was very high. Increasing the ethene concentration up to 45 vol.% led to a much higher initial growth rate, but shortened the mean lifetime strongly. Due to the fast deactivation at high ethene concentrations, the predicted maximum yield decreased considerably approaching the yield obtained after 5 min of time on stream. © 2013 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2013.02.038
  • 2013 • 37 Structural mimicking of inorganic catalyst supports with polydivinylbenzene to improve performance in the selective aerobic oxidation of ethanol and glycerol in water
    Richter, F.H. and Meng, Y. and Klasen, T. and Sahraoui, L. and Schüth, F.
    Journal of Catalysis 308 341-351 (2013)
    Many forms of polymers have been prepared and studied as polymeric catalyst support for metal nanoparticles and solid acid catalysts. The nanocasted mesoporous polydivinylbenzene (PDVB)-supported platinum catalysts presented here are distinguished by their customized mesoporosity and bulk morphology that are comparable to typical carbon-and alumina-supported powdered catalysts. Platinum nanoparticles are deposited on PDVB at loadings between 1 wt% and 9 wt% and a mean size between 2.7 nm and 6.2 nm, dependent on the synthesis method. Bifunctional catalysts containing platinum and acidic functionality are prepared by gas-phase sulfonation of the Pt/PDVB catalysts. The PDVB-supported catalysts are active for the oxidation of ethanol with molecular oxygen in water with up to 94% yield of acetic acid. In the analogous oxidation of glycerol, up to 60% yield of glyceric acid is reached with the bifunctional catalyst, and the polymer-supported catalysts feature lower formation of unidentified side products than Pt/C and Pt/Al2O3. Altogether, we find the polymers to be more active than the alumina and more selective than the carbon supports and thus overall have optimized performance. © 2013 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2013.08.014
  • 2013 • 36 Thermodynamics of carbon solubility in ferrite and vacancy formation in cementite in strained pearlite
    Nematollahi, G.A. and Von Pezold, J. and Neugebauer, J. and Raabe, D.
    Acta Materialia 61 1773-1784 (2013)
    In order to investigate the thermodynamic driving force for the experimentally observed accumulation of C in ferritic layers of severely plastically deformed pearlitic wires, the stabilities of C interstitials in ferrite and of C vacancies in cementite are investigated as a function of uniaxial stain, using density-functional theory. In the presence of an applied strain along [1 1 0] or [1 1 1], the C interstitial in ferrite is significantly stabilized, while the C vacancy in cementite is moderately destabilized by the corresponding strain states in cementite [1 0 0] and ([0 1 0]). The enhanced stabilization of the C interstitial gives rise to an increase in the C concentration within the ferritic layers by up to two orders of magnitude. Our results thus suggest that in addition to the generally assumed non-equilibrium, dislocation-based mechanism, there is also a strain-induced thermodynamic driving force for the experimentally observed accumulation of C in ferrite. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.12.001
  • 2013 • 35 Trace metal residues promote the activity of supposedly metal-free nitrogen-modified carbon catalysts for the oxygen reduction reaction
    Masa, J. and Zhao, A. and Xia, W. and Sun, Z. and Mei, B. and Muhler, M. and Schuhmann, W.
    Electrochemistry Communications 34 113-116 (2013)
    We show in this study that the presence of trace metal residues in some supposedly metal-free catalysts for oxygen reduction, at concentrations which are difficult to detect using conventional methods such as XPS and EDX, can profoundly promote the ORR activity of the catalysts. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.elecom.2013.05.032
  • 2013 • 34 Understanding the detection of carbon in austenitic high-Mn steel using atom probe tomography
    Marceau, R.K.W. and Choi, P. and Raabe, D.
    Ultramicroscopy 132 239-247 (2013)
    A high-Mn TWIP steel having composition Fe-22Mn-0.6C (wt%) is considered in this study, where the need for accurate and quantitative analysis of clustering and short-range ordering by atom probe analysis requires a better understanding of the detection of carbon in this system. Experimental measurements reveal that a high percentage of carbon atoms are detected as molecular ion species and on multiple hit events, which is discussed with respect to issues such as optimal experimental parameters, correlated field evaporation and directional walk/migration of carbon atoms at the surface of the specimen tip during analysis. These phenomena impact the compositional and spatial accuracy of the atom probe measurement and thus require careful consideration for further cluster-finding analysis. © 2013 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2013.01.010
  • 2012 • 33 Atomic scale effects of alloying, partitioning, solute drag and austempering on the mechanical properties of high-carbon bainitic-austenitic TRIP steels
    Seol, J.-B. and Raabe, D. and Choi, P.-P. and Im, Y.-R. and Park, C.-G.
    Acta Materialia 60 6183-6199 (2012)
    Understanding alloying and thermal processing at an atomic scale is essential for the optimal design of high-carbon (0.71 wt.%) bainitic-austenitic transformation-induced plasticity (TRIP) steels. We investigate the influence of the austempering temperature, chemical composition (especially the Si:Al ratio) and partitioning on the nanostructure and mechanical behavior of these steels by atom probe tomography. The effects of the austempering temperature and of Si and Al on the compositional gradients across the phase boundaries between retained austenite and bainitic ferrite are studied. We observe that controlling these parameters (i.e. Si, Al content and austempering temperature) can be used to tune the stability of the retained austenite and hence the mechanical behavior of these steels. We also study the atomic scale redistribution of Mn and Si at the bainitic ferrite/austenite interface. The observations suggest that either para-equilibrium or local equilibrium-negligible partitioning conditions prevail depending on the Si:Al ratio during bainite transformation. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.07.064
  • 2012 • 32 Deposition of hard and adherent TiBCN films for cutting tools applications
    Tillmann, W. and Bejarano, G. and Hoffmann, F.
    Physica Status Solidi (A) Applications and Materials Science 209 1520-1525 (2012)
    Metal cutting tools having wear resistant and chemically stable ceramic coatings are in many applications superior in performance to uncoated tools. Titanium boron carbon nitride (TiBCN) is a hard material particularly suitable as a protective coating for cutting tools due to its excellent properties, such as a high hardness and high wear and corrosion resistance, among other. TiBCN films were grown on Si (100) and high speed steel substrates by means of reactively pulsed DC magnetron sputtering technique. Two B 4C- and two Ti-targets, to which a pulsed DC voltage of middle frequency was applied, were used for the deposition of TiBCN. A chromium layer was first deposited to obtain a better adhesion of TiBCN to the substrates. The mechanical properties of these coatings deposited under different N 2 contents were investigated. The substrates were biased through a medium frequency power supply. The bias voltage value was -90 V for all coatings. The total film thickness was maintained at approximately 2 μm. The hardness of the coatings increased with reduced nitrogen content, while the adhesion decreased from 40.8 to 24.2 N, and the wear rate increased from 0.154 to 0.744 × 10 -16 m 3/N.m, the latter probably caused by the low content of the self-lubricating amorphous matrix of our coatings. However, the sample deposited by a nitrogen gas flow of 60 sccm presented a wear rate of four orders of magnitude smaller than the uncoated sample. The deposition method presented in this work seems very promising for the manufacture of TiBCN coatings. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssa.201228130
  • 2012 • 31 Determination of pre-steady-state rate constants on the escherichia coli pyruvate dehydrogenase complex reveals that loop movement controls the rate-limiting step
    Balakrishnan, A. and Nemeria, N.S. and Chakraborty, S. and Kakalis, L. and Jordan, F.
    Journal of the American Chemical Society 134 18644-18655 (2012)
    Spectroscopic identification and characterization of covalent and noncovalent intermediates on large enzyme complexes is an exciting and challenging area of modern enzymology. The Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc), consisting of multiple copies of enzymic components and coenzymes, performs the oxidative decarboxylation of pyruvate to acetyl-CoA and is central to carbon metabolism linking glycolysis to the Krebs cycle. On the basis of earlier studies, we hypothesized that the dynamic regions of the E1p component, which undergo a disorder-order transition upon substrate binding to thiamin diphosphate (ThDP), play a critical role in modulation of the catalytic cycle of PDHc. To test our hypothesis, we kinetically characterized ThDP-bound covalent intermediates on the E1p component, and the lipoamide-bound covalent intermediate on the E2p component in PDHc and in its variants with disrupted active-site loops. Our results suggest that formation of the first covalent predecarboxylation intermediate, C2α-lactylthiamin diphosphate (LThDP), is rate limiting for the series of steps culminating in acetyl-CoA formation. Substitutions in the active center loops produced variants with up to 900-fold lower rates of formation of the LThDP, demonstrating that these perturbations directly affected covalent catalysis. This rate was rescued by up to 5-fold upon assembly to PDHc of the E401K variant. The E1p loop dynamics control covalent catalysis with ThDP and are modulated by PDHc assembly, presumably by selection of catalytically competent loop conformations. This mechanism could be a general feature of 2-oxoacid dehydrogenase complexes because such interfacial dynamic regions are highly conserved. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ja3062375
  • 2012 • 30 Electrochemical synthesis of metal-polypyrrole composites and their activation for electrocatalytic reduction of oxygen by thermal treatment
    Masa, J. and Schilling, T. and Bron, M. and Schuhmann, W.
    Electrochimica Acta 60 410-418 (2012)
    This work presents a new approach for synthesis of oxygen reduction catalysts constituted of a transition metal, nitrogen and carbon, by thermal treatment of electrochemically synthesized metal-polypyrrole (M-PPy) composites on glassy carbon electrodes. The synthesis procedure involves immobilization of PPy on glassy carbon followed by dosing of metal (M = Mn, Fe and Co) particles, alternately, by electropolymerization and electrochemical reduction respectively. Electrochemical characterization by cyclic voltammetry (CV) and hydrodynamic rotating disk electrode (RDE) measurements show that the M-PPy composites inherently catalyse the electroreduction of oxygen under acidic conditions. The activity of the composites is significantly augmented when they are heat treated at high temperatures (450-850 °C) under a continuous flow of nitrogen. The presence of metallic entities within the M-PPy composite structures and in the structures ensuing after heat treatment was confirmed by energy dispersive X-ray (EDX) analysis. © 2011 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.electacta.2011.11.076
  • 2012 • 29 Enhanced direct electron transfer between laccase and hierarchical carbon microfibers/carbon nanotubes composite electrodes. Comparison of three enzyme immobilization methods
    Gutiérrez-Sánchez, C. and Jia, W. and Beyl, Y. and Pita, M. and Schuhmann, W. and De Lacey, A.L. and Stoica, L.
    Electrochimica Acta 82 218-223 (2012)
    Three immobilization protocols were investigated with respect to direct electron transfer between hierarchical carbon microfibers/carbon nanotubes composite material on graphite rod electrodes and Trametes hirsuta laccase. Immobilization was done by covalent binding of laccase to aminophenyl-modified electrodes via amide-bond formation with carboxylic acid residues or imino-bond formation with aldehyde groups introduced by oxidation of sugar residues of the enzyme's glycosylation shell. Moreover, immobilization was achieved by adsorbing laccase to electrodes hydrophilized with pyrene-hexanoic acid. High current densities for biocatalytic oxygen reduction were obtained for all immobilization strategies. The formation of the imino bonds let to the binding of laccase in close to 100% direct electron transfer configuration and consequently to the highest oxygen reduction currents. © 2012 Elsevier Ltd.
    view abstractdoi: 10.1016/j.electacta.2011.12.134
  • 2012 • 28 Fabrication, laser structuring and field emission properties of carbon nanowalls
    Neubert, M. and Behrenberg, D. and Hartmann, N. and Buck, V. and Serbun, P. and Navitski, A. and Muller, G.
    Technical Digest - 25th International Vacuum Nanoelectronics Conference, IVNC 2012 354-355 (2012)
    We have synthesized carbon nanowalls (CNWs) on Si substrate by inductively/capacitively coupled plasma enhanced chemical vapor deposition (ICP/CCP-PECVD). The shape and density of CNWs are controlled by adjusting the synthesis parameters. Local field emission measurements of Ø 30 μm spots reproducibly yielded stable current up to 1 μA. Integral pulsed measurements results on the unstructured cathodes showed fairly homogeneous emission and current density of at least 3 mA/cm 2 at 5.6 V/μm, limited by the power load on the phosphor screen. In order to get cathodes for gate controlled devices and to improve the emission homogeneity, structuring by laser was performed. © 2012 IEEE.
    view abstractdoi: 10.1109/IVNC.2012.6316966
  • 2012 • 27 How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry
    Armbrüster, M. and Behrens, M. and Cinquini, F. and Föttinger, K. and Grin, Y. and Haghofer, A. and Klötzer, B. and Knop-Gericke, A. and Lorenz, H. and Ota, A. and Penner, S. and Prinz, J. and Rameshan, C. and Révay, Z. and Ro...
    ChemCatChem 4 1048-1063 (2012)
    Discussed are the recent experimental and theoretical results on palladium-based catalysts for selective hydrogenation of alkynes obtained by a number of collaborating groups in a joint multi-method and multi-material approach. The critical modification of catalytically active Pd surfaces by incorporation of foreign species X into the sub-surface of Pd metal was observed by insitu spectroscopy for X=H, C under hydrogenation conditions. Under certain conditions (low H 2 partial pressure) alkyne fragmentation leads to formation of a Pd, C surface phase in the reactant gas feed. The insertion of C as a modifier species in the sub-surface increases considerably the selectivity of alkyne semi-hydrogenation over Pd-based catalysts through the decoupling of bulk hydrogen from the outmost active surface layer. DFT calculations confirm that Pd-C hinders the diffusion of hydridic hydrogen. Its formation is dependent on the chemical potential of carbon (reactant partial pressure) and is suppressed when the hydrogen/alkyne pressure ratio is high, which leads to rather unselective hydrogenation over insitu formed bulk Pd-H. The beneficial effect of the modifier species X on the selectivity, however, is also present in intermetallic compounds with X=Ga. As a great advantage, such Pd xGa y catalysts show extended stability under insitu conditions. Metallurgical, clean samples were used to determine the intrinsic catalytic properties of PdGa and Pd 3Ga 7. For high performance catalysts, supported nanostructured intermetallic compounds are more preferable and partial reduction of Ga 2O 3, upon heating of Pd/Ga 2O 3 in hydrogen, was shown to lead to formation of Pd-Ga intermetallic compounds at moderate temperatures. In this way, Pd 5Ga 2 and Pd 2Ga are accessible in the form of supported nanoparticles, in thin film models, and realistic powder samples, respectively. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201200100
  • 2012 • 26 Mesoporous nitrogen-rich carbon materials as catalysts for the oxygen reduction reaction in alkaline solution
    Nagaiah, T.C. and Bordoloi, A. and Sánchez, M.D. and Muhler, M. and Schuhmann, W.
    ChemSusChem 5 637-641 (2012)
    ORR MNC, FTW! Mesoporous nitrogen-rich carbon (MNC) materials are synthesized by using polymer-loaded SBA-15 pyrolyzed at different temperatures. The activity and stability of the catalysts in the oxygen reduction reaction (ORR) are investigated by using cyclic voltammetry and rotating-disk electrode measurements. The MNC material pyrolyzed at 800 °C exhibits a high electrocatalytic activity towards the ORR in alkaline medium. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201100284
  • 2012 • 25 Multistage strain hardening through dislocation substructure and twinning in a high strength and ductile weight-reduced Fe-Mn-Al-C steel
    Gutierrez-Urrutia, I. and Raabe, D.
    Acta Materialia 60 5791-5802 (2012)
    We investigate the kinetics of the deformation structure evolution and its contribution to the strain hardening of a Fe-30.5Mn-2.1Al-1.2C (wt.%) steel during tensile deformation by means of transmission electron microscopy and electron channeling contrast imaging combined with electron backscatter diffraction. The alloy exhibits a superior combination of strength and ductility (ultimate tensile strength of 1.6 GPa and elongation to failure of 55%) due to the multiple-stage strain hardening. We explain this behavior in terms of dislocation substructure refinement and subsequent activation of deformation twinning. The early hardening stage is fully determined by the size of the dislocation substructure, namely, Taylor lattices, cell blocks and dislocation cells. The high carbon content in solid solution has a pronounced effect on the evolving dislocation substructure. We attribute this effect to the reduction of the dislocation cross-slip frequency by solute carbon. With increasing applied stress, the cross-slip frequency increases. This results in a gradual transition from planar (Taylor lattices) to wavy (cells, cell blocks) dislocation configurations. The size of such dislocation substructures scales inversely with the applied resolved stress. We do not observe the so-called microband-induced plasticity effect. In the present case, due to texture effects, microbanding is not favored during tensile deformation and, hence, has no effect on strain hardening. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.07.018
  • 2012 • 24 Nanoscale austenite reversion through partitioning, segregation and kinetic freezing: Example of a ductile 2 GPa Fe-Cr-C steel
    Yuan, L. and Ponge, D. and Wittig, J. and Choi, P. and Jiménez, J.A. and Raabe, D.
    Acta Materialia 60 2790-2804 (2012)
    Austenite reversion during tempering of a Fe-13.6 Cr-0.44 C (wt.%) martensite results in an ultra-high-strength ferritic stainless steel with excellent ductility. The austenite reversion mechanism is coupled to the kinetic freezing of carbon during low-temperature partitioning at the interfaces between martensite and retained austenite and to carbon segregation at martensite-martensite grain boundaries. An advantage of austenite reversion is its scalability, i.e. changing tempering time and temperature tailors the desired strength-ductility profiles (e.g. tempering at 400 °C for 1 min produces a 2 GPa ultimate tensile strength (UTS) and 14% elongation while 30 min at 400 °C results in a UTS of ∼1.75 GPa with an elongation of 23%). The austenite reversion process, carbide precipitation and carbon segregation have been characterized by X-ray diffraction, electron back-scatter diffraction, transmission electron microscopy and atom probe tomography in order to develop the structure-property relationships that control the material's strength and ductility. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.01.045
  • 2012 • 23 Numerical simulation of dynamic strain-induced austenite-ferrite transformation and post-dynamic kinetics in a low carbon steel
    Zheng, C. and Raabe, D. and Li, D.
    Materials Science Forum 706-709 1592-1597 (2012)
    2-D cellular automaton model was developed to simulate the dynamic strain-induced transformation (DSIT) from austenite (?) to ferrite (a) and the post-dynamic kinetic behavior in a low carbon steel with the purpose of developing a methodology of mesoscopic computer simulation for an improved understanding of the formation of ultra-fine ferrite (UFF) in DSIT and the conservation of this microstructure during the post-deformation period. The predicted microstructure obtained after DSIT was compared with a quenched dual-phase steel. Its microstructure, consisting of fine-grained ferrite and fine islands of retained austenite dispersed in the matrix, were found to be in good agreement with the predictions. The simulated results indicate that the refinement of ferrite grains produced via DSIT can be interpreted in terms of unsaturated nucleation and limited growth mechanisms. It is also revealed that continuing transformation from retained austenite to ferrite and the reverse transformation both could take place simultaneously during the post-deformation isothermal holding. A competition between them exists at the early stage of the post-dynamic transformation. © 2012 Trans Tech Publications, Switzerland.
    view abstractdoi: 10.4028/www.scientific.net/MSF.706-709.1592
  • 2012 • 22 On the effect of molecular and hydrocarbon-bonded hydrogen on carbon particle formation in C 3O 2 pyrolysis behind shock waves
    Böhm, H. and Emelianov, A. and Eremin, A. and Schulz, C. and Jander, H.
    Combustion and Flame 159 932-939 (2012)
    The effect of H 2 and C 2H 2 addition on particle formation in the pyrolysis of C 3O 2/Ar mixtures was studied behind reflected shock waves. An existing reaction mechanism for the pyrolysis of highly-diluted C 3O 2 in argon was expanded to conditions with higher C 3O 2 concentrations (up to 33volume%) at elevated pressures and high temperatures and was validated against experimental data. The simulations for the gas-phase chemistry were performed with the program CHEMKIN. The heterogeneous particle formation was modeled by post-processing using the program PREDICI relying on the Galerkin method. It was found that in C 3O 2/H 2/Ar pyrolysis, the induction times and rate constants of particle formation do not differ significantly from those of pure C 3O 2/Ar pyrolysis. However, the presence of H 2 reduced the particle volume fraction, the mean diameter of particles, the particle number density, and the maximum temperature rise of the mixture. Hydrocarbon-bonded hydrogen in C 3O 2/C 2H 2/Ar pyrolysis caused significantly increased induction times for particle formation, decreased particle volume fractions, and decreased temperature rises. The different reaction channels for carbon particle formation were identified in view of the role of hydrogen. An alternating reaction channel including C 2 species played an important role in forming polycyclic aromatic hydrocarbons (PAH) in the mixtures. © 2011 The Combustion Institute.
    view abstractdoi: 10.1016/j.combustflame.2011.09.012
  • 2012 • 21 On the role of the residual iron growth catalyst in the gasification of multi-walled carbon nanotubes with carbon dioxide
    Jin, C. and Xia, W. and Chen, P. and Muhler, M.
    Catalysis Today 186 128-133 (2012)
    The gasification of carbon with CO 2 was applied to examine the role of the residual iron growth catalyst in multi-walled carbon nanotubes (CNTs), which were pre-treated either by refluxing in nitric acid at 120 °C or by nitric acid vapor at 200 °C. Temperature-programmed desorption (TPD) and surface reaction (TPSR) experiments were performed in He and CO 2, respectively. The Fe nanoparticles were retained after the treatment in HNO 3 vapor, whereas the liquid HNO 3 treatment was able to remove the accessible residual Fe catalyst. The exposed Fe nanoparticles were found to catalyze the gasification of CNTs with CO 2 according to the reverse Boudouard reaction C + CO 2 = 2CO. In case of the CNTs pretreated in HNO 3 vapor, evolving CO 2 formed due to the decomposition of oxygen-containing functional groups during the TPD experiments was fully converted above 750 °C into desorbing CO, and the addition of 2000 ppm CO 2 in the feed gas during the TPSR experiments resulted in full conversion at 1000 °C. X-ray photoelectron spectroscopy studies show that the treatment in HNO 3 vapor at 200 °C favors the formation of oxygen species doubly bound to carbon (CO groups). During the TPSR experiments, CO 2 as a weak oxidant partially oxidized the CNTs leading to the formation of CO groups, and a much higher amount of these groups was detected on HNO 3 vapor-treated CNTs with residual Fe catalyst. Their presence suggests that CO groups are reaction intermediates of the CNT gasification with CO 2, which is considered an effective test reaction for the presence of residual catalytically active nanoparticles. © 2012 Elsevier B.V.
    view abstractdoi: 10.1016/j.cattod.2012.02.052
  • 2012 • 20 Surface Diels-Alder reactions as an effective method to synthesize functional carbon materials
    Kaper, H. and Grandjean, A. and Weidenthaler, C. and Schüth, F. and Goettmann, F.
    Chemistry - A European Journal 18 4099-4106 (2012)
    The post-synthesis chemical modification of various porous carbon materials with unsaturated organic compounds is reported. By this method, amine, alcohol, carboxylate, and sulfonic acid functional groups can be easily incorporated into the materials. Different carbonaceous materials with surface areas ranging from 240 to 1500 m 2 g -1 and pore sizes between 3.0 and 7.0 nm have been studied. The resulting materials were analyzed by elemental analysis, nitrogen sorption, FTIR spectroscopy, zeta-potential measurements, thermogravimetric analysis, photoelectron spectroscopy, and small-angle X-ray scattering. These analyses indicated that the degree of functionalization is dependent on the nature of the dienophile (reactivity, steric hindrance) and the porosity of the carbon material. As possible applications, the functionalized carbonaceous materials were studied as catalysts in the Knoevenagel reaction and as adsorbents for Pb 2+ from aqueous solution. Making grafting on carbon as easy as grafting on silica? A new and easy approach, based on surface Diels-Alder reactions, allows the introduction of organic functionalities into the framework of mesoporous carbon (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201102718
  • 2012 • 19 Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis
    Kundu, S. and Nagaiah, T.C. and Chen, X. and Xia, W. and Bron, M. and Schuhmann, W. and Muhler, M.
    Carbon 50 4534-4542 (2012)
    A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells. © 2012 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2012.05.037
  • 2012 • 18 The influence of secondary phase carbide particles on the passivity behaviour of NiTi shape memory alloys
    Neelakantan, L. and Monchev, B. and Frotscher, M. and Eggeler, G.
    Materials and Corrosion 63 979-984 (2012)
    The current investigation aims at studying the passivity behaviour of NiTi shape memory alloys with different levels of secondary phase titanium carbide (TiC) particles in an electrolyte of 0.9% sodium chloride at 37 °C. The influence of carbides and thermo-mechanical treatment/cold working on the passivity breakdown is highlighted. The polarisation studies on the as-cast and cold worked NiTi with high (0.05 wt%) and low (0.005 wt%) carbon levels show a significant difference in oxide stability. The alloy with extremely low carbon content shows a higher breakdown potential. Higher carbon levels result in higher density of larger TiC and these carbide/matrix interfaces are more susceptible to pitting. The qualitative behaviour of passive layer formed at 0.5 V on the cold worked NiTi alloy with different carbon levels was ascertained by electrochemical impedance spectroscopy (EIS). The oxide on the NiTi alloy with high (0.05 wt%) carbon levels showed lower resistance and poor stability at this condition. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/maco.201106402
  • 2012 • 17 The Role of Oxygen and Surface Reactions in the Deposition of Silicon Oxide like Films from HMDSO at Atmospheric Pressure
    Reuter, R. and Rugner, K. and Ellerweg, D. and de los Arcos, T. and von Keudell, A. and Benedikt, J.
    Plasma Processes and Polymers 9 1116--1124 (2012)
    The deposition of thin SiO2-like films by means of atmospheric pressure microplasma jets with admixture of hexamethyldisiloxane (HMDSO) and oxygen and the role of surface reactions in film growth are investigated. Two types of microplasma jets, one with a planar electrodes and operated in helium gas and the other one with a coaxial geometry operated in argon, are used to study the deposition process. The growth rate of the film and the carbon-content in the film are measured as a function of the O2 and HMDSO admixture in the planar jet and are compared to mass spectrometry measurements of the consumption of HMDSO. Additionally, the localized nature of the jetsubstrate interaction is utilized to study surface reactions by applying two jets on a rotating substrate. The addition of oxygen into the gas mixture increases HMDSO depletion and the growth rate and results in the deposition of carbon free films. The surface reaction is responsible for the carbon removal from the growing film. Moreover, carbon free films can be deposited even without addition of oxygen, when coaxial jet operated with argon is used for the surface treatment. We hypothesize that ions or excited species (metastables) could be responsible for the observed effect.
    view abstractdoi: 10.1002/ppap.201100146
  • 2012 • 16 The tribological difference between biomedical steels and CoCrMo-alloys
    Fischer, A. and Weiß, S. and Wimmer, M.A.
    Journal of the Mechanical Behavior of Biomedical Materials 9 50-62 (2012)
    In orthopedic surgery, different self-mating metal couples are used for sliding wear applications. Despite the fact that in mechanical engineering, self-mating austenitic alloys often lead to adhesion and seizure in biomedical engineering, the different grades of Co-base alloys show good clinical results, e.g., as hip joints. The reason stems from the fact that they generate a so-called tribomaterial during articulation, which consists of a mixture of nanometer small metallic grains and organic substances from the interfacial medium, which act as a boundary lubricant. Even though stainless steel also generate such a tribomaterial, they were ruled out from the beginning already in the 1950s as "inappropriate". On the basis of materials with a clinical track record, this contribution shows that the cyclic creep characteristics within the shear zone underneath the tribomaterial are another important criterion for a sufficient wear behavior. By means of sliding wear and torsional fatigue tests followed by electron microscopy, it is shown that austenitic materials generate wear particles of either nano- or of microsize. The latter are produced by crack initiation and propagation within the shear fatigue zone which is related to the formation of subsurface dislocation cells and, therefore, by the fact that an Ni-containing CrNiMo solid solution allows for wavy-slip. In contrast to this, an Ni-free CrMnMo solid solution with further additions of C and N only shows planar slip. This leads to the formation of nanosize wear particles and distinctly improves the wear behavior. Still, the latter does not fully achieve that of CoCrMo, which also shows a solely planar-slip behavior. This explains why for metallurgical reasons the Ni-containing 316L-type of steels had to fail in such boundary lubricated sliding wear tribosystems. © 2012 Elsevier Ltd.
    view abstractdoi: 10.1016/j.jmbbm.2012.01.007
  • 2012 • 15 Toward highly stable electrocatalysts via nanoparticle pore confinement
    Galeano, C. and Meier, J.C. and Peinecke, V. and Bongard, H. and Katsounaros, I. and Topalov, A.A. and Lu, A. and Mayrhofer, K.J.J. and Schüth, F.
    Journal of the American Chemical Society 134 20457-20465 (2012)
    The durability of electrode materials is a limiting parameter for many electrochemical energy conversion systems. In particular, electrocatalysts for the essential oxygen reduction reaction (ORR) present some of the most challenging instability issues shortening their practical lifetime. Here, we report a mesostructured graphitic carbon support, Hollow Graphitic Spheres (HGS) with a specific surface area exceeding 1000 m2 g-1 and precisely controlled pore structure, that was specifically developed to overcome the long-term catalyst degradation, while still sustaining high activity. The synthetic pathway leads to platinum nanoparticles of approximately 3 to 4 nm size encapsulated in the HGS pore structure that are stable at 850 C and, more importantly, during simulated accelerated electrochemical aging. Moreover, the high stability of the cathode electrocatalyst is also retained in a fully assembled polymer electrolyte membrane fuel cell (PEMFC). Identical location scanning and scanning transmission electron microscopy (IL-SEM and IL-STEM) conclusively proved that during electrochemical cycling the encapsulation significantly suppresses detachment and agglomeration of Pt nanoparticles, two of the major degradation mechanisms in fuel cell catalysts of this particle size. Thus, beyond providing an improved electrocatalyst, this study describes the blueprint for targeted improvement of fuel cell catalysts by design of the carbon support. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ja308570c
  • 2011 • 14 Atom probe tomography characterization of heavily cold drawn pearlitic steel wire
    Lia, Y.J. and Choi, P. and Borchers, C. and Chen, Y.Z. and Goto, S. and Raabe, D. and Kirchheim, R.
    Ultramicroscopy 111 628-632 (2011)
    Atom Probe Tomography (APT) was used to analyze the carbon distribution in a heavily cold drawn pearlitic steel wire with a true strain of 6.02. The carbon concentrations in cementite and ferrite were separately measured by a sub-volume method and compared with the literature data. It is found that the carbon concentration in ferrite saturates with strain. The carbon concentration in cementite decreases with the lamellar thickness, while the carbon atoms segregate at dislocations or cell/grain boundaries in ferrite. The mechanism of cementite decomposition is discussed in terms of the evolution of dislocation structure during severe plastic deformation. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2010.11.010
  • 2011 • 13 Carbon nanowalls deposited by inductively coupled plasma enhanced chemical vapor deposition using aluminum acetylacetonate as precursor
    Jain, H.G. and Karacuban, H. and Krix, D. and Becker, H.-W. and Nienhaus, H. and Buck, V.
    Carbon 49 4987-4995 (2011)
    Well aligned carbon nanowalls, a few nanometers thick, were fabricated by continuous flow of aluminum acetylacetonate (Al (acac)3) without a catalyst, and independent of substrate material. The nanowalls were grown on Si, and steel substrates using inductively coupled plasma-enhanced chemical vapor deposition. Deposition parameters like flow of argon gas and substrate temperature were correlated with the growth of carbon nanowalls. For a high flow of argon carrier gas, an increased amount of aluminum in the film and a reduced lateral size of the carbon walls were found. The aluminum is present inside the carbon nanowall matrix in the form of well crystallized nanosized Al4C3 precipitates. © 2011 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.carbon.2011.07.002
  • 2011 • 12 Nano-energy research trends: Bibliometrical analysis of nanotechnology research in the energy sector
    Menéndez-Manjón, A. and Moldenhauer, K. and Wagener, P. and Barcikowski, S.
    Journal of Nanoparticle Research 13 3911-3922 (2011)
    Nano-energy, the part of nanotechnology dedicated to the study and improvement of the Energy Supply Sector, is a promising and perspective research field. A robust method to quantify international scientific activities in this field is the literature search. An evaluative bibliometric approach applied to the Science Citation Index has been done to retrieve a set of articles related to nano-energy and get knowledge of the direction and trends followed by this particular scientific topic. The resulting database showed an exponential increase of the number of publications issuing nano-based investigations in the energy sector in the last decade, accelerating to an annual growth rate of 1,100%. The most cited articles and the material-clustering protocol revealed that carbon-nanoelements and their application in solar energy harvesting and conversion, and energy storage devices have been principally investigated and represent the main focus in that continuously growing research field. The number of nanotechnology-related papers in the energy database increased monotonically for harvesting, conversion, and storage the last decade, being energy distribution and usage not affected. TiO2 or SnO2 nanoparticles or thin films, and nanocomposites occupied the following top positions in the investigated material ranking. This trend was constant along the decade, as confirmed by network analyses. Supported by discipline- clustering, we observed the fundamental character of the research developed between 2000 and 2009, relying mainly on material science and chemistry. Hence, further implementation of nanotechnology findings is needed to stimulate nano-based energy-focused technologies reaching widespread commercial applications. © Springer Science+Business Media B.V. 2011.
    view abstractdoi: 10.1007/s11051-011-0344-9
  • 2011 • 11 Nucleation mechanism for the direct graphite-to-diamond phase transition
    Khaliullin, R.Z. and Eshet, H. and Kühne, T.D. and Behler, J. and Parrinello, M.
    Nature Materials 10 693-697 (2011)
    Graphite and diamond have comparable free energies, yet forming diamond from graphite in the absence of a catalyst requires pressures that are significantly higher than those at equilibrium coexistence. At lower temperatures, the formation of the metastable hexagonal polymorph of diamond is favoured instead of the more stable cubic diamond. These phenomena cannot be explained by the concerted mechanism suggested in previous theoretical studies. Using an ab initio quality neural-network potential, we carried out a large-scale study of the graphite-to-diamond transition assuming that it occurs through nucleation. The nucleation mechanism accounts for the observed phenomenology and reveals its microscopic origins. We demonstrate that the large lattice distortions that accompany the formation of diamond nuclei inhibit the phase transition at low pressure, and direct it towards the hexagonal diamond phase at higher pressure. The proposed nucleation mechanism should improve our understanding of structural transformations in a wide range of carbon-based materials. © 2011 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/nmat3078
  • 2011 • 10 Quantitative detection of C-deuterated drugs by CARS microscopy and Raman microspectroscopy
    Bergner, G. and Albert, C.R. and Schiller, M. and Bringmann, G. and Schirmeister, T. and Dietzek, B. and Niebling, S. and Schlücker, S. and Popp, J.
    Analyst 136 3686-3693 (2011)
    The introduction of carbon-deuterium (C-D) bonds into drug compounds by organic synthesis is a non-invasive labelling approach, which does not alter the chemical and physiological properties of the drug itself. C-deuterated drugs exhibit characteristic vibrational signatures in the C-D stretching region around 2100-2300 cm -1, which avoids spectral interference with contributions from a complex biological environment. In this paper, the quantitative detection of C-deuterated drugs by Raman microspectroscopy and single-band CARS microscopy is examined. Concentration-dependent studies on drugs with aliphatic and aromatic C-D moieties were performed in a two-channel microfluidic chip, using the corresponding non-deuterated (C-H) isotopologues as an internal reference. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c0an00956c
  • 2011 • 9 Structurally designed synthesis of mechanically stable poly(benzoxazine-co- resol)-based porous carbon monoliths and their application as high-performance CO2 capture sorbents
    Hao, G.-P. and Li, W.-C. and Qian, D. and Wang, G.-H. and Zhang, W.-P. and Zhang, T. and Wang, A.-Q. and Schüth, F. and Bongard, H.-J. and Lu, A.-H.
    Journal of the American Chemical Society 133 11378-11388 (2011)
    Porous carbon monoliths with defined multilength scale pore structures, a nitrogen-containing framework, and high mechanical strength were synthesized through a self-assembly of poly(benzoxazine-co-resol) and a carbonization process. Importantly, this synthesis can be easily scaled up to prepare carbon monoliths with identical pore structures. By controlling the reaction conditions, porous carbon monoliths exhibit fully interconnected macroporosity and mesoporosity with cubic Im3m symmetry and can withstand a press pressure of up to 15.6 MPa. The use of amines in the synthesis results in a nitrogen-containing framework of the carbon monolith, as evidenced by the cross-polarization magic-angle-spinning NMR characterization. With such designed structures, the carbon monoliths show outstanding CO2 capture and separation capacities, high selectivity, and facile regeneration at room temperature. At 1 bar, the equilibrium capacities of the monoliths are in the range of 3.3 - 4.9 mmol g- 1 at 0 °C and of 2.6 - 3.3 mmol g - 1 at 25 °C, while the dynamic capacities are in the range of 2.7 - 4.1 wt % at 25 °C using 14% (v/v) CO2 in N2. The carbon monoliths exhibit high selectivity for the capture of CO2 over N2 from a CO2/N2 mixture, with a separation factor ranging from 13 to 28. Meanwhile, they undergo a facile CO2 release in an argon stream at 25 °C, indicating a good regeneration capacity. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja203857g
  • 2010 • 8 A European aerosol phenomenology - 3: Physical and chemical characteristics of particulate matter from 60 rural, urban, and kerbside sites across Europe
    Putaud, J.-P. and Van Dingenen, R. and Alastuey, A. and Bauer, H. and Birmili, W. and Cyrys, J. and Flentje, H. and Fuzzi, S. and Gehrig, R. and Hansson, H.C. and Harrison, R.M. and Herrmann, H. and Hitzenberger, R. and Hüglin, C...
    Atmospheric Environment 44 1308-1320 (2010)
    This paper synthesizes data on aerosol (particulate matter, PM) physical and chemical characteristics, which were obtained over the past decade in aerosol research and monitoring activities at more than 60 natural background, rural, near-city, urban, and kerbside sites across Europe. The data include simultaneously measured PM10 and/or PM2.5 mass on the one hand, and aerosol particle number concentrations or PM chemistry on the other hand. The aerosol data presented in our previous works (Van Dingenen et al., 2004; Putaud et al., 2004) were updated and merged to those collected in the framework of the EU supported European Cooperation in the field of Scientific and Technical action COST633 (Particulate matter: Properties related to health effects). A number of conclusions from our previous studies were confirmed. There is no single ratio between PM2.5 and PM10 mass concentrations valid for all sites, although fairly constant ratios ranging from 0.5 to 0.9 are observed at most individual sites. There is no general correlation between PM mass and particle number concentrations, although particle number concentrations increase with PM2.5 levels at most sites. The main constituents of both PM10 and PM2.5 are generally organic matter, sulfate and nitrate. Mineral dust can also be a major constituent of PM10 at kerbside sites and in Southern Europe. There is a clear decreasing gradient in SO4 2- and NO3 - contribution to PM10 when moving from rural to urban to kerbside sites. In contrast, the total carbon/PM10 ratio increases from rural to kerbside sites. Some new conclusions were also drawn from this work: the ratio between ultrafine particle and total particle number concentration decreases with PM2.5 concentration at all sites but one, and significant gradients in PM chemistry are observed when moving from Northwestern, to Southern to Central Europe. Compiling an even larger number of data sets would have further increased the significance of our conclusions, but collecting all the aerosol data sets obtained also through research projects remains a tedious task. © 2009 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.atmosenv.2009.12.011
  • 2010 • 7 An aqueous emulsion route to synthesize mesoporous carbon vesicles and their nanocomposites
    Gu, D. and Bongard, H. and Deng, Y. and Feng, D. and Wu, Z. and Fang, Y. and Mao, J. and Tu, B. and Schüth, F. and Zhao, D.
    Advanced Materials 22 833-837 (2010)
    Onionlike mesoporous carbon and carbonsilica nanocomposites with multilayer vesicle structures can be synthesized by an organic-inorganic co-assembly method under hydrothermal conditions in an aqueous emulsion solution (see figure). The nanocomposite vesicles have ordered lamellar mesostructures with about 3-9 layers and carbon pillars are located between the neighboring shells. (Chemical Equation Persentation). © 2010 WILEY-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/adma.200902550
  • 2010 • 6 Easy synthesis of hollow polymer, carbon, and graphitized microspheres
    Lu, A.-H. and Li, W.-C. and Hao, G.-P. and Spliethoff, B. and Bongard, H.-J. and Schaack, B.B. and Schüth, F.
    Angewandte Chemie - International Edition 49 1615-1618 (2010)
    "Chemical Equation Presented" Balls galorel A new approach was developed for the easy synthesis of hollow microspheres with amorphous or graphitized microstructure. Starting from one type of solid polymer sphere, a simple water washing treatment led to the formation of hollow structures. Diverse products such as hollow carbon or graphitized spheres can be obtained, depending on subsequent treatment methods (see picture). © 2010 Wlley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.200906445
  • 2010 • 5 Electrochemical synthesis of core-shell catalysts for electrocatalytic applications
    Kulp, C. and Chen, X. and Puschhof, A. and Schwamborn, S. and Somsen, C. and Schuhmann, W. and Bron, M.
    ChemPhysChem 11 2854-2861 (2010)
    A novel electrochemical method to prepare platinum shells around carbon-supported metal nanoparticles (Ru and Au) by pulsed electrodeposition from solutions containing Pt ions is presented. Shell formation is confirmed by characteristic changes in the cyclic voltammograms, and is further evidenced by monitoring particle growth by transmission electron microscopy as well as by energy-dispersive analysis of X rays (EDX). Scanning electrochemical microscopy and EDX measurements indicate a selective Pt deposition on the metal/carbon catalyst, but not on the glassy carbon substrate. The thus prepared carbon-supported core-shell nanoparticles are investigated with regard to their activity in electrocatalytic oxygen reduction, which demonstrates the applicability of these materials in electrocatalysis or sensors. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cphc.200900881
  • 2010 • 4 Hydrogen vibrational modes on graphene and relaxation of the C-H stretch excitation from first-principles calculations
    Sakong, S. and Kratzer, P.
    Journal of Chemical Physics 133 (2010)
    Density functional theory (DFT) calculations are used to determine the vibrational modes of hydrogen adsorbed on graphene in the low-coverage limit. Both the calculated adsorption energy of a H atom of 0.8 eV and calculated C-H stretch vibrational frequency of 2552 cm-1 are unusually low for hydrocarbons, but in agreement with data from electron energy loss spectroscopy on hydrogenated graphite. The clustering of two adsorbed H atoms observed in scanning tunneling microscopy images shows its fingerprint also in our calculated spectra. The energetically preferred adsorption on different sublattices correlates with a blueshift of the C-H stretch vibrational modes in H adatom clusters. The C-H bending modes are calculated to be in the 1100 cm-1 range, resonant with the graphene phonons. Moreover, we use our previously developed methods to calculate the relaxation of the C-H stretch mode via vibration-phonon interaction, using the Born-Oppenheimer surface for all local modes as obtained from the DFT calculations. The total decay rate of the H stretch into other H vibrations, thereby creating or annihilating one graphene phonon, is determined from Fermi's golden rule. Our calculations using the matrix elements derived from DFT calculations show that the lifetime of the H stretch mode on graphene is only several picoseconds, much shorter than on other semiconductor surfaces such as Ge(001) and Si(001). © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3474806
  • 2010 • 3 Modified DLC-coated guide pads for BTA deep hole drilling tools
    Biermann, D. and Kessler, N. and Upmeier, T. and Stucky, T.
    Key Engineering Materials 438 195-202 (2010)
    The BTA (Boring and Trepanning Association) deep hole drilling process is commonly used to machine boreholes with a large drilling depth-to-diameter ratio (l/D) and outstanding workpiece quality. The asymmetric tool design leads to a nonzero radial component of the cutting force and the passive force, which are conducted to the borehole wall by so-called guide pads. These guide pads smooth the borehole wall by a forming process and improve the surface quality. Processes, that machine materials with a high adhesion tendency, such as high alloy stainless steel, suffer from poor surface quality in the borehole and the adhesion from the workpiece material on the guide pads. In this paper modified Diamond-Like-Carbon (DLC) coated guide pads for BTA deep hole drilling tools are investigated. The scope of the experiments was the reduction of the adhesion by reducing the friction coefficient of the guide pads, as well as the improvement of the quality of the borehole wall. © (2010) Trans Tech Publications.
    view abstractdoi: 10.4028/www.scientific.net/KEM.438.195
  • 2010 • 2 Online dual gradient reversed-phase/porous graphitized carbon nanoHPLC for proteomic applications
    Lewandrowski, U. and Sickmann, A.
    Analytical Chemistry 82 5391-5396 (2010)
    The analysis of proteolytic peptide mixtures is among the dominant tasks within proteomic workflows. In order to limit undersampling effects during mass spectrometric detection, online-coupled liquid chromatography is the method of choice, with reversed-phase chromatography being the most important separation mode. Since hydrophilic compounds such as short peptides and some glycosylated species as well as oligosaccharides from glycoproteomic workflows are commonly not accessible by this analytical setup, we hereby present a dual gradient system combining reversed-phase and porous graphitic carbon retention modes within a single nanoHPLC setup. Samples in the low femtomole range are analyzed consecutively first by reversed phase, and nonretained molecules are directly separated by porous graphitic carbon. Both gradient elution systems allow for online coupled mass spectrometric detection and are demonstrated to enable analysis of protein, peptide, and oligosaccharide mixtures within the same setup. Thereby, the accessible range for proteomic and glycoproteomic applications may be extended far beyond the limits of conventional reversed-phase nanoHPLC setups. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ac100853w
  • 2010 • 1 Shearforce-based constant-distance scanning electrochemical microscopy as fabrication tool for needle-type carbon-fiber nanoelectrodes
    Hussien, E.M. and Schuhmann, W. and Schulte, A.
    Analytical Chemistry 82 5900-5905 (2010)
    Carbon fiber nanoelectrodes with nanometer radii tip curvatures were fabricated using a shearforce-based constant-distance scanning electrochemical microscope and electrochemically induced polymer deposition. A simple DC etching procedure in alkaline solution provided conically sharpened single carbon fibers with well-formed nanocones at their bottom. Coating the stems but not the end of the tips of the tapered structures with anodic electrodeposition paint was the strategy for limiting the bare carbon to the foremost end and restricting a feasible voltammetry current response to exactly this section. The electrodeposition of the polymer was prevented at the foremost end of the tip using a shearforce-based tip-to-sample distance control that allowed approaching the etched tips carefully in just touching distance to a film of a silicone elastomer. Analysis of the steady-state cyclic voltammograms in presence of a reversible redox compound revealed effective radii for the obtained needle-type carbon-fiber nanoelectrodes down to as small as 46 nm. The method offers an alternative pathway toward the fabrication of highly miniaturized carbon electrodes. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ac100738b