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 • 306 Catalytic effects of molybdate and chromate–molybdate films deposited on platinum for efficient hydrogen evolution
    Diaz-Morales, O. and Lindberg, A. and Smulders, V. and Anil, A. and Simic, N. and Wildlock, M. and Alvarez, G.S. and Mul, G. and Mei, B. and Cornell, A.
    Journal of Chemical Technology and Biotechnology 98 1269-1278 (2023)
    BACKGROUND: Sodium chlorate (NaClO3) is extensively used in the paper industry, but its production uses strictly regulated highly toxic Na2Cr2O7 to reach high hydrogen evolution reaction (HER) Faradaic efficiencies. It is therefore important to find alternatives either to replace Na2Cr2O7 or reduce its concentration. RESULTS: The Na2Cr2O7 concentration can be significantly reduced by using Na2MoO4 as an electrolyte co-additive. Na2MoO4 in the millimolar range shifts the platinum cathode potential to less negative values due to an activating effect of cathodically deposited Mo species. It also acts as a stabilizer of the electrodeposited chromium hydroxide but has a minor effect on the HER Faradaic efficiency. X-ray photoelectron spectroscopy (XPS) results show cathodic deposition of molybdenum of different oxidation states, depending on deposition conditions. Once Na2Cr2O7 was present, molybdenum was not detected by XPS, as it is likely that only trace levels were deposited. Using electrochemical measurements and mass spectrometry we quantitatively monitored H2 and O2 production rates. The results indicate that 3 μmol L−1 Na2Cr2O7 (contrary to current industrial 10–30 mmol L−1) is sufficient to enhance the HER Faradaic efficiency on platinum by 15%, and by co-adding 10 mmol L−1 Na2MoO4 the cathode is activated while avoiding detrimental O2 generation from chemical and electrochemical reactions. Higher concentrations of Na2MoO4 led to increased oxygen production. CONCLUSION: Careful tuning of the molybdate concentration can enhance performance of the chlorate process using chromate in the micromolar range. These insights could be also exploited in the efficient hydrogen generation by photocatalytic water splitting and in the remediation of industrial wastewater. © 2023 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI). © 2023 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI).
    view abstractdoi: 10.1002/jctb.7345
  • 2022 • 305 A guide to direct mechanocatalysis
    Hwang, S. and Grätz, S. and Borchardt, L.
    Chemical Communications 58 1661-1671 (2022)
    Direct mechanocatalysis (DM) describes solvent-free catalytic reactions that are initiated by mechanical forces in mechanochemical reactors such as ball mills. The distinctive feature of DM is that the milling materials, e.g. the milling balls themselves are the catalyst of the reaction. In this article we follow the historical evolution of this novel concept and give a guide to this emerging, powerful synthesis tool. Within this perspective we seek to highlight the impact of the relevant milling parameters, the nature of the catalyst and potential additives, the scope of reactions that are currently accessible by this method, and the thus far raised hypotheses on the underlying mechanisms of direct mechanochemical transformations. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/d1cc05697b
  • 2022 • 304 Advancing Critical Chemical Processes for a Sustainable Future: Challenges for Industry and the Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT)
    Bowker, M. and DeBeer, S. and Dummer, N.F. and Hutchings, G.J. and Scheffler, M. and Schüth, F. and Taylor, S.H. and Tüysüz, H.
    Angewandte Chemie - International Edition (2022)
    Catalysis is involved in around 85 % of manufacturing industry and contributes an estimated 25 % to the global domestic product, with the majority of the processes relying on heterogeneous catalysis. Despite the importance in different global segments, the fundamental understanding of heterogeneously catalysed processes lags substantially behind that achieved in other fields. The newly established Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT) targets innovative concepts that could contribute to the scientific developments needed in the research field to achieve net zero greenhouse gas emissions in the chemical industries. This Viewpoint Article presents some of our research activities and visions on the current and future challenges of heterogeneous catalysis regarding green industry and the circular economy by focusing explicitly on critical processes. Namely, hydrogen production, ammonia synthesis, and carbon dioxide reduction, along with new aspects of acetylene chemistry. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/anie.202209016
  • 2022 • 303 Atom Pair Frequencies as a Quantitative Structure-Activity Relationship for Catalytic 2-Propanol Oxidation over Nanocrystalline Cobalt-Iron-Spinel
    Geiss, J. and Falk, T. and Ognjanovic, S. and Anke, S. and Peng, B. and Muhler, M. and Winterer, M.
    Journal of Physical Chemistry C 126 10346-10358 (2022)
    The purpose of this study is to find a direct and quantitative correlation of the structure of Co3-xFexO4nanoparticles with catalytic performance in 2-propanol oxidation. Eight nanocrystalline samples with varying iron contents are synthesized, and quantitative information regarding their structure is obtained from nitrogen physisorption, X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analyzed by reverse Monte Carlo simulations. The catalytic performance is tested in 2-propanol oxidation in the gas phase. Overall, catalytic conversion data as a function of temperature are deconvoluted to obtain conversion and half-conversion temperatures as quantitative parameters for the different catalytic reaction channels. The crystal structure is described by a spinel structure with interstitial cation defects. These defects result in a reduced electronic state of the nanoparticles. The defect density depends on the cationic composition. We also observe a complex cationic distribution on tetrahedral and octahedral sites, which is strongly influenced by the overall cationic composition. In the catalytic tests, the samples exhibit a low-temperature pathway, which is deactivated in subsequent runs but can be recovered by an oxidative treatment of the catalyst. We find that the frequency of cation pairs CoO-CoOand CoO-CoTof the individual samples correlates directly to their catalytic activity and selectivity. © 2022 American Chemical Society. All rights reserved.
    view abstractdoi: 10.1021/acs.jpcc.2c00788
  • 2022 • 302 Efficient Nitrate Conversion to Ammonia on f-Block Single-Atom/Metal Oxide Heterostructure via Local Electron-Deficiency Modulation
    Kumar, A. and Lee, J. and Kim, M.G. and Debnath, B. and Liu, X. and Hwang, Y. and Wang, Y. and Shao, X. and Jadhav, A.R. and Liu, Y. and Tüysüz, H. and Lee, H.
    ACS Nano 16 15297-15309 (2022)
    Exploring single-atom catalysts (SACs) for the nitrate reduction reaction (NO3-NitRR) to value-added ammonia (NH3) offers a sustainable alternative to both the Haber-Bosch process and NO3--rich wastewater treatment. However, due to the insufficient electron deficiency and unfavorable electronic structure of SACs, resulting in poor NO3--adsorption, sluggish proton (H*) transfer kinetics, and preferred hydrogen evolution, their NO3--to-NH3selectivity and yield rate are far from satisfactory. Herein, a systematic theoretical prediction reveals that the local electron deficiency of an f-block Gd single atom (GdSA) can be significantly regulated upon coordination with oxygen-defect-rich NiO (GdSA-D-NiO400) support. Thus, facilitating stronger NO3-adsorption via strong Gd5d-O2porbital coupling and further improving the protonation kinetics of adsorption intermediates by rapid H∗ capture from water dissociation catalyzed by the adjacent oxygen vacancy site along with suppressed H∗ dimerization synergistically boosts the NH3selectivity/yield rate. Motivated by DFT prediction, we delicately stabilized electron-deficient (strongly electrophilic) GdSAon D-NiO400(?84% strong electrophilic sites), which exhibited excellent alkaline NitRR activity (NH3Faradaic efficiency ?97% and yield rate ?628 μg/(mgcath)) along with superior structural stability, as revealed by in situ Raman spectroscopy, significantly outperforming weakly electrophilic Gd nanoparticles, defect-free GdSA-P-NiO400, and reported state-of-the-art catalysts. © 2022 American Chemical Society. All rights reserved.
    view abstractdoi: 10.1021/acsnano.2c06747
  • 2022 • 301 Enhanced heterogeneous activation of peroxymonosulfate by Ruddlesden-Popper-type La2CoO4+δ nanoparticles for bisphenol A degradation
    Hammad, M. and Alkan, B. and Al-kamal, A.K. and Kim, C. and Ali, M.Y. and Angel, S. and Wiedemann, H.T.A. and Klippert, D. and Schmidt, T.C. and Kay, C.W.M. and Wiggers, H.
    Chemical Engineering Journal 429 (2022)
    The scalable synthesis of stable catalysts for environmental remediation applications remains challenging. Nonetheless, metal leaching is a serious environmental issue hindering the practical application of transition-metal based catalysts including Co-based catalysts. Herein, for the first time, we describe a facile one-step and scalable spray-flame synthesis of high surface area La2CoO4+δ nanoparticles containing excess oxygen interstitials (+δ) and use them as a stable and efficient catalyst for activating peroxymonosulfate (PMS) towards the degradation of bisphenol A. Importantly, the La2CoO4+δ catalyst exhibits higher catalytic degradation of bisphenol A (95% in 20 min) and stability than LaCoO3–x nanoparticles (60%) in the peroxymonosulfate activation system. The high content of Co2+ in the structure showed a strong impact on the catalytic performance of the La2CoO4+δ + PMS system. Despite its high specific surface area, our results showed a very low amount of leached cobalt (less than 0.04 mg/L in 30 min), distinguishing it as a material with high chemical stability. According to the radical quenching experiments and the electron paramagnetic resonance technology, SO4[rad]–, [rad]OH, and 1O2 were generated and SO4[rad]– played a dominant role in bisphenol A degradation. Moreover, the La2CoO4+δ + PMS system maintained conspicuous catalytic performance for the degradation of other organic pollutants including methyl orange, rhodamine B, and methylene blue. Overall, our results showed that we developed a new synthesis method for stable La2CoO4+δ nanoparticles that can be used as a highly active heterogeneous catalyst for PMS-assisted oxidation of organic pollutants. © 2021 Elsevier B.V.
    view abstractdoi: 10.1016/j.cej.2021.131447
  • 2022 • 300 Gold(I) NHC Catalysts Immobilized to Amphiphilic Block Copolymers: A Versatile Approach to Micellar Gold Catalysis in Water
    Petersen, H. and Ballmann, M. and Krause, N. and Weberskirch, R.
    ChemCatChem 14 (2022)
    Fifteen gold(I)-NHC-functionalized amphiphilic block copolymers that differ in the type of linker (ethyl, pentyl, octyl and benzyl) that attaches the gold(I) NHC catalyst to the block copolymer backbone, as well as, the substitution pattern of the NHC ligand (i. e. mesityl, methyl, 2,6-diisopropylphenyl and n-hexyl) were synthesized by a reversible addition and fragmentation transfer (RAFT) polymerization process. Micelle formation of the gold(I) NHC polymers was analyzed by electron microscopy and dynamic light scattering and revealed spherical and rod-like particles from 12 to 96 nm. In the micellar, gold(I) catalyzed cycloisomerization of an allene to the corresponding dihydrofuran, linker flexibility and substitution pattern of the NHC-ligand showed a strong effect on the catalytic activity. Best results were obtained were obtained for gold(I) NHC catalysts bound to the polymer backbone by pentyl linker whereas the rather stiff benzyl linker gave lowest catalyst conversion. Moreover, the polymer catalyst could be recycled in four consecutive runs and gave activities from 35 to 84 % in the fourth run and underscores the importance of fine tuning structural parameters to achieve high conversion under micellar reaction conditions. © 2022 The Authors. ChemCatChem published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/cctc.202200727
  • 2022 • 299 Identification of the main mixing process in the synthesis of alloy nanoparticles by laser ablation of compacted micropowder mixtures
    Waag, F. and Fares, W.I.M.A. and Li, Y. and Andronescu, C. and Gökce, B. and Barcikowski, S.
    Journal of Materials Science 57 3041-3056 (2022)
    Alloy nanoparticles offer the possibility to tune functional properties of nanoscale structures. Prominent examples of tuned properties are the local surface plasmon resonance for sensing applications and adsorption energies for applications in catalysis. Laser synthesis of colloidal nanoparticles is well suited for generating alloy nanoparticles of desired compositions. Not only bulk alloys but also compacted mixtures of single-metal micropowders can serve as ablation targets. However, it is still unknown how mixing of the individual metals transfers from the micro- to the nanoscale. This work experimentally contributes to the elucidation of the mixing processes during the laser-based synthesis of alloy nanoparticles. Key parameters, such as the initial state of mixing in the ablation target, the laser pulse duration, the laser spot size, and the ablation time, are varied. Experiments are performed on a cobalt-iron alloy, relevant for application in oxidation catalysis, in ethanol. The extent of mixing in the targets after ablation and in individual nanoparticles are studied by energy-dispersive X-ray spectroscopy and by cyclic voltammetry at relevant conditions for the oxygen evolution reaction, as model reaction. The results point at the benefits of well pre-mixed ablation targets and longer laser pulse durations for the laser-based synthesis of alloy nanoparticles. Graphical abstract: [Figure not available: see fulltext.] © 2021, The Author(s).
    view abstractdoi: 10.1007/s10853-021-06731-2
  • 2022 • 298 In Situ Monitoring of Palladium-Catalyzed Chemical Reactions by Nanogap-Enhanced Raman Scattering using Single Pd Cube Dimers
    Wang, D. and Shi, F. and Jose, J. and Hu, Y. and Zhang, C. and Zhu, A. and Grzeschik, R. and Schlücker, S. and Xie, W.
    Journal of the American Chemical Society 144 5003-5009 (2022)
    The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneously catalyzed reactions is the need of plasmonically active nanostructures for signal enhancement. Here, we show that the assembly of catalytically active transition-metal nanoparticles into dimers boosts their intrinsically insufficient plasmonic activity at the monomer level by several orders of magnitude, thereby enabling the in situ SERS monitoring of various important heterogeneously catalyzed reactions at the single-dimer level. Specifically, we demonstrate that Pd nanocubes (NCs), which alone are not sufficiently plasmonically active as monomers, can act as a monometallic yet bifunctional platform with both catalytic and satisfactory plasmonic activity via controlled assembly into single dimers with an ∼1 nm gap. Computer simulations reveal that the highest enhancement factors (EFs) occur at the corners of the gap, which has important implications for the SERS-based detection of catalytic conversions: it is sufficient for molecules to come in contact with the "hot spot corners", and it is not required that they diffuse deeply into the gap. For the widely employed Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, we demonstrate that such Pd NC dimers can be employed for in situ kinetic SERS monitoring, using a whole series of aryl halides as educts. Our generic approach based on the controlled assembly into dimers can easily be extended to other transition-metal nanostructures. © 2022 American Chemical Society.
    view abstractdoi: 10.1021/jacs.1c13240
  • 2022 • 297 In-situ Investigations of Co@Al2O3 Ammonia Decomposition Catalysts: The Interaction between Support and Catalyst
    Weidenthaler, C. and Schmidt, W. and Leiting, S. and Ternieden, J. and Kostis, A. and Ulucan, T.H. and Budiyanto, E.
    ChemCatChem 14 (2022)
    Cracking of ammonia, a hydrogen carrier with high storage capacity, gains increasing attention for fuel cell systems for heavy load transportation. In this work, we studied the influence of metal loading and synthesis temperatures on the properties of Co@Al2O3 catalysts. The combination of in situ bulk characterization methods with in situ surface spectroscopy provides insights into the structure-property relation of the Co catalyst on the γ-Al2O3 support. At too high temperatures, the formation of CoAl2O4 during synthesis or during the catalytic reaction itself results in inactive mixed metal aluminium spinels which do not contribute to the catalytic reaction. The amount of ‘active’ Co catalyst thus varies significantly as well as its catalytic activity. The latter is correlated to the size of the reduced Co particles on the alumina support. The experiments also highlight that the state of the catalyst changes after reaction which strongly emphasizes the necessity of in situ studies. © 2022 The Authors. ChemCatChem published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/cctc.202200688
  • 2022 • 296 Influence of the Moiré Pattern of Ag(111)-Supported Graphitic ZnO on Water Distribution
    Hung, T.-C. and Le, D. and Rahman, T. and Morgenstern, K.
    Journal of Physical Chemistry C 126 12500-12506 (2022)
    The distribution of water on metal supported oxides is an important step in understanding heterogeneous catalysis such as in the water gas shift reaction. Here, we study water structures on Ag(111)-supported graphitic zinc oxide islands by variable temperature scanning tunneling microscopy around 150 K and ab initio calculations. Water clusters, accumulating on the ZnO islands, are confined to the hcp regions of the ZnO moiré pattern. A significantly higher cluster density at the island border is related to the dimensions of its capture zone. This suggests an upward mass transport of the water from the supporting metal to the ultrathin oxide film, increasing the water density at the active metal-oxide border. © 2022 American Chemical Society. All rights reserved.
    view abstractdoi: 10.1021/acs.jpcc.2c03274
  • 2022 • 295 Introducing Stacking Faults into Three-Dimensional Branched Nickel Nanoparticles for Improved Catalytic Activity
    Ramadhan, Z.R. and Poerwoprajitno, A.R. and Cheong, S. and Webster, R.F. and Kumar, P.V. and Cychy, S. and Gloag, L. and Benedetti, T.M. and Marjo, C.E. and Muhler, M. and Wang, D.-W. and Gooding, J.J. and Schuhmann, W. and Tilley, R.D.
    Journal of the American Chemical Society 144 11094-11098 (2022)
    Creating high surface area nanocatalysts that contain stacking faults is a promising strategy to improve catalytic activity. Stacking faults can tune the reactivity of the active sites, leading to improved catalytic performance. The formation of branched metal nanoparticles with control of the stacking fault density is synthetically challenging. In this work, we demonstrate that varying the branch width by altering the size of the seed that the branch grows off is an effective method to precisely tune the stacking fault density in branched Ni nanoparticles. A high density of stacking faults across the Ni branches was found to lower the energy barrier for Ni2+/Ni3+oxidation and result in enhanced activity for electrocatalytic oxidation of 5-hydroxylmethylfurfural. These results show the ability to synthetically control the stacking fault density in branched nanoparticles as a basis for enhanced catalytic activity. © 2022 American Chemical Society. All rights reserved.
    view abstractdoi: 10.1021/jacs.2c04911
  • 2022 • 294 One-Dimensional Water Structures upon Cs Hydration on the Moiré Pattern of Graphitic ZnO
    Hung, T.-C. and Morgenstern, K.
    Journal of Physical Chemistry C 126 15229-15234 (2022)
    Water nucleation on alkali precovered metal-supported oxide surfaces is an important step in understanding water as one of the reactants in alkali-assisted heterogeneous catalysis. For instance, alkali metals as catalyst dopants enhance the water-gas shift reaction that catalyzes on ZnO-metal nanostructures. Here, we investigate the hydration of cesium on a Ag(111)-supported graphitic zinc oxide ultrathin film using scanning tunneling microscopy at (160 ± 30) K. Upon hydrating the pristine graphitic ZnO film, the water forms well-separated clusters on the hcp regions of the ZnO moiré pattern at water coverages below 85% ML. In the presence of cesium on the fcc regions of the ZnO moiré pattern, the water clusters coalesce across hcp regions at water coverages above ∼32% ML, forming unique one-dimensional water-Cs chains along the high-symmetry directions of the ZnO moiré pattern. Our study demonstrates that the alkali doping of an oxide surface alters the dimensionality of water structures redirecting it partially to other adsorption regions, possibly influencing its reactivity. © 2022 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.2c05166
  • 2022 • 293 Progress in alumina ceramic membranes for water purification: Status and prospects
    Wang, Y. and Ma, B. and Ulbricht, M. and Dong, Y. and Zhao, X.
    Water Research 226 (2022)
    Ceramic membranes have gained increasing attention in recent years for the removal of various contaminants from water. Alumina membrane is considered as one of the most important ceramic membranes, which plays important roles not only in separation processes such as microfiltration, ultrafiltration, and nanofiltration, but also in catalysis- and adsorption- enhanced separation applications in water purification and wastewater treatment. However, there is currently still lack of a comprehensive critical review about alumina membranes for water purification. In this review, we first discuss recent developments of alumina membranes, and then critically introduce the state-of-the-art strategies for lowering fabrication cost, improving membrane performances and mitigating membrane fouling. Especially, aiming to improve membrane performance, some emerging methods are summarized such as tailoring membrane structure, developing flexible membranes, designing nano-pores for precise separation, and enhancing multi-functionalities. In addition, engineering applications of alumina membranes for water purification are also briefly introduced. Finally, the prospects for future research on alumina membranes are proposed, such as economic preparation/application, challenging precise separation, enriching multi-functionalities, and clarifying separation mechanisms. © 2022 Elsevier Ltd
    view abstractdoi: 10.1016/j.watres.2022.119173
  • 2022 • 292 Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia
    He, W. and Zhang, J. and Dieckhöfer, S. and Varhade, S. and Brix, A.C. and Lielpetere, A. and Seisel, S. and Junqueira, J.R.C. and Schuhmann, W.
    Nature Communications 13 (2022)
    Electrocatalytic recycling of waste nitrate (NO3−) to valuable ammonia (NH3) at ambient conditions is a green and appealing alternative to the Haber−Bosch process. However, the reaction requires multi-step electron and proton transfer, making it a grand challenge to drive high-rate NH3 synthesis in an energy-efficient way. Herein, we present a design concept of tandem catalysts, which involves coupling intermediate phases of different transition metals, existing at low applied overpotentials, as cooperative active sites that enable cascade NO3−-to-NH3 conversion, in turn avoiding the generally encountered scaling relations. We implement the concept by electrochemical transformation of Cu−Co binary sulfides into potential-dependent core−shell Cu/CuOx and Co/CoO phases. Electrochemical evaluation, kinetic studies, and in−situ Raman spectra reveal that the inner Cu/CuOx phases preferentially catalyze NO3− reduction to NO2−, which is rapidly reduced to NH3 at the nearby Co/CoO shell. This unique tandem catalyst system leads to a NO3−-to-NH3 Faradaic efficiency of 93.3 ± 2.1% in a wide range of NO3− concentrations at pH 13, a high NH3 yield rate of 1.17 mmol cm−2 h−1 in 0.1 M NO3− at −0.175 V vs. RHE, and a half-cell energy efficiency of ~36%, surpassing most previous reports. © 2022, The Author(s).
    view abstractdoi: 10.1038/s41467-022-28728-4
  • 2022 • 291 Teaming up main group metals with metallic iron to boost hydrogenation catalysis
    Färber, C. and Stegner, P. and Zenneck, U. and Knüpfer, C. and Bendt, G. and Schulz, S. and Harder, S.
    Nature Communications 13 (2022)
    Hydrogenation of unsaturated bonds is a key step in both the fine and petrochemical industries. Homogeneous and heterogeneous catalysts are historically based on noble group 9 and 10 metals. Increasing awareness of sustainability drives the replacement of costly, and often harmful, precious metals by abundant 3d-metals or even main group metals. Although not as efficient as noble transition metals, metallic barium was recently found to be a versatile hydrogenation catalyst. Here we show that addition of finely divided Fe0, which itself is a poor hydrogenation catalyst, boosts activities of Ba0 by several orders of magnitude, enabling rapid hydrogenation of alkynes, imines, challenging multi-substituted alkenes and non-activated arenes. Metallic Fe0 also boosts the activity of soluble early main group metal hydride catalysts, or precursors thereto. This synergy originates from cooperativity between a homogeneous, highly reactive, polar main group metal hydride complex and a heterogeneous Fe0 surface that is responsible for substrate activation. © 2022, The Author(s).
    view abstractdoi: 10.1038/s41467-022-30840-4
  • 2022 • 290 The Direct Mechanocatalytic Suzuki–Miyaura Reaction of Small Organic Molecules
    Pickhardt, W. and Beaković, C. and Mayer, M. and Wohlgemuth, M. and Kraus, F.J.L. and Etter, M. and Grätz, S. and Borchardt, L.
    Angewandte Chemie - International Edition (2022)
    The molecular Suzuki cross-coupling reaction was conducted mechanochemically, without solvents, ligands, or catalyst powders. Utilizing one catalytically active palladium milling ball, products could be formed in quantitative yield in as little as 30 min. In contrast to previous reports, the adjustment of milling parameters led to the complete elimination of abrasion from the catalyst ball, thus enabling the first reported systematic catalyst analysis. XPS, in situ XRD, and reference experiments provided evidence that the milling ball surface was the location of the catalysis, allowing a mechanism to be proposed. The versatility of the approach was demonstrated by extending the substrate scope to deactivated and even sterically hindered aryl iodides and bromides. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/anie.202205003
  • 2022 • 289 Transient uptake measurements with a physisorption instrument: Trends in gas-phase diffusivities within mesoporous materials
    Joshi, H. and Hopf, A. and Losch, P. and Schmidt, W. and Schüth, F.
    Microporous and Mesoporous Materials 330 (2022)
    The measurement of diffusivity within porous solids is vital for the characterization of materials, especially in heterogeneous catalysis and separation processes. Numerous methods have been developed to measure gas-phase diffusivities within materials. However, establishing correlations between the diffusivities and the properties of a material is challenging. Herein, we report a method for obtaining trends in gas-phase diffusivity of N2 at 77 K within three different sets of mesoporous materials, disordered, ordered silica, and carbons-based materials. Synthesis procedures are reproducible and controlled precisely to achieve monodisperse particle size and defined pore size distributions. A standard physisorption device, Micromeritics 3Flex, is used to obtain the required transient data. These two aspects offer a suitable database of materials to identify trends and reduce the challenges associated with obtaining experimental data. A simplified model is fitted over the transient data with MATLAB to obtain empirical diffusivities used for trend analysis. The trends are based on a constant Dτ, an ensemble value representing various diffusion processes occurring during a transient uptake process. The analysis identifies several correlations between the diffusivity and properties of materials, such as type of pore structure, pore size, and the chemical nature of the material. Based on the principles reported, this study can be extended to other adsorptive molecules or different temperatures. The possibility of using standard sorption instrumentation will allow a broader user community to employ the reported methodology. © 2021 Elsevier Inc.
    view abstractdoi: 10.1016/j.micromeso.2021.111627
  • 2021 • 288 -Hydrogenases: Maturation and reactivity of enzymatic systems and overview of biomimetic models
    Kleinhaus, J.T. and Wittkamp, F. and Yadav, S. and Siegmund, D. and Apfel, U.-P.
    Chemical Society Reviews 50 1668-1784 (2021)
    While hydrogen plays an ever-increasing role in modern society, nature has utilized hydrogen since a very long time as an energy carrier and storage molecule. Among the enzymatic systems that metabolise hydrogen, [FeFe]-hydrogenases are one of the most powerful systems to perform this conversion. In this light, we will herein present an overview on developments in [FeFe]-hydrogenase research with a strong focus on synthetic mimics and their application within the native enzymatic environment. This review spans from the biological assembly of the natural enzyme and the highly controversial discussed mechanism for the hydrogen generation to the synthesis of multiple mimic platforms as well as their electrochemical behaviour. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/d0cs01089h
  • 2021 • 287 A safety cap protects hydrogenase from oxygen attack
    Winkler, M. and Duan, J. and Rutz, A. and Felbek, C. and Scholtysek, L. and Lampret, O. and Jaenecke, J. and Apfel, U.-P. and Gilardi, G. and Valetti, F. and Fourmond, V. and Hofmann, E. and Léger, C. and Happe, T.
    Nature Communications 12 (2021)
    [FeFe]-hydrogenases are efficient H2-catalysts, yet upon contact with dioxygen their catalytic cofactor (H-cluster) is irreversibly inactivated. Here, we combine X-ray crystallography, rational protein design, direct electrochemistry, and Fourier-transform infrared spectroscopy to describe a protein morphing mechanism that controls the reversible transition between the catalytic Hox-state and the inactive but oxygen-resistant Hinact-state in [FeFe]-hydrogenase CbA5H of Clostridium beijerinckii. The X-ray structure of air-exposed CbA5H reveals that a conserved cysteine residue in the local environment of the active site (H-cluster) directly coordinates the substrate-binding site, providing a safety cap that prevents O2-binding and consequently, cofactor degradation. This protection mechanism depends on three non-conserved amino acids situated approximately 13 Å away from the H-cluster, demonstrating that the 1st coordination sphere chemistry of the H-cluster can be remote-controlled by distant residues. © 2021, The Author(s).
    view abstractdoi: 10.1038/s41467-020-20861-2
  • 2021 • 286 An Efficient Method for Covalent Surface Functionalization of Ultrasmall Metallic Nanoparticles by Surface Azidation Followed by Copper-Catalyzed Azide-Alkyne Cycloaddition (Click Chemistry)
    Klein, K. and Loza, K. and Heggen, M. and Epple, M.
    ChemNanoMat (2021)
    The azidation of glutathione (GSH)-functionalized ultrasmall gold nanoparticles (2 nm) by the azide transfer reagent imidazole-1-sulfonyl azide hydrogen sulfate leads to azide-terminated nanoparticles with high yield. A subsequent copper-catalyzed azide-alkyne cycloaddition (CuAAC), i. e. a click reaction, leads to covalently functionalized nanoparticles. This was demonstrated with two alkyne-functionalized dyes, i. e. FAM-alkyne and AlexaFluor-647-alkyne, that were covalently coupled to the nanoparticles. The integrity of the glutathione ligand and the successful surface azidation were demonstrated by one-dimensional and two-dimensional NMR spectroscopy. The surface composition of the nanoparticles was determined by quantitative NMR spectroscopy and UV/vis spectroscopy. Each nanoparticle carries 125 glutathione molecules of which 118 were substituted by an azide group. After dye conjugation, either 6 FAM molecules or 11 AlexaFluor-647 molecules were present on each nanoparticle, respectively. The dye-clicked nanoparticles were highly fluorescent due to the absence of surface plasmon resonance. The post-functionalization of GSH avoids a chemical reaction of a functional ligand during the reduction reaction, gives a high yield (up to 50 mg nanoparticles per batch), is based on water as solvent, and is applicable for metallic nanoparticles in general. © 2021 The Authors. ChemNanoMat published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/cnma.202100359
  • 2021 • 285 Catalytic reactions in ball mills
    Amrute, A.P. and Schüth, F.
    Catalysis 33 307-346 (2021)
    Over the past two decades mechanochemistry has emerged as an important tool in catalysis research. It has not only shown promise for catalyst synthesis, resulting in properties that are often unattainable by conventional methods, but is also a very effective tool for performing catalytic reactions with exceptional selectivities. Besides, in several instances, it allows reactions under much milder conditions compared to thermochemical methods. In this chapter, we attempt to give an overview of these efforts with a focus on catalytic reactions in ball mills. Through the selection of prominent examples from the literature, from early mentions in 300 B.C. to recent times, we try to analyze how mechanical forces lead to chemical reactions and what effect they cause to materials or chemical reactions. We also discuss the state-of-the-art milling devices, and then cover broadly chemical reactions in ball mills. The latter part briefly tackles materials synthesis, but mainly focuses on chemical reactions of solid-solid and gas-solid nature from both organic synthesis and heterogeneous catalysis. The chapter also touches on the aspects of in situ analysis and scale-up with relevant literature. The latter areas are currently in the focus of attention to develop deeper understanding and to eventually find ways to make mechanocatalysis industrially applicable. © The Royal Society of Chemistry 2021.
    view abstractdoi: 10.1039/9781839163128-00307
  • 2021 • 284 Facet-Dependent Surface Charge and Hydration of Semiconducting Nanoparticles at Variable pH
    Su, S. and Siretanu, I. and van den Ende, D. and Mei, B. and Mul, G. and Mugele, F.
    Advanced Materials 33 (2021)
    Understanding structure and function of solid–liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO3 nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO2) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/adma.202106229
  • 2021 • 283 Hydrogen electrocatalysis revisited: Weak bonding of adsorbed hydrogen as the design principle for active electrode materials
    Exner, K.S.
    Current Opinion in Electrochemistry 26 (2021)
    Hydrogen electrocatalysis has been spurred by theoretical predictions, using simple ab initio thermodynamic considerations, in that the free-binding energy of adsorbed hydrogen has been applied in a heuristic fashion to search for sustainable electrocatalysts as a replacement for scarce platinum in electrolyzers and fuel cells. The original volcano model of Nørskov et al. is given in [14] purports that the optimum hydrogen-evolution catalyst binds adsorbed hydrogen thermoneutrally at zero overpotential, a paradigm based on pure thermodynamic considerations. Recently, the Sabatier principle was revisited by factoring the applied overpotential and kinetics into the analysis. The extended Sabatier principle suggests that the optimum hydrogen-evolution catalyst binds adsorbed hydrogen weakly rather than thermoneutrally. This notion is corroborated by the fact that the most active hydrogen-evolution catalysts, Pt, MoS2, or Mo2C, indeed bind hydrogen weakly by about (100–200) meV rather than thermoneutrally at zero overpotential. © 2020 Elsevier B.V.
    view abstractdoi: 10.1016/j.coelec.2020.100673
  • 2021 • 282 Insights into lithium manganese oxide-water interfaces using machine learning potentials
    Eckhoff, M. and Behler, J.
    Journal of Chemical Physics 155 (2021)
    Unraveling the atomistic and the electronic structure of solid-liquid interfaces is the key to the design of new materials for many important applications, from heterogeneous catalysis to battery technology. Density functional theory (DFT) calculations can, in principle, provide a reliable description of such interfaces, but the high computational costs severely restrict the accessible time and length scales. Here, we report machine learning-driven simulations of various interfaces between water and lithium manganese oxide (LixMn2O4), an important electrode material in lithium ion batteries and a catalyst for the oxygen evolution reaction. We employ a high-dimensional neural network potential to compute the energies and forces several orders of magnitude faster than DFT without loss in accuracy. In addition, a high-dimensional neural network for spin prediction is utilized to analyze the electronic structure of the manganese ions. Combining these methods, a series of interfaces is investigated by large-scale molecular dynamics. The simulations allow us to gain insights into a variety of properties, such as the dissociation of water molecules, proton transfer processes, and hydrogen bonds, as well as the geometric and electronic structure of the solid surfaces, including the manganese oxidation state distribution, Jahn-Teller distortions, and electron hopping. © 2021 Author(s).
    view abstractdoi: 10.1063/5.0073449
  • 2021 • 281 Interface Phenomena
    Engstfeld, A.K. and Hoster, H. and Magnussen, O.M.
    ChemPhysChem 22 2497 (2021)
    doi: 10.1002/cphc.202100712
  • 2021 • 280 Metal–Organic-Framework-Supported Molecular Electrocatalysis for the Oxygen Reduction Reaction
    Liang, Z. and Guo, H. and Zhou, G. and Guo, K. and Wang, B. and Lei, H. and Zhang, W. and Zheng, H. and Apfel, U.-P. and Cao, R.
    Angewandte Chemie - International Edition 60 8472-8476 (2021)
    Synthesizing molecule@support hybrids is appealing to improve molecular electrocatalysis. We report herein metal–organic framework (MOF)-supported Co porphyrins for the oxygen reduction reaction (ORR) with improved activity and selectivity. Co porphyrins can be grafted on MOF surfaces through ligand exchange. A variety of porphyrin@MOF hybrids were made using this method. Grafted Co porphyrins showed boosted ORR activity with large (>70 mV) anodic shift of the half-wave potential compared to ungrafted porphyrins. By using active MOFs for peroxide reduction, the number of electrons transferred per O2 increased from 2.65 to 3.70, showing significantly improved selectivity for the 4e ORR. It is demonstrated that H2O2 generated from O2 reduction at Co porphyrins is further reduced at MOF surfaces, leading to improved 4e ORR. As a practical demonstration, these hybrids were used as air electrode catalysts in Zn-air batteries, which exhibited equal performance to that with Pt-based materials. © 2021 Wiley-VCH GmbH
    view abstractdoi: 10.1002/anie.202016024
  • 2021 • 279 Method to Construct Volcano Relations by Multiscale Modeling: Building Bridges between the Catalysis and Biosimulation Communities
    Exner, K.S. and Ivanova, A.
    Journal of Physical Chemistry B 125 2098-2104 (2021)
    Understanding the complex interactions of different building blocks within a sophisticated drug-delivery system (DDS), aimed at targeted transport of the drug to malignant cells, requires modeling techniques on different time and length scales. On the example of the anthracycline antibiotic doxorubicin (DOX), we investigate a potential DDS component, consisting of a gold nanoparticle and a short peptide sequence as carriers of DOX. The combination of atomistic molecular dynamics simulations and density functional theory calculations facilitates compiling a volcano plot, which allows deriving general conclusions on DDS constituents for chemotherapeutic agents within the class of anthracycline antibiotics: the nanoparticle and peptide carrier moieties need to be chosen in such a way that the anthracycline body of the drug is able to intercalate between both entities or between two (π-stacking) residues of the peptide. Using the popular volcano framework as a guideline, the present article connects the catalysis and biosimulation communities, thereby identifying a strategy to overcome the limiting volcano relation by tuning the coordination number of the drug in the DDS component. ©
    view abstractdoi: 10.1021/acs.jpcb.1c00836
  • 2021 • 278 Multidimensional thermally-induced transformation of nest-structured complex Au-Fe nanoalloys towards equilibrium
    Johny, J. and Prymak, O. and Kamp, M. and Calvo, F. and Kim, S.-H. and Tymoczko, A. and El-Zoka, A. and Rehbock, C. and Schürmann, U. and Gault, B. and Kienle, L. and Barcikowski, S.
    Nano Research (2021)
    Bimetallic nanoparticles are often superior candidates for a wide range of technological and biomedical applications owing to their enhanced catalytic, optical, and magnetic properties, which are often better than their monometallic counterparts. Most of their properties strongly depend on their chemical composition, crystallographic structure, and phase distribution. However, little is known of how their crystal structure, on the nanoscale, transforms over time at elevated temperatures, even though this knowledge is highly relevant in case nanoparticles are used in, e.g., high-temperature catalysis. Au-Fe is a promising bimetallic system where the low-cost and magnetic Fe is combined with catalytically active and plasmonic Au. Here, we report on the in situ temporal evolution of the crystalline ordering in Au-Fe nanoparticles, obtained from a modern laser ablation in liquids synthesis. Our in-depth analysis, complemented by dedicated atomistic simulations, includes a detailed structural characterization by X-ray diffraction and transmission electron microscopy as well as atom probe tomography to reveal elemental distributions down to a single atom resolution. We show that the Au-Fe nanoparticles initially exhibit highly complex internal nested nanostructures with a wide range of compositions, phase distributions, and size-depended microstrains. The elevated temperature induces a diffusion-controlled recrystallization and phase merging, resulting in the formation of a single face-centered-cubic ultrastructure in contact with a body-centered cubic phase, which demonstrates the metastability of these structures. Uncovering these unique nanostructures with nested features could be highly attractive from a fundamental viewpoint as they could give further insights into the nanoparticle formation mechanism under non-equilibrium conditions. Furthermore, the in situ evaluation of the crystal structure changes upon heating is potentially relevant for high-temperature process utilization of bimetallic nanoparticles, e.g., during catalysis. © 2021, The Author(s).
    view abstractdoi: 10.1007/s12274-021-3524-7
  • 2021 • 277 Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation
    Cychy, S. and Lechler, S. and Huang, Z. and Braun, M. and Brix, A.C. and Blümler, P. and Andronescu, C. and Schmid, F. and Schuhmann, W. and Muhler, M.
    Chinese Journal of Catalysis 42 2206-2215 (2021)
    The influence of the drop-casted nickel boride catalyst loading on glassy carbon electrodes was investigated in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in alkaline glycerol electrooxidation. The continuously operated radial flow cell consisted of a borehole electrode positioned 50 µm above an internal reflection element enabling operando FTIR spectroscopy. It is identified as a suitable tool for facile and reproducible screening of electrocatalysts under well-defined conditions, additionally providing access to the selectivities in complex reaction networks such as glycerol oxidation. The fast product identification by ATR-IR spectroscopy was validated by the more time-consuming quantitative HPLC analysis of the pumped electrolyte. High degrees of glycerol conversion were achieved under the applied laminar flow conditions using 0.1 M glycerol and 1 M KOH in water and a flow rate of 5 µL min−1. Conversion and selectivity were found to depend on the catalyst loading, which determined the catalyst layer thickness and roughness. The highest loading of 210 µg cm−2 resulted in 73% conversion and a higher formate selectivity of almost 80%, which is ascribed to longer residence times in rougher films favoring readsorption and C–C bond scission. The lowest loading of 13 µg cm−2 was sufficient to reach 63% conversion, a lower formate selectivity of 60%, and, correspondingly, higher selectivities of C2 species such as glycolate amounting to 8%. Thus, only low catalyst loadings resulting in very thin films in the few μm thickness range are suitable for reliable catalyst screening. © 2021 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences
    view abstractdoi: 10.1016/S1872-2067(20)63766-4
  • 2021 • 276 Photoelectron Photoion Coincidence Spectroscopy Provides Mechanistic Insights in Fuel Synthesis and Conversion
    Hemberger, P. and Bodi, A. and Bierkandt, T. and Köhler, M. and Kaczmarek, D. and Kasper, T.
    Energy and Fuels 35 16265-16302 (2021)
    Clean combustion, i.e., the reduction of NOx and soot emissions, and carbon neutrality, achieved in part by biofuel synthesis, are major milestones in the transition to a sustainable future. To overcome empiric and time-consuming process optimization steps, we need detailed reaction mechanistic and chemical insights on these processes. Be it in combustion or in catalysis, highly reactive intermediates, such as radicals, carbenes, and ketenes drive chemical reactions. Knowing the fate of these species helps develop strategies to optimize chemical energy conversion processes. This calls for advanced mass spectrometric tools, which enable the detection of transient species. In this review, we report on the application of state-of-the-art photoelectron photoion coincidence (PEPICO) spectroscopy with vacuum ultraviolet (VUV) synchrotron radiation as advanced diagnostic tools in catalysis and combustion research. We discuss reaction mechanisms in biomass conversion to sustainable fuels, where we report on the pyrolysis of wood samples probed using VUV photoionization mass spectrometry (PIMS) and obtain deep mechanistic insights in the (non)catalytic pyrolysis of lignin model compounds with PEPICO detection. PEPICO is also shown to contribute to the mechanistic understanding of catalysis by unveiling catalytic alkane valorization mechanisms. We discuss how PEPICO detection advances combustion diagnostics, thanks to the application of photoelectron spectroscopy and velocity map imaging. We report on mechanistic aspects of ignition, such as fuel radical formation and oxidation to peroxy species, and discuss reaction pathways of pollutant formation. In addition, we zoom into the elementary reactions of combustion and discuss isomer-selective kinetics experiments on radical oxidation. Newly revealed reaction pathways to polycyclic aromatic hydrocarbon (PAH) formation are also detailed. Finally, we describe current instrumental developments to improve PEPICO detection and report on innovative sources, reactors, and reaction sampling approaches to be combined with this technique. © 2021 American Chemical Society.
    view abstractdoi: 10.1021/acs.energyfuels.1c01712
  • 2021 • 275 Properties of α-Brass Nanoparticles II: Structure and Composition
    Weinreich, J. and Paleico, M.L. and Behler, J.
    Journal of Physical Chemistry C 125 14897-14909 (2021)
    Nanoparticles have become increasingly interesting for a wide range of applications because in principle it is possible to tailor their properties by controlling size, shape, and composition. One of these applications is heterogeneous catalysis, and a fundamental understanding of the structural details of the nanoparticles is essential for any knowledge-based improvement of reactivity and selectivity. In this work, we investigate the atomic structure of brass nanoparticles containing up to 5000 atoms as a typical example for a binary alloy consisting of Cu and Zn. As systems of this size are too large for electronic structure calculations, in our simulations, we use a recently parameterized machine learning potential providing close to density functional theory accuracy. This potential is employed for a structural characterization as a function of chemical composition by various types of simulations such as Monte Carlo in the semigrand canonical ensemble and simulated annealing molecular dynamics. Our analysis reveals that the distribution of both elements in the nanoparticles is inhomogeneous, and zinc accumulates in the outermost layer, while the first subsurface layer shows an enrichment of copper. Only for high zinc concentrations, alloying can be found in the interior of the nanoparticles, and regular patterns corresponding to crystalline bulk phases of α-brass can then be observed. The surfaces of the investigated clusters exhibit well-ordered single-crystal facets, which can give rise to grain boundaries inside the clusters. The melting temperature of the nanoparticles is found to decrease with increasing zinc-atom fraction, a trend which is well known also for the bulk phase diagram of brass. © 2021 The Authors. Published by American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.1c02314
  • 2021 • 274 Scalable and Recyclable All-Organic Colloidal Cascade Catalysts
    Chen, C. and Janoszka, N. and Wong, C.K. and Gramse, C. and Weberskirch, R. and Gröschel, A.H.
    Angewandte Chemie - International Edition 60 237-241 (2021)
    We report on the synthesis of core–shell microparticles (CSMs) with an acid catalyst in the core and a base catalyst in the shell by surfactant-free emulsion polymerization (SFEP). The organocatalytic monomers were separately copolymerized in three synthetic steps allowing the spatial separation of incompatible acid and base catalysts within the CSMs. Importantly, a protected and thermo-decomposable sulfonate monomer was used as acid source to circumvent the neutralization of the base catalyst during shell formation, which was key to obtain stable, catalytically active CSMs. The catalysts showed excellent performance in an established one-pot model cascade reaction in various solvents (including water), which involved an acid-catalyzed deacetalization followed by a base-catalyzed Knoevenagel condensation. The CSMs are easily recycled, modified, and their synthesis is scalable, making them promising candidates for organocatalytic applications. © 2020 The Authors. Published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/anie.202008104
  • 2021 • 273 Searching novel complex solid solution electrocatalysts in unconventional element combinations
    Krysiak, O.A. and Schumacher, S. and Savan, A. and Schuhmann, W. and Ludwig, A. and Andronescu, C.
    Nano Research (2021)
    Despite outstanding accomplishments in catalyst discovery, finding new, more efficient, environmentally neutral, and noble metal-free catalysts remains challenging and unsolved. Recently, complex solid solutions consisting of at least five different elements and often named as high-entropy alloys have emerged as a new class of electrocatalysts for a variety of reactions. The multicomponent combinations of elements facilitate tuning of active sites and catalytic properties. Predicting optimal catalyst composition remains difficult, making testing of a very high number of them indispensable. We present the high-throughput screening of the electrochemical activity of thin film material libraries prepared by combinatorial co-sputtering of metals which are commonly used in catalysis (Pd, Cu, Ni) combined with metals which are not commonly used in catalysis (Ti, Hf, Zr). Introducing unusual elements in the search space allows discovery of catalytic activity for hitherto unknown compositions. Material libraries with very similar composition spreads can show different activities vs. composition trends for different reactions. In order to address the inherent challenge of the huge combinatorial material space and the inability to predict active electrocatalyst compositions, we developed a high-throughput process based on co-sputtered material libraries, and performed high-throughput characterization using energy dispersive X-ray spectroscopy (EDS), scanning transmission electron microscopy (SEM), X-ray diffraction (XRD) and conductivity measurements followed by electrochemical screening by means of a scanning droplet cell. The results show surprising material compositions with increased activity for the oxygen reduction reaction and the hydrogen evolution reaction. Such data are important input data for future data-driven materials prediction. [Figure not available: see fulltext.] © 2021, The Author(s).
    view abstractdoi: 10.1007/s12274-021-3637-z
  • 2021 • 272 Single-Particle Hyperspectral Imaging Reveals Kinetics of Silver Ion Leaching from Alloy Nanoparticles
    Al-Zubeidi, A. and Stein, F. and Flatebo, C. and Rehbock, C. and Hosseini Jebeli, S.A. and Landes, C.F. and Barcikowski, S. and Link, S.
    ACS Nano 15 8363-8375 (2021)
    Gold-silver alloy nanoparticles are interesting for multiple applications, including heterogeneous catalysis, optical sensing, and antimicrobial properties. The inert element gold acts as a stabilizer for silver to prevent particle corrosion, or conversely, to control the release kinetics of antimicrobial silver ions for long-term efficiency at minimum cytotoxicity. However, little is known about the kinetics of silver ion leaching from bimetallic nanoparticles and how it is correlated with silver content, especially not on a single-particle level. To characterize the kinetics of silver ion release from gold-silver alloy nanoparticles, we employed a combination of electron microscopy and single-particle hyperspectral imaging with an acquisition speed fast enough to capture the irreversible silver ion leaching. Single-particle leaching profiles revealed a reduction in silver ion leaching rate due to the alloying with gold as well as two leaching stages, with a large heterogeneity in rate constants. We modeled the initial leaching stage as a shrinking-particle with a rate constant that exponentially depends on the silver content. The second, slower leaching stage is controlled by the electrochemical oxidation potential of the alloy being steadily increased by the change in relative gold content and diffusion of silver atoms through the lattice. Interestingly, individual nanoparticles with similar sizes and compositions exhibited completely different silver ion leaching yields. Most nanoparticles released silver completely, but 25% of them appeared to arrest leaching. Additionally, nanoparticles became slightly porous. Alloy nanoparticles, produced by scalable laser ablation in liquid, together with kinetic studies of silver ion leaching, provide an approach to design the durability or bioactivity of alloy nanoparticles. ©
    view abstractdoi: 10.1021/acsnano.0c10150
  • 2021 • 271 Solvent Selection in Homogeneous Catalysis - Optimization of Kinetics and Reaction Performance
    Huxoll, F. and Jameel, F. and Bianga, J. and Seidensticker, T. and Stein, M. and Sadowski, G. and Vogt, D.
    ACS Catalysis 11 590-594 (2021)
    Solvents have an enormous impact on yield and turnover of chemical reactions in complex media. There is, however, a lack of consistent model-based tools to a priori identify the appropriate solvent for homogeneously catalyzed reactions. Here, a thermodynamically consistent approach for a reductive amination reaction is presented. It combines solvent screening using a thermodynamic-activity model and quantum chemical calculations. The optimization of activity coefficient-based predicted kinetics gives a suitable list of candidate solvents. The results were confirmed by batch experiments in selected solvents. This approach allows reducing time and lab resources for solvent selection to a minimum. ©
    view abstractdoi: 10.1021/acscatal.0c04431
  • 2021 • 270 The electrochemical-step asymmetry index
    Exner, K.S.
    MethodsX 8 (2021)
    The development of oxygen-evolution reaction (OER) electrocatalysts has been spurred by thermodynamic considerations on the free-energy landscape. Most commonly, electrocatalytic activity is approximated by the analysis of the free-energy changes among the mechanistic description, thereby taking only reaction steps with weak-binding adsorbates into account. Herein, a new method, denoted as the electrochemical-step asymmetry index (ESAI), is presented, which approximates electrocatalytic activity by penalizing both too strong as well as too weak bonding of intermediate states in order to mimic the well-known Sabatier principle. • The electrochemical-step asymmetry index (ESAI) is a descriptor to approximate electrocatalytic activity based on the analysis of the free-energy changes for a given mechanistic description, exemplified by the oxygen evolution reaction (OER). • The concept of the ESAI is based on the assumption that the optimum free-energy landscape has an asymmetric shape because this may factor overpotential and kinetic effects in the analysis, and the ESAI penalizes both too strong as well as too weak bonding of intermediate states to render a thorough representation of the Sabatier principle feasible. • The ESAI is a conceptual development of the earlier proposed electrochemical-step symmetry index (ESSI), which relies on a symmetric distribution of the free-energy changes as thermodynamic optimum and which takes only weak-binding adsorbates into account. © 2021
    view abstractdoi: 10.1016/j.mex.2021.101590
  • 2021 • 269 The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions
    Ooka, H. and Huang, J. and Exner, K.S.
    Frontiers in Energy Research 9 (2021)
    The Sabatier principle, which states that the binding energy between the catalyst and the reactant should be neither too strong nor too weak, has been widely used as the key criterion in designing and screening electrocatalytic materials necessary to promote the sustainability of our society. The widespread success of density functional theory (DFT) has made binding energy calculations a routine practice, turning the Sabatier principle from an empirical principle into a quantitative predictive tool. Given its importance in electrocatalysis, we have attempted to introduce the reader to the fundamental concepts of the Sabatier principle with a highlight on the limitations and challenges in its current thermodynamic context. The Sabatier principle is situated at the heart of catalyst development, and moving beyond its current thermodynamic framework is expected to promote the identification of next-generation electrocatalysts. © Copyright © 2021 Ooka, Huang and Exner.
    view abstractdoi: 10.3389/fenrg.2021.654460
  • 2020 • 268 Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
    Wang, Z. and Li, T. and Jiang, Y. and Lafon, O. and Liu, Z. and Trébosc, J. and Baiker, A. and Amoureux, J.-P. and Huang, J.
    Nature Communications 11 (2020)
    Amorphous silica-aluminas (ASAs) are widely used in acid-catalyzed C-H activation reactions and biomass conversions in large scale, which can be promoted by increasing the strength of surface Brønsted acid sites (BAS). Here, we demonstrate the first observation on a synergistic effect caused by two neighboring Al centers interacting with the same silanol group in flame-made ASAs with high Al content. The two close Al centers decrease the electron density on the silanol oxygen and thereby enhance its acidity, which is comparable to that of dealuminated zeolites, while ASAs with small or moderate Al contents provide mainly moderate acidity, much lower than that of zeolites. The ASAs with enhanced acidity exhibit outstanding performances in C–H bond activation of benzene and glucose dehydration to 5-hydroxymethylfurfural, simultaneously with an excellent calcination stability and resistance to leaching, and they offer an interesting potential for a wide range of acid and multifunctional catalysis. © 2020, The Author(s).
    view abstractdoi: 10.1038/s41467-019-13907-7
  • 2020 • 267 Beyond thermodynamic-based material-screening concepts: Kinetic scaling relations exemplified by the chlorine evolution reaction over transition-metal oxides
    Exner, K.S.
    Electrochimica Acta 334 (2020)
    State-of-the-art material screening in the field of electrocatalysis mainly uses the concept of linear scaling relationships in order to express the (free) adsorption energies of different reaction intermediates, adsorbed on the surface of a solid-state electrocatalyst, as function of a descriptor. This thermodynamic analysis, based on the application of the computational hydrogen electrode approach (CHE), ultimately results in the construction of a Volcano plot, which facilitates identifying promising catalysts within a class of materials. The conventional ab initio Volcano concept, however, lacks of two critical aspects: on the one hand the applied overpotential, which constitutes the driving force of an electrocatalytic reaction, is not included in the underlying approach, since the thermodynamic analysis refers to the standard equilibrium potential of the electrocatalytic process; on the other hand, the kinetics is not accounted for. Herein, an alternate material-screening concept is presented, which promotes a discussion of the catalytic performance within a class of materials by explicitly including both the kinetic description and applied overpotential: kinetic scaling relations enable resolving the rate-determining reaction step in a homologous series of single-crystalline electrocatalysts in the overpotential regime of interest for practical applications. The proposed methodology is exemplified by the chlorine evolution reaction over transition-metal oxides, which corresponds to the anode reaction in the industrially relevant chlor-alkali process for the production of gaseous chlorine as basic chemical. © 2019 Elsevier Ltd
    view abstractdoi: 10.1016/j.electacta.2019.135555
  • 2020 • 266 Chemisorption and Physisorption at the Metal/Organic Interface: Bond Energies of Naphthalene and Azulene on Coinage Metal Surfaces
    Kachel, S.R. and Klein, B.P. and Morbec, J.M. and Schöniger, M. and Hutter, M. and Schmid, M. and Kratzer, P. and Meyer, B. and Tonner, R. and Gottfried, J.M.
    Journal of Physical Chemistry C 124 8257-8268 (2020)
    Organic/inorganic hybrid interfaces play a prominent role in organic (opto)electronics, heterogeneous catalysis, sensors, and other current fields of technology. The performance of the related devices and processes depends critically on the nature and strength of interfacial interaction. Here, we use the molecular isomers naphthalene (Nt) and azulene (Az) on the Ag(111) and Cu(111) surfaces as model systems that cover different bonding regimes from physisorption to chemisorption. Az also serves as a model for nonalternant molecular electronic materials and for topological 5-7 defects in graphene. The interaction energies are determined from the quantitative analysis of temperature-programmed desorption data. On both surfaces, Az binds more strongly than Nt, with zero-coverage desorption energies (in kJ/mol) of 120 for Az/Ag and 179 for Az/Cu, compared to 103 for Nt/Ag and 114 for Nt/Cu. The integrated experimental energies are compared with adsorption energies from density-functional theory (DFT) calculations, which include van der Waals contributions using four different correction schemes for the PBE functional: (1) the DFT-D3 scheme with Becke-Johnson damping, (2) the vdWsurf correction based on DFT-TS, (3) a many-body dispersion correction scheme, and (4) the D3surf scheme. Differences in the performance of these methods are discussed. Periodic energy decomposition analysis reveals details of the surface chemical bond and confirms that Az/Cu forms a chemisorptive bond, while the other systems are physisorbed. The variation of the adsorbate-substrate interaction with the topology of the Ï-electron system and the type of surface can be employed to modify the interface properties in graphene-based and organic electronic devices. © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.0c00915
  • 2020 • 265 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 • 264 Direct Mechanocatalysis: Using Milling Balls as Catalysts
    Pickhardt, W. and Grätz, S. and Borchardt, L.
    Chemistry - A European Journal 26 12903-12911 (2020)
    Direct mechanocatalysis describes catalytic reactions under the involvement of mechanical energy with the distinct feature of milling equipment itself being the catalyst. This novel type of catalysis features no solubility challenges of the catalysts nor the substrate and on top offering most facile way of separation. © 2020 The Authors. Published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/chem.202001177
  • 2020 • 263 Electrochemical CO2 Reduction-The Effect of Chalcogenide Exchange in Ni-Isocyclam Complexes
    Gerschel, P. and Battistella, B. and Siegmund, D. and Ray, K. and Apfel, U.-P.
    Organometallics 39 1497-1510 (2020)
    Among the numerous homogeneous electrochemical CO2 reduction catalysts, [Ni(cyclam)]2+ is known as one of the most potent catalysts. Likewise, [Ni(isocyclam)]2+ was reported to enable electrochemical CO2 conversion but has received significantly less attention. However, for both catalysts, a purposeful substitution of a single nitrogen donor group by chalcogen atoms was never reported. In this work, we report a series of isocyclam-based Ni complexes with {ON3}, {SN3}, {SeN3}, and {N4} moieties and investigated the influence of nitrogen/chalcogen substitution on electrochemical CO2 reduction. While [Ni(isocyclam)]2+ showed the highest selectivity toward CO2 reduction within this series with a Faradaic efficiency of 86% for the generation of CO at an overpotential of-1.20 V and acts as a homogeneous catalyst, the O-and S-containing Ni complexes revealed comparable catalytic activities at ca. 0.3 V milder overpotential but tend to form deposits on the electrode, acting as precursors for a heterogeneous catalysis. Moreover, the heterogeneous species generated from the O-and S-containing complexes enable a catalytic hydride transfer to acetonitrile, resulting in the generation of acetaldehyde. The incorporation of selenium, however, resulted in loss of CO2 reduction activity, mainly leading to hydrogen generation that is also catalyzed by a heterogeneous electrodeposit. Copyright © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acs.organomet.0c00129
  • 2020 • 262 Electrolyte Engineering as a Key Strategy Towards a Sustainable Energy Scenario?
    Exner, K.S.
    ChemElectroChem 7 594-595 (2020)
    Major challenges still need to be resolved on the way towards a sustainable energy scenario. A future vision comprises the development of electrocatalysts, refraining from using scarce noble metals, for electrocatalytic key processes, such as hydrogen and oxygen evolution and reduction reactions or CO2 reduction. Hitherto, the focus was set on the investigation of electrode materials, whereas only little emphasis was put on the electrolyte solution. Recently, it was reported that, under non-acidic pH conditions, the composition of the electrolyte solution has a non-negligible effect on the activity of electrocatalytic processes: this outcome puts forth the idea of electrolyte engineering, a promising strategy that, besides the study of enhanced electrode materials, should be put in the focus of future research investigations in electrocatalysis. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/celc.201902009
  • 2020 • 261 Establishing structure-sensitivity of ceria reducibility: Real-Time observations of surface-hydrogen interactions
    Duchoň, T. and Hackl, J. and Mueller, D.N. and Kullgren, J. and Du, D. and Senanayake, S.D. and Mouls, C. and Gottlob, D.M. and Khan, M.I. and Cramm, S. and Veltruská, K. and Matolín, V. and Nemšák, S. and Schneider, C.M.
    Journal of Materials Chemistry A 8 5501-5507 (2020)
    The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure-reducibility relationship under identical conditions. Kinetic rate constants of Ce4+ to Ce3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts. This journal is © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c9ta11784a
  • 2020 • 260 Heterobifunctional Rotaxanes for Asymmetric Catalysis
    Pairault, N. and Zhu, H. and Jansen, D. and Huber, A. and Daniliuc, C.G. and Grimme, S. and Niemeyer, J.
    Angewandte Chemie - International Edition 59 5102-5107 (2020)
    Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine-based thread and a chiral 1,1′-binaphthyl-phosphoric-acid-based macrocycle. High-level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non-interlocked counterparts in terms of reaction rates and stereoselectivities. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201913781
  • 2020 • 259 In Situ X-ray Microscopy Reveals Particle Dynamics in a NiCo Dry Methane Reforming Catalyst under Operating Conditions
    Beheshti Askari, A. and Al Samarai, M. and Morana, B. and Tillmann, L. and Pfänder, N. and Wandzilak, A. and Watts, B. and Belkhou, R. and Muhler, M. and Muhler, M. and Debeer, S.
    ACS Catalysis 10 6223-6230 (2020)
    Herein, we report the synthesis of a γ-Al2O3-supported NiCo catalyst for dry methane reforming (DMR) and study the catalyst using in situ scanning transmission X-ray microscopy (STXM) during the reduction (activation step) and under reaction conditions. During the reduction process, the NiCo alloy particles undergo elemental segregation with Co migrating toward the center of the catalyst particles and Ni migrating to the outer surfaces. Under DMR conditions, the segregated structure is maintained, thus hinting at the importance of this structure to optimal catalytic functions. Finally, the formation of Ni-rich branches on the surface of the particles is observed during DMR, suggesting that the loss of Ni from the outer shell may play a role in the reduced stability and hence catalyst deactivation. These findings provide insights into the morphological and electronic structural changes that occur in a NiCo-based catalyst during DMR. Further, this study emphasizes the need to study catalysts under operating conditions in order to elucidate material dynamics during the reaction. © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.9b05517
  • 2020 • 258 Microscale Atmospheric Pressure Plasma Jet as a Source for Plasma-Driven Biocatalysis
    Yayci, A. and Dirks, T. and Kogelheide, F. and Alcalde, M. and Hollmann, F. and Awakowicz, P. and Bandow, J.E.
    ChemCatChem 12 5893-5897 (2020)
    The use of a microscale atmospheric pressure plasma jet (μAPPJ) was investigated for its potential to supply hydrogen peroxide in biocatalysis. Compared to a previously employed dielectric barrier discharge (DBD), the μAPPJ offered significantly higher H2O2 production rates and better handling of larger reaction volumes. The performance of the μAPPJ was evaluated with recombinant unspecific peroxygenase from Agrocybe aegerita (rAaeUPO). Using plasma-treated buffer, no side reactions with other plasma-generated species were detected. For long-term treatment, rAaeUPO was immobilized, transferred to a rotating bed reactor, and reactions performed using the μAPPJ. The enzyme had a turnover of 36,415 mol mol−1 and retained almost full activity even after prolonged plasma treatment. Overall, the μAPPJ presents a promising plasma source for plasma-driven biocatalysis. © 2020 The Authors. Published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/cctc.202001225
  • 2020 • 257 One-Pot Cooperation of Single-Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization-Hydrosilylation Process
    Sarma, B.B. and Kim, J. and Amsler, J. and Agostini, G. and Weidenthaler, C. and Pfänder, N. and Arenal, R. and Concepción, P. and Plessow, P. and Studt, F. and Prieto, G.
    Angewandte Chemie - International Edition 59 5806-5815 (2020)
    Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201915255
  • 2020 • 256 Origin of Laser-Induced Colloidal Gold Surface Oxidation and Charge Density, and Its Role in Oxidation Catalysis
    Ziefuß, A.R. and Haxhiaj, I. and Müller, S. and Gharib, M. and Gridina, O. and Rehbock, C. and Chakraborty, I. and Peng, B. and Muhler, M. and Parak, W.J. and Barcikowski, S. and Reichenberger, S.
    Journal of Physical Chemistry C 124 20981-20990 (2020)
    Laser fragmentation in liquids (LFL) allows the synthesis of fully inorganic, ultrasmall gold nanoparticles, usAu NPs (<3 nm). Although the general method is well established, there is a lack of understanding the chemical processes that are triggered by the laser pulses, which may dictate the surface properties that are highly important in heterogeneous oxidation catalytic reactions. We observed the formation of radical oxygen species during LFL, which suggested that LFL is a physicochemical process that leads to particle size reductions and initiates oxidative processes. When the ionic strength in the nanoenvironment was increased, the oxidation of the first atomic layer saturated at 50%, whereby the surface charge density increases continuously. We found a correlation between the surface charge density after synthesis of colloidal nanoparticles and its behavior in catalysis. The properties of the laser-generated nanoparticles in the colloidal state appear to have predetermined the catalytic performance. We found that a smaller surface charge density of the usAu NPs was beneficial for the catalytic activity in CO and ethanol oxidation, while their peroxidase-like activity was affected less. The catalytic activity was 2 times higher for samples prepared by chloride-free LFL after ozone pretreatment compared to samples prepared in pure water. Copyright © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.0c06257
  • 2020 • 255 Paradigm change in hydrogen electrocatalysis: The volcano's apex is located at weak bonding of the reaction intermediate
    Exner, K.S.
    International Journal of Hydrogen Energy 45 27221-27229 (2020)
    Volcano plots are a powerful tool to screen electrode materials in the catalysis and battery science communities. Commonly, simple binding energies are analyzed by the concept of linear scaling relationships to describe activity trends in a homologous series of materials, putting forward the picture that an optimum electrode material in the hydrogen evolution reaction (HER) binds the reaction intermediate (RI) thermoneutrally at zero overpotential. This approach, however, consists of various oversimplifications since the applied overpotential and kinetics are not accounted for in the evaluation. In the present article, the apex of the HER volcano is modeled by microkinetics. It is demonstrated that the volcano's top shifts to weak bonding of the RI with increasing driving force as soon as kinetic effects are factored in the analysis. This paradigm change is corroborated by the fact that the constructed volcano plots, using microkinetics and scaling relations for the apex and legs of the volcano respectively, reproduce the high activities of Pt in the HER and RuO2 in the chlorine evolution reaction. © 2020 Hydrogen Energy Publications LLC
    view abstractdoi: 10.1016/j.ijhydene.2020.07.088
  • 2020 • 254 Present and future of surface-enhanced Raman scattering
    Langer, J. and de Aberasturi, D.J. and Aizpurua, J. and Alvarez-Puebla, R.A. and Auguié, B. and Baumberg, J.J. and Bazan, G.C. and Bell, S.E.J. and Boisen, A. and Brolo, A.G. and Choo, J. and Cialla-May, D. and Deckert, V. and Fa...
    ACS Nano 14 28-117 (2020)
    The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article. © 2020 American Chemical Society. All rights reserved.
    view abstractdoi: 10.1021/acsnano.9b04224
  • 2020 • 253 Properties of α-Brass Nanoparticles. 1. Neural Network Potential Energy Surface
    Weinreich, J. and Römer, A. and Paleico, M.L. and Behler, J.
    Journal of Physical Chemistry C 124 12682-12695 (2020)
    Binary metal clusters are of high interest for applications in heterogeneous catalysis and have received much attention in recent years. To gain insights into their structure and composition at the atomic scale, computer simulations can provide valuable information if reliable interatomic potentials are available. In this paper we describe the construction of a high-dimensional neural network potential (HDNNP) intended for simulations of large brass nanoparticles with thousands of atoms, which is also applicable to bulk α-brass and its surfaces. The HDNNP, which is based on reference data obtained from density-functional theory calculations, is very accurate with a root-mean-square error of 1.7 meV/atom for total energies and 39 meV Å-1 for the forces of structures not included in the training set. The potential has been thoroughly validated for a wide range of energetic and structural properties of bulk α-brass, its surfaces as well as clusters of different size and composition demonstrating its suitability for large-scale molecular dynamics and Monte Carlo simulations with first-principles accuracy. © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.0c00559
  • 2020 • 252 Protection strategies for biocatalytic proteins under plasma treatment
    Yayci, A. and Dirks, T. and Kogelheide, F. and Alcalde, M. and Hollmann, F. and Awakowicz, P. and Bandow, J.E.
    Journal of Physics D: Applied Physics 54 (2020)
    In plasma-driven biocatalysis, enzymes are employed to carry out reactions using species generated by non-thermal plasmas as the precursors. We have previously demonstrated that this is feasible in principle, but that the approach suffers from the short lifetime of the biocatalyst under operating conditions. In this work, protection strategies were investigated to prevent the dielectric barrier discharge plasma-induced inactivation of biocatalysts, using recombinant unspecific peroxygenase from Agrocybe aegerita (rAaeUPO), one of the most promising enzymes for plasma-driven biocatalysis. Treatment in oxygen-free atmospheres did not provide any advantage over treatment in synthetic air, indicating that the detrimental reactive species did not originate from oxygen in the plasma phase. Chemical scavengers were employed to eliminate undesired reactive species, without any long-term effect on enzyme lifetime. Similarly, chaperones, including the known stress response proteins Hsp33, CnoX, and RidA did not increase the lifetime of rAaeUPO. Immobilization of the biocatalyst proved effective in preserving enzyme activity. The residual activity of rAaeUPO after plasma treatment strongly depended on the specific immobilization support. Essentially complete protection for at least 15 min of plasma exposure was achieved with an epoxy-butyl-functionalized carrier. This study presents new insights into plasma-protein interactions and plots a path forward for protecting biocatalytic proteins from plasma-mediated inactivation. © 2020 IOP Publishing Ltd.
    view abstractdoi: 10.1088/1361-6463/abb979
  • 2020 • 251 Sequencing of metals in multivariate metal-organic frameworks
    Ji, Z. and Li, T. and Yaghi, O.M.
    Science 369 674-680 (2020)
    We mapped the metal sequences within crystals of metal-oxide rods in multivariate metal-organic framework-74 containing mixed combinations of cobalt (Co), cadmium (Cd), lead (Pb), and manganese (Mn). Atom probe tomography of these crystals revealed the presence of heterogeneous spatial sequences of metal ions that we describe, depending on the metal and synthesis temperature used, as random (Co, Cd, 120°C), short duplicates (Co, Cd, 85°C), long duplicates (Co, Pb, 85°C), and insertions (Co, Mn, 85°C). Three crystals were examined for each sequence type, and the molar fraction of Co among all 12 samples was observed to vary from 0.4 to 0.9, without changing the sequence type. Compared with metal oxides, metal-organic frameworks have high tolerance for coexistence of different metal sizes in their rods and therefore assume various metal sequences. © 2020 American Association for the Advancement of Science. All rights reserved.
    view abstractdoi: 10.1126/science.aaz4304
  • 2020 • 250 Shedding Light on Proton and Electron Dynamics in [FeFe] Hydrogenases
    Lorent, C. and Katz, S. and Duan, J. and Kulka, C.J. and Caserta, G. and Teutloff, C. and Yadav, S. and Apfel, U.-P. and Winkler, M. and Happe, T. and Horch, M. and Zebger, I.
    Journal of the American Chemical Society 142 5493-5497 (2020)
    [FeFe] hydrogenases are highly efficient catalysts for reversible dihydrogen evolution. H2 turnover involves different catalytic intermediates including a recently characterized hydride state of the active site (H-cluster). Applying cryogenic infrared and electron paramagnetic resonance spectroscopy to an [FeFe] model hydrogenase from Chlamydomonas reinhardtii (CrHydA1), we have discovered two new hydride intermediates and spectroscopic evidence for a bridging CO ligand in two reduced H-cluster states. Our study provides novel insights into these key intermediates, their relevance for the catalytic cycle of [FeFe] hydrogenase, and novel strategies for exploring these aspects in detail. Copyright © 2020 American Chemical Society.
    view abstractdoi: 10.1021/jacs.9b13075
  • 2020 • 249 Synergistic Effect of Molybdenum and Tungsten in Highly Mixed Carbide Nanoparticles as Effective Catalysts in the Hydrogen Evolution Reaction under Alkaline and Acidic Conditions
    Fu, Q. and Peng, B. and Masa, J. and Chen, Y.-T. and Xia, W. and Schuhmann, W. and Muhler, M.
    ChemElectroChem 7 983-988 (2020)
    Monometallic Mo and W carbides as well as highly mixed (Mo,W) carbides with various Mo/W ratios were synthesized directly on oxygen-functionalized carbon nanotubes (OCNTs), and used as noble-metal-free electrocatalysts in the hydrogen evolution reaction (HER) under both acidic and alkaline conditions. A purely orthorhombic structure was found in both monometallic and mixed carbide samples by X-ray diffraction. Transmission electron microscopy images showed that the carbide particles were highly dispersed on the OCNTs with well-controlled particle size. The homogeneous distribution of Mo and W in the carbides was confirmed by elemental mapping. (Mo,W)2C/OCNT with a Mo/W ratio of 3 : 1 showed the lowest overpotential to reach a current density of 10 mA/cm2 (87 mV in 0.1 M KOH and 92 mV in 0.5 M H2SO4), and the smallest Tafel slope of 34 mV/dec. Long-term stability under both alkaline and acidic conditions was demonstrated for 24 h. Our results revealed that an optimal amount of W in the mixed carbide can significantly improve its performance in the HER following the Tafel reaction pathway, most likely due to the weakened Mo−Hads bond. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/celc.202000047
  • 2020 • 248 Synthesis, Structure, Properties, and Applications of Bimetallic Nanoparticles of Noble Metals
    Loza, K. and Heggen, M. and Epple, M.
    Advanced Functional Materials 30 (2020)
    Bimetallic nanoparticles of noble metals are of high interest in imaging, biomedical devices, including nanomedicine, and heterogeneous catalysis. Synthesis, properties, characterization, biological properties, and practical applicability of nanoparticles on the basis of platinum group metals and the coin metals Ag and Au are discussed, also in comparison with the corresponding monometallic nanoparticles. In addition to the parameters that are required to characterize monometallic nanoparticles (mainly size, size distribution, shape, crystallographic nature, surface functionalization, charge), further information is required for a full characterization of bimetallic nanoparticles. This concerns the overall elemental composition of a bimetallic nanoparticle population (ratio of the two metals) and the internal distribution of the elements in individual nanoparticles (e.g., the presence of homogeneous alloys, core–shell systems, and possible intermediate stages). It is also important to ensure that all particles are identical in terms of elemental composition, that is, that the homogeneity of the particle population is given. Macroscopic properties like light absorption, antibacterial effects, and catalytic activity depend on these properties. The currently available methods for a full characterization of bimetallic nanoparticles are discussed, and future developments in this field are outlined. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/adfm.201909260
  • 2020 • 247 Thermodynamics and kinetics of glycolytic reactions. Part i: Kinetic modeling based on irreversible thermodynamics and validation by calorimetry
    Vogel, K. and Greinert, T. and Reichard, M. and Held, C. and Harms, H. and Maskow, T.
    International Journal of Molecular Sciences 21 1-20 (2020)
    In systems biology, material balances, kinetic models, and thermodynamic boundary conditions are increasingly used for metabolic network analysis. It is remarkable that the reversibility of enzyme‐catalyzed reactions and the influence of cytosolic conditions are often neglected in kinetic models. In fact, enzyme‐catalyzed reactions in numerous metabolic pathways such as in glycolysis are often reversible, i.e., they only proceed until an equilibrium state is reached and not until the substrate is completely consumed. Here, we propose the use of irreversible thermodynamics to describe the kinetic approximation to the equilibrium state in a consistent way with very few adjustable parameters. Using a flux‐force approach allowed describing the influence of cytosolic conditions on the kinetics by only one single parameter. The approach was applied to reaction steps 2 and 9 of glycolysis (i.e., the phosphoglucose isomerase reaction from glucose 6‐ phosphate to fructose 6‐phosphate and the enolase‐catalyzed reaction from 2‐phosphoglycerate to phosphoenolpyruvate and water). The temperature dependence of the kinetic parameter fulfills the Arrhenius relation and the derived activation energies are plausible. All the data obtained in this work were measured efficiently and accurately by means of isothermal titration calorimetry (ITC). The combination of calorimetric monitoring with simple flux‐force relations has the potential for adequate consideration of cytosolic conditions in a simple manner. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
    view abstractdoi: 10.3390/ijms21218341
  • 2020 • 246 Thermodynamics and kinetics of glycolytic reactions. Part II: Influence of cytosolic conditions on thermodynamic state variables and kinetic parameters
    Vogel, K. and Greinert, T. and Reichard, M. and Held, C. and Harms, H. and Maskow, T.
    International Journal of Molecular Sciences 21 1-20 (2020)
    For systems biology, it is important to describe the kinetic and thermodynamic properties of enzyme-catalyzed reactions and reaction cascades quantitatively under conditions prevailing in the cytoplasm. While in part I kinetic models based on irreversible thermodynamics were tested, here in part II, the influence of the presumably most important cytosolic factors was investigated using two glycolytic reactions (i.e., the phosphoglucose isomerase reaction (PGI) with a uni-uni-mechanism and the enolase reaction with an uni-bi-mechanism) as examples. Crowding by macromolecules was simulated using polyethylene glycol (PEG) and bovine serum albumin (BSA). The reactions were monitored calorimetrically and the equilibrium concentrations were evaluated using the equation of state ePC-SAFT. The pH and the crowding agents had the greatest influence on the reaction enthalpy change. Two kinetic models based on irreversible thermodynamics (i.e., single parameter flux-force and two-parameter Noor model) were applied to investigate the influence of cytosolic conditions. The flux-force model describes the influence of cytosolic conditions on reaction kinetics best. Concentrations of magnesium ions and crowding agents had the greatest influence, while temperature and pH-value had a medium influence on the kinetic parameters. With this contribution, we show that the interplay of thermodynamic modeling and calorimetric process monitoring allows a fast and reliable quantification of the influence of cytosolic conditions on kinetic and thermodynamic parameters. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
    view abstractdoi: 10.3390/ijms21217921
  • 2020 • 245 Universality in Oxygen Evolution Electrocatalysis: High-Throughput Screening and a Priori Determination of the Rate-Determining Reaction Step
    Exner, K.S.
    ChemCatChem 12 2000-2003 (2020)
    Material screening is commonly based on the assessment of linear scaling relations that translate to a Volcano curve in order to identify promising electrode materials, situated at the apex of the Volcano. Recently, an advanced material-screening approach, entitled ESSI-descriptor activity maps, has been introduced by the author. This methodology goes beyond the thermodynamic framework of Volcano plots, as the concept of ESSI-descriptor activity maps evaluates, besides binding energies, the kinetics, applied overpotential, and catalytic symmetry in terms of the electrochemical-step symmetry index (ESSI). Herein, the concept of ESSI-descriptor activity maps is exerted to the oxygen evolution reaction (OER) to derive universal relationships. In contrast to the common procedure in the literature, a suitable range of values for the linear scaling relation's offset is a priori included in the presented model, which enables high-throughput screening of OER catalysts and determination of the rate-determining reaction step (rds) at overpotentials corresponding to typical reaction conditions (ηOER=0.40 V). © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201902363
  • 2020 • 244 What is the role of acid-acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts
    Jansen, D. and Gramüller, J. and Niemeyer, F. and Schaller, T. and Letzel, M.C. and Grimme, S. and Zhu, H. and Gschwind, R.M. and Niemeyer, J.
    Chemical Science 11 4381-4390 (2020)
    Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids. © The Royal Society of Chemistry 2020.
    view abstractdoi: 10.1039/d0sc01026j
  • 2019 • 243 A Z-Scheme-Inspired Photobioelectrochemical H 2 O/O 2 Cell with a 1 V Open-Circuit Voltage Combining Photosystem II and PbS Quantum Dots
    Riedel, M. and Wersig, J. and Ruff, A. and Schuhmann, W. and Zouni, A. and Lisdat, F.
    Angewandte Chemie - International Edition 58 801-805 (2019)
    A biohybrid photobioanode mimicking the Z-scheme has been developed by functional integration of photosystem II (PSII) and PbS quantum dots (QDs) within an inverse opal TiO 2 architecture giving rise to a rather negative water oxidation potential of about −0.55 V vs. Ag/AgCl, 1 m KCl at neutral pH. The electrical linkage between both light-sensitive entities has been established through an Os-complex-modified redox polymer (P Os ), which allows the formation of a multi-step electron-transfer chain under illumination starting with the photo-activated water oxidation at PSII followed by an electron transfer from PSII through P Os to the photo-excited QDs and finally to the TiO 2 electrode. The photobioanode was coupled to a novel, transparent, inverse-opal ATO cathode modified with an O 2 -reducing bilirubin oxidase for the construction of a H 2 O/O 2 photobioelectrochemical cell reaching a high open-circuit voltage of about 1 V under illumination. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201811172
  • 2019 • 242 A Z-Scheme-Inspired Photobioelectrochemical H2O/O2 Cell with a 1 V Open-Circuit Voltage Combining Photosystem II and PbS Quantum Dots
    Riedel, M. and Wersig, J. and Ruff, A. and Schuhmann, W. and Zouni, A. and Lisdat, F.
    Angewandte Chemie - International Edition 58 801-805 (2019)
    A biohybrid photobioanode mimicking the Z-scheme has been developed by functional integration of photosystem II (PSII) and PbS quantum dots (QDs) within an inverse opal TiO2 architecture giving rise to a rather negative water oxidation potential of about −0.55 V vs. Ag/AgCl, 1 m KCl at neutral pH. The electrical linkage between both light-sensitive entities has been established through an Os-complex-modified redox polymer (POs), which allows the formation of a multi-step electron-transfer chain under illumination starting with the photo-activated water oxidation at PSII followed by an electron transfer from PSII through POs to the photo-excited QDs and finally to the TiO2 electrode. The photobioanode was coupled to a novel, transparent, inverse-opal ATO cathode modified with an O2-reducing bilirubin oxidase for the construction of a H2O/O2 photobioelectrochemical cell reaching a high open-circuit voltage of about 1 V under illumination. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201811172
  • 2019 • 241 Activity-Stability Volcano Plots for Material Optimization in Electrocatalysis
    Exner, K.S.
    ChemCatChem 11 3234-3241 (2019)
    In the last two decades, research in electrocatalysis has been spurred by theoretical calculations and predictions based on the concept of ab initio thermodynamics, which has become a valuable tool for computational researchers in material screening. These investigations most commonly result into the construction of activity-based volcano plots in order to predict potential electrocatalysts for the application in practice. However, the prototypical activity-based volcano concept neither captures the influence of the applied overpotential on the activity nor the stability of electrode surfaces. Herein, the well-established volcano approach is expanded by constructing activity-stability volcano plots, which, beside the activity, also enclose the stability and the applied overpotential into the analysis. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201900500
  • 2019 • 240 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 • 239 Direct Growth of Highly Strained Pt Islands on Branched Ni Nanoparticles for Improved Hydrogen Evolution Reaction Activity
    Alinezhad, A. and Gloag, L. and Benedetti, T.M. and Cheong, S. and Webster, R.F. and Roelsgaard, M. and Iversen, B.B. and Schuhmann, W. and Gooding, J.J. and Tilley, R.D.
    Journal of the American Chemical Society 141 16202-16207 (2019)
    The direct growth of Pt islands on lattice mismatched Ni nanoparticles is a major synthetic challenge and a promising strategy to create highly strained Pt atoms for electrocatalysis. By using very mild reaction conditions, Pt islands with tunable strain were formed directly on Ni branched particles. The highly strained 1.9 nm Pt-island on branched Ni nanoparticles exhibited high specific activity and the highest mass activity for hydrogen evolution (HER) in a pH 13 electrolyte. These results show the ability to synthetically tune the size of the Pt islands to control the strain to give higher HER activity. Copyright © 2019 American Chemical Society.
    view abstractdoi: 10.1021/jacs.9b07659
  • 2019 • 238 Direct Mechanocatalysis: Palladium as Milling Media and Catalyst in the Mechanochemical Suzuki Polymerization
    Vogt, C.G. and Grätz, S. and Lukin, S. and Halasz, I. and Etter, M. and Evans, J.D. and Borchardt, L.
    Angewandte Chemie - International Edition 58 18942-18947 (2019)
    The milling ball is the catalyst. We introduce a palladium-catalyzed reaction inside a ball mill, which makes catalyst powders, ligands, and solvents obsolete. We present a facile and highly sustainable synthesis concept for palladium-catalyzed C−C coupling reactions, exemplarily showcased for the Suzuki polymerization of 4-bromo or 4-iodophenylboronic acid giving poly(para-phenylene). Surprisingly, we observe one of the highest degrees of polymerization (199) reported so far. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201911356
  • 2019 • 237 Direct, Selective Production of Aromatic Alcohols from Ethanol Using a Tailored Bifunctional Cobalt-Hydroxyapatite Catalyst
    Wang, Q.-N. and Weng, X.-F. and Zhou, B.-C. and Lv, S.-P. and Miao, S. and Zhang, D. and Han, Y. and Scott, S.L. and Schüth, F. and Lu, A.-H.
    ACS Catalysis 9 7204-7216 (2019)
    Aromatic alcohols are essential components of many solvents, coatings, plasticizers, fine chemicals, and pharmaceuticals. Traditional manufacturing processes involving the oxidation of petroleum-derived aromatic hydrocarbons suffer from low selectivity due to facile overoxidation reactions which produce aromatic aldehydes, acids, and esters. Here we report a Co-containing hydroxyapatite (HAP) catalyst that converts ethanol directly to methylbenzyl alcohols (MB-OH, predominantly 2-MB-OH) at 325 °C. The dehydrogenation of ethanol to acetaldehyde, which is catalyzed by Co2+, has the highest reaction barrier. Acetaldehyde undergoes rapid, HAP-catalyzed condensation and forms the key intermediate, 2-butenal, which yields aromatic aldehydes through self-condensation and then MB-OH via hydrogenation. In the presence of Co2+, 2-butenal is selectively hydrogenated to 2-butenol. This reaction does not hinder aromatization because cross-coupling between 2-butenal and 2-butenol leads directly to MB-OH without passing through MBâ•O. Using these insights a dual-bed catalyst configuration was designed for use in a single reactor to improve the aromatic alcohol selectivity. Its successful use supports the proposed reaction mechanism. Copyright © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.9b02566
  • 2019 • 236 Encapsulation of sub-micrometer sized zeolites by porous silica – towards a rational design strategy for functional yolk-shells
    Joshi, H. and Schmidt, W. and Schüth, F.
    Microporous and Mesoporous Materials 1-8 (2019)
    Catalysis often requires spatial separation of active centres. In material science this translates to a challenge in the synthesis of such materials, namely core-shells. Yolk-shell materials, a type of core-shell materials, possess a void between the core and shell that can be advantageous in catalysis. Yolk-shell materials with zeolitic core have not been reported extensively, despite their potential applicability in catalysis. This stems from the non-spherical morphology and surface properties of the zeolites, which makes controlled coating without defects difficult. Herein, we report a strategy for the encapsulation of beta zeolite (HBEA) with disordered mesoporous silica shell (HBEA@void@mSiO 2 ). HBEA is chosen as the centre (yolk) due to its cuboidal shape. The process involves creation of two shells, (a) sacrificial shell composed of resorcinol and formaldehyde, and (b) mesoporous silica shell. The result is an organic@inorganic hybrid that is thermally treated to obtain the corresponding hybrid. Polyvinylpyrrolidone (PVP) is an important component of the synthesis which assists in obtaining a uniform coating around the core. Thorough morphological, structural, fractal and textural characterization of this material was performed by electron microscopy, XRD, SAXS and sorption techniques. The hybrid possesses a hierarchical structure with an increasing porosity and spatial isolation of the core by the presence of a void. The siliceous nature of HBEA@void@mSiO 2 also enables a post-synthesis treatment for functional modification with mercaptosilane groups. The synthesis process shown here is highly controllable and has laid a solid foundation for a generalized synthesis strategy to build functional yolk-shell materials based on zeolites. © 2019
    view abstractdoi: 10.1016/j.micromeso.2019.03.013
  • 2019 • 235 Excellent Oxygen Reduction Reaction Performance in Self-Assembled Amyloid-β/Platinum Nanoparticle Hybrids with Effective Platinum-Nitrogen Bond Formation
    Jindal, A. and Tashiro, K. and Kotani, H. and Takei, T. and Reichenberger, S. and Marzun, G. and Barcikowski, S. and Kojima, T. and Yamamoto, Y.
    ACS Applied Energy Materials 2 6536-6541 (2019)
    The development of highly efficient catalysts for electrochemical oxygen reduction reactions (ORRs) is crucial for energy applications such as metal-air batteries and fuel cells. Here, we show an enhanced electrocatalytic activity of a new functional material composed of Pt nanoparticles (PtNPs) and self-assembled β-sheet peptides (βPs). The PtNP/βP hybrids, under an optimized assembly condition, display an ORR electrocatalytic activity that is higher than that of a commercially available benchmark Pt/C electrocatalyst in terms of the onset potential and reaction kinetics. Moreover, the PtNP/βP hybrids show one order of magnitude higher ORR mass activity than previously reported peptide-based ORR electrocatalysts. The superb ORR activity with high durability is derived from the well-dispersed PtNPs on βPs, where 50% of the amine groups on the side chain bound with Pt to form Pt-N bonds that function as active sites for the catalytic reaction. This work opens new avenues for efficient ORR electrocatalysts using self-assembled peptides. Copyright © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acsaem.9b01103
  • 2019 • 234 Is Thermodynamics a Good Descriptor for the Activity? Re-Investigation of Sabatier's Principle by the Free Energy Diagram in Electrocatalysis
    Exner, K.S.
    ACS Catalysis 5320-5329 (2019)
    The computational hydrogen electrode (CHE) approach has spurred ab initio investigations in the field of electrocatalysis, since the underlying concept enables to quantify free energy changes, ?G (thermodynamics), for the formation of reaction intermediates on an electrocatalyst surface. The connection between thermodynamics and kinetics (activity) is achieved by Sabatier's principle: the optimum situation to realize an active electrocatalyst is ascribed to reaction intermediates that are thermoneutrally bound (?G = 0 eV) at zero overpotential. In order to validate the linkage between thermodynamics and kinetics at zero overpotential for two-electron processes, free energy diagrams as a function of the applied electrode potential are compiled. Herein, the chlorine evolution reaction (CER) over RuO2(110), one of the best understood model systems in electrocatalysis, is used as a starting point for this investigation. It turns out that the connection between thermodynamics and kinetics at zero overpotential does not reproduce activity trends correctly if the Tafel slope is overpotential dependent. Therefore, it appears expedient to include the applied overpotential into the thermodynamic framework: for electrocatalysts with a change in the Tafel slope, it is suggested to employ the absolute free energy change for the formation of a reaction intermediate at respective overpotential ?, |?G(?)|, as thermodynamic descriptor for the kinetics of two-electron processes, which may aid the construction of overpotential-dependent Volcano plots for improved material screening. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.9b00732
  • 2019 • 233 Magnesium based materials for hydrogen based energy storage: Past, present and future
    Yartys, V.A. and Lototskyy, M.V. and Akiba, E. and Albert, R. and Antonov, V.E. and Ares, J.R. and Baricco, M. and Bourgeois, N. and Buckley, C.E. and Bellosta von Colbe, J.M. and Crivello, J.-C. and Cuevas, F. and Denys, R.V. and...
    International Journal of Hydrogen Energy 44 7809-7859 (2019)
    Magnesium hydride owns the largest share of publications on solid materials for hydrogen storage. The “Magnesium group” of international experts contributing to IEA Task 32 “Hydrogen Based Energy Storage” recently published two review papers presenting the activities of the group focused on magnesium hydride based materials and on Mg based compounds for hydrogen and energy storage. This review article not only overviews the latest activities on both fundamental aspects of Mg-based hydrides and their applications, but also presents a historic overview on the topic and outlines projected future developments. Particular attention is paid to the theoretical and experimental studies of Mg-H system at extreme pressures, kinetics and thermodynamics of the systems based on MgH 2 , nanostructuring, new Mg-based compounds and novel composites, and catalysis in the Mg based H storage systems. Finally, thermal energy storage and upscaled H storage systems accommodating MgH 2 are presented. © 2019 The Authors
    view abstractdoi: 10.1016/j.ijhydene.2018.12.212
  • 2019 • 232 Micellar Brønsted Acid Mediated Synthesis of DNA-Tagged Heterocycles
    Škopić, M.K. and Götte, K. and Gramse, C. and Dieter, M. and Pospich, S. and Raunser, S. and Weberskirch, R. and Brunschweiger, A.
    Journal of the American Chemical Society 141 10546-10555 (2019)
    The translation of well-established molecular biology methods such as genetic coding, selection, and DNA sequencing to combinatorial organic chemistry and compound identification has made extremely large compound collections, termed DNA-encoded libraries, accessible for drug screening. However, the reactivity of the DNA imposes limitations on the choice of chemical methods for encoded library synthesis. For example, strongly acidic reaction conditions must be avoided because they damage the DNA by depurination, i.e. the cleavage of purine bases from the oligomer. Application of micellar catalysis holds much promise for encoded chemistry. Aqueous micellar dispersions enabled compound synthesis under often appealingly mild conditions. Amphiphilic block copolymers covalently functionalized with sulfonic acid moieties in the lipophilic portion assemble in water and locate the Brønsted catalyst in micelles. These acid nanoreactors enabled the reaction of DNA-conjugated aldehydes to diverse substituted tetrahydroquinolines and aminoimidazopyridines by Povarov and Groebke-Blackburn-Bienaymé reactions, respectively, and the cleavage of tBoc protective groups from amines. The polymer micelle design was successfully translated to the Cu/Bipyridine/TEMPO system mediating the oxidation of DNA-coupled alcohols to the corresponding aldehydes. These results suggest a potentially broad applicability of polymer micelles for encoded chemistry. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/jacs.9b05696
  • 2019 • 231 Milling Down to Nanometers: A General Process for the Direct Dry Synthesis of Supported Metal Catalysts
    Schreyer, H. and Eckert, R. and Immohr, S. and de Bellis, J. and Felderhoff, M. and Schüth, F.
    Angewandte Chemie - International Edition 58 11262-11265 (2019)
    Supported catalysts are among the most important classes of catalysts. They are typically prepared by wet-chemical methods, such as impregnation or co-precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of a support oxide leads in many cases to supported catalysts with particles in the nanometer size range. Various supports, including TiO2, Al2O3, Fe2O3, and Co3O4, and different metals, such as Au, Pt, Ag, Cu, and Ni, were studied, and for each of the supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts. The method thus provides a simple and cost-effective alternative to the conventionally used impregnation methods. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201903545
  • 2019 • 230 Modular Pd/Zeolite Composites Demonstrating the Key Role of Support Hydrophobic/Hydrophilic Character in Methane Catalytic Combustion
    Losch, P. and Huang, W. and Vozniuk, O. and Goodman, E.D. and Schmidt, W. and Cargnello, M.
    ACS Catalysis 9 4742-4753 (2019)
    Complete catalytic oxidation of methane in the presence of steam at low temperatures (T &lt; 400 °C) is a crucial reaction for emission control, yet it presents profound challenges. The activation of the strong C-H bond of methane at low temperature is difficult, and the water present in any realistic application poisons the active surface and promotes sintering of Pd particles during the reaction. Finding materials that can deliver high reaction rates while being more resistant to the presence of water is imperative for advancing several technological applications of natural gas-based systems. However, methods to fairly compare the activity of Pd catalysts (the most active metal for methane combustion) are needed in order to perform useful structure-property relationship studies. Here, we report a method to study how zeolite hydrophobicity affects the activity of Pd nanoparticles in the reaction, which led to a significant improvement in the water resistance. Mesoporous zeolites were synthesized starting from commercially available microporous zeolites. In this way, a variety of hierarchically porous zeolites, with different hydrophobic/hydrophilic character, were prepared. Preformed colloidal Pd nanoparticles could be deposited within mesostructured zeolites. This approach enabled the systematic study of key parameters such as zeolite framework, Al content, and the Pd loading while maintaining the same Pd particle size and structure for all the samples. Detailed catalytic studies revealed an optimum hydrophobic/hydrophilic character, and a promising steam-resistant catalyst, namely, 3.2 nm Pd particles supported on mesoporous zeolite beta or USY with a Si/Al ratio of 40, emerged from this multiparametric study with a T50 of 355 °C and T90 of 375 °C (where T50 and T90 are temperature values at which the samples reach 50% and 90% methane conversion, respectively) in steam-containing reaction conditions. Finally, we verified that the designed catalysts were stable by in-depth postcatalysis characterization and operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) analyses confirming that water adsorbs less strongly on the active PdO surface due to interaction with the zeolite acid sites. This method can be of general use to study how zeolite supports affect the reactivity of supported metals in several catalytic applications. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.9b00596
  • 2019 • 229 MOFs for Electrocatalysis: From Serendipity to Design Strategies
    Aiyappa, H.B. and Masa, J. and Andronescu, C. and Muhler, M. and Fischer, R.A. and Schuhmann, W.
    Small Methods 3 (2019)
    The rapid upsurge of metal–organic frameworks (MOFs) as well as MOF-derived materials has stimulated profound interest to capitalize on their many potential untapped benefits in electrocatalysis for energy applications. The possibility of tuning the metal–ligand junctions of the MOF architecture opens new avenues to design robust, extended heterostructures for addressing the present-day energy challenges. Interestingly, despite having detailed crystallographic information, it is often difficult to envisage the interplay of charge transport (electrons and ions), mass transport (pore system) together with the specific effects of the molecularly defined reaction center of MOFs for a given electrocatalytic reaction. Here, guidelines are offered for judiciously engineering the electronic structure of MOFs to deliver targeted electrocatalytic function. Some of the pivotal works on MOF-based materials for electrocatalysis are discussed, which can be correlated to the biological models in terms of their structural resemblance and an instructive insight is provided about the “new chemistry” that can be explored based on the lessons learned from nature in combination with the theoretical understanding of the energetics of the reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/smtd.201800415
  • 2019 • 228 Molecular cobalt corrole complex for the heterogeneous electrocatalytic reduction of carbon dioxide
    Gonglach, S. and Paul, S. and Haas, M. and Pillwein, F. and Sreejith, S.S. and Barman, S. and De, R. and Müllegger, S. and Gerschel, P. and Apfel, U.-P. and Coskun, H. and Aljabour, A. and Stadler, P. and Schöfberger, W. and Roy, S.
    Nature Communications 10 (2019)
    Electrochemical conversion of CO2 to alcohols is one of the most challenging methods of conversion and storage of electrical energy in the form of high-energy fuels. The challenge lies in the catalyst design to enable its real-life implementation. Herein, we demonstrate the synthesis and characterization of a cobalt(III) triphenylphosphine corrole complex, which contains three polyethylene glycol residues attached at the meso-phenyl groups. Electron-donation and therefore reduction of the cobalt from cobalt(III) to cobalt(I) is accompanied by removal of the axial ligand, thus resulting in a square-planar cobalt(I) complex. The cobalt(I) as an electron-rich supernucleophilic d8-configurated metal centre, where two electrons occupy and fill up the antibonding dz 2 orbital. This orbital possesses high affinity towards electrophiles, allowing for such electronically configurated metals reactions with carbon dioxide. Herein, we report the potential dependent heterogeneous electroreduction of CO2 to ethanol or methanol of an immobilized cobalt A3-corrole catalyst system. In moderately acidic aqueous medium (pH = 6.0), the cobalt corrole modified carbon paper electrode exhibits a Faradaic Efficiency (FE%) of 48 % towards ethanol production. © 2019, The Author(s).
    view abstractdoi: 10.1038/s41467-019-11868-5
  • 2019 • 227 Nanoscopic Porous Iridium/Iridium Dioxide Superstructures (15 nm): Synthesis and Thermal Conversion by In Situ Transmission Electron Microscopy
    Pappert, K. and Loza, K. and Shviro, M. and Hagemann, U. and Heggen, M. and Dunin-Borkowski, R.E. and Schierholz, R. and Maeda, T. and Kaneko, K. and Epple, M.
    Chemistry - A European Journal 25 11048-11057 (2019)
    Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201901623
  • 2019 • 226 New Insights into the Catalytic Activity of Cobalt Orthophosphate Co3(PO4)2 from Charge Density Analysis
    Keil, H. and Hellström, M. and Stückl, C. and Herbst-Irmer, R. and Behler, J. and Stalke, D.
    Chemistry - A European Journal 25 15786-15794 (2019)
    An extensive characterization of Co3(PO4)2 was performed by topological analysis according to Bader‘s Quantum Theory of Atoms in Molecules from the experimentally and theoretically determined electron density. This study sheds light on the reactivity of cobalt orthophosphate as a solid-state heterogeneous oxidative-dehydration and -dehydrogenation catalyst. Various faces of the bulk catalyst were identified as possible reactive sites given their topological properties. The charge accumulations and depletions around the two independent five- and sixfold-coordinated cobalt atoms, found in the topological analysis, are correlated to the orientation and population of the d-orbitals. It is shown that the (011) face has the best structural features for catalysis. Fivefold-coordinated ions in close proximity to advantageously oriented vacant coordination sites and electron depletions suit the oxygen lone pairs of the reactant, mainly for chemisorption. This is confirmed both from the multipole refinement as well as from density functional theory calculations. Nearby basic phosphate ions are readily available for C−H activation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/chem.201902303
  • 2019 • 225 On the Theory of Electrolytic Dissociation, the Greenhouse Effect, and Activation Energy in (Electro)Catalysis: A Tribute to Svante Augustus Arrhenius
    Masa, J. and Barwe, S. and Andronescu, C. and Schuhmann, W.
    Chemistry - A European Journal 25 158-166 (2019)
    Svante Augustus Arrhenius (1859, Vik - 1927, Stockholm) received the Nobel Prize for Chemistry in 1903 “in recognition of the extraordinary services he rendered to the advancement of chemistry by his electrolytic theory of dissociation”. Arrhenius was a physicist, and he received his PhD from the University of Uppsala, where he later became a professor for phyiscal chemistry, the first in the country for this subject. He was offered several positions as professor abroad, but decided to remain in Sweden and to build a Nobel Institute for physical chemistry using the Nobel funds. He remained director of the Institute until his death. There are powerful lessons to take from Svante August Arrhenius’ journey leading to a Nobel laureate as there are from his tremendous contributions to chemistry and science in general, including climate science, immunochemistry and cosmology. The theory of electrolytic dissociation for which Arrhenius received the 1903 Nobel Prize in Chemistry has had a profound impact on our understanding of the chemistry of solutions, chemical reactivity, mechanisms underlying chemical transformations as well as physiological processes. As a tribute to Arrhenius, we present a brief historical perspective and present status of the theory of electrolytic dissociation, its relevance and role to the development of electrochemistry, as well as some perspectives on the possible role of the theory to future advancements in electroanalysis, electrocatalysis and electrochemical energy storage. The review briefly highlights Arrhenius’ contribution to climate science owing to his studies on the potential effects of increased anthropogenic CO2 emissions on the global climate. These studies were far ahead of their time and revealed a daunting global dilemma, global warming, that we are faced with today. Efforts to abate or reverse CO2 accumulation constitute one of the most pressing scientific problems of our time, “man's urgent strive to save self from the adverse effects of his self-orchestrated change on the climate”. Finally, we review the application of the Arrhenius equation that correlates reaction rate constants (k) and temperature (T); (Formula presented.), in determining reaction barriers in catalysis with a particular focus on recent modifications of the equation to account for reactions exhibiting non-linear Arrhenius behavior with concave curvature due to prevalence of quantum mechanical tunneling, as well as infrequent convexity of Arrhenius plots due to decrease of the microcanonical rate coefficient with energy as observed for some enzyme catalyzed reactions. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201805264
  • 2019 • 224 Oxygen Evolution Electrocatalysis of a Single MOF-Derived Composite Nanoparticle on the Tip of a Nanoelectrode
    Aiyappa, H.B. and Wilde, P. and Quast, T. and Masa, J. and Andronescu, C. and Chen, Y.-T. and Muhler, M. and Fischer, R.A. and Schuhmann, W.
    Angewandte Chemie - International Edition 58 8927-8931 (2019)
    Determination of the intrinsic electrocatalytic activity of nanomaterials by means of macroelectrode techniques is compromised by ensemble and film effects. Here, a unique “particle on a stick” approach is used to grow a single metal–organic framework (MOF; ZIF-67) nanoparticle on a nanoelectrode surface which is pyrolyzed to generate a cobalt/nitrogen-doped carbon (CoN/C) composite nanoparticle that exhibits very high catalytic activity towards the oxygen evolution reaction (OER) with a current density of up to 230 mA cm−2 at 1.77 V (vs. RHE), and a high turnover frequency (TOF) of 29.7 s−1 at 540 mV overpotential. Identical location transmission electron microscopy (IL-TEM) analysis substantiates the “self-sacrificial” template nature of the MOF, while post-electrocatalysis studies reveal agglomeration of Co centers within the CoN/C composite during the OER. “Single-entity” electrochemical analysis allows for deriving the intrinsic electrocatalytic activity and furnishes insight into the transient behavior of the electrocatalyst under reaction conditions. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201903283
  • 2019 • 223 Perspective of Surfactant-Free Colloidal Nanoparticles in Heterogeneous Catalysis
    Reichenberger, S. and Marzun, G. and Muhler, M. and Barcikowski, S.
    ChemCatChem 11 4489-4518 (2019)
    Due to material gaps and synthesis-related cross-correlations in heterogeneous catalysis, chemists and physicists are constantly motivated to develop novel catalyst preparation methods for independent control of morphology, size, and composition. Within this article, advances, opportunities, and the current limits of laser-based catalyst preparation technique, as well as synergies with conventional methods will be reviewed in terms of purity, particle size, morphology, composition, and nanoparticle-support interaction. It will be shown, that the surfactant-free particles represent ideal model materials to validate kinetic models and conduct parametric activity studies by independent adjustment of functional properties like nanoparticle size, composition, and load. Consequently, the importance of transient plasma dynamics tailoring nanoparticle formation will be pointed out, comparing experimental studies with own calculations and novel simulations taken from literature. Finally, perspectives of surfactant-free colloidal nanoparticles for unrevealing active sites in heterogeneous catalysts are presented. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201900666
  • 2019 • 222 Predicting the high concentration co-solvent influence on the reaction equilibria of the ADH-catalyzed reduction of acetophenone
    Wangler, A. and Loll, R. and Greinert, T. and Sadowski, G. and Held, C.
    Journal of Chemical Thermodynamics 128 275-282 (2019)
    The use of co-solvents for the enhancement of the reaction parameters reaction rate, yield and enantioselectivity is an established optimization strategy in biotechnology. To determine the influence of co-solvents on even one of these reaction parameters requires a great amount of experimental data. Thus, predictive and physically sound models are desired to decrease the amount of experimental effort. This work aims at providing such a framework, which was applied to the ADH (alcohol dehydrogenase)-catalyzed reduction of acetophenone at 303.15 K and 1 bar in water (neat) and under the influence of up to 20 wt-% of polyethylene glycol (PEG) and 15 wt-% trisodium citrate (Na3Cit). In a first step, the equilibrium composition was measured at constant pH. It was then shown that high concentration of PEG or Na3Cit changed the equilibrium position significantly (up to a factor of 13) compared to neat reaction mixtures. To be able to predict this strong co-solvent influence on the reaction equilibrium, the experimentally determined equilibrium compositions of the neat reaction were converted into a thermodynamic equilibrium constant Kth using the activity coefficients γi of the reacting agents. The latter were predicted by electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC–SAFT). These finally allowed quantitatively predicting the high concentration co-solvent influence on the equilibrium position. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.jct.2018.08.021
  • 2019 • 221 Recent Advancements Towards Closing the Gap between Electrocatalysis and Battery Science Communities: The Computational Lithium Electrode and Activity–Stability Volcano Plots
    Exner, K.S.
    ChemSusChem 12 2330-2344 (2019)
    Despite of the fact that the underlying processes are of electrochemical nature, electrocatalysis and battery research are commonly perceived as two disjointed research fields. Herein, recent advancements towards closing this apparent community gap by discussing the concepts of the constrained ab initio thermodynamics approach and the volcano relationship, which were originally introduced for studying heterogeneously catalyzed reactions by first-principles methods at the beginning of the 21st century, are summarized. The translation of the computational hydrogen electrode (CHE) approach or activity-based volcano plots to a computational lithium electrode (CLiE) or activity–stability volcano plots, respectively, for the investigation of electrode surfaces in batteries may refine theoretical modeling with the aim that enhancements of the underlying concepts are transferred between the research communities. The presented strategy of developing novel approaches by interdisciplinary research activities may trigger further progress of improved theoretical concepts in the near future. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201900298
  • 2019 • 220 Thermodynamic Activity-Based Solvent Design for Bioreactions
    Wangler, A. and Held, C. and Sadowski, G.
    Trends in Biotechnology 37 1038-1041 (2019)
    To improve the kinetics of enzyme-catalyzed reactions, cosolvents are commonly added to reaction mixtures. The search for a good cosolvent is still empirical and experimentally based. We discuss a thermodynamic activity-based approach that improves biocatalytic processes by predicting cosolvent influences on Michaelis constants, ultimately reducing time and cost. © 2019 Elsevier Ltd
    view abstractdoi: 10.1016/j.tibtech.2019.04.015
  • 2019 • 219 Towards maximized utilization of iridium for the acidic oxygen evolution reaction
    Ledendecker, M. and Geiger, S. and Hengge, K. and Lim, J. and Cherevko, S. and Mingers, A.M. and Göhl, D. and Fortunato, G.V. and Jalalpoor, D. and Schüth, F. and Scheu, C. and Mayrhofer, K.J.J.
    Nano Research 12 2275-2280 (2019)
    The reduction in noble metal content for efficient oxygen evolution catalysis is a crucial aspect towards the large scale commercialisation of polymer electrolyte membrane electrolyzers. Since catalytic stability and activity are inversely related, long service lifetime still demands large amounts of low-abundant and expensive iridium. In this manuscript we elaborate on the concept of maximizing the utilisation of iridium for the oxygen evolution reaction. By combining different tin oxide based support materials with liquid atomic layer deposition of iridium oxide, new possibilities are opened up to grow thin layers of iridium oxide with tuneable noble metal amounts. In-situ, time- and potential-resolved dissolution experiments reveal how the stability of the substrate and the catalyst layer thickness directly affect the activity and stability of deposited iridium oxide. Based on our results, we elaborate on strategies how to obtain stable and active catalysts with maximized iridium utilisation for the oxygen evolution reaction and demonstrate how the activity and durability can be tailored correspondingly. Our results highlight the potential of utilizing thin noble metal films with earth abundant support materials for future catalytic applications in the energy sector. [Figure not available: see fulltext.]. © 2019, The author(s).
    view abstractdoi: 10.1007/s12274-019-2383-y
  • 2019 • 218 Viewpoint: Atomic-Scale Design Protocols toward Energy, Electronic, Catalysis, and Sensing Applications
    Belviso, F. and Claerbout, V.E.P. and Comas-Vives, A. and Dalal, N.S. and Fan, F.-R. and Filippetti, A. and Fiorentini, V. and Foppa, L. and Franchini, C. and Geisler, B. and Ghiringhelli, L.M. and Groß, A. and Hu, S. and Íñigu...
    Inorganic Chemistry 58 14939-14980 (2019)
    Nanostructured materials are essential building blocks for the fabrication of new devices for energy harvesting/storage, sensing, catalysis, magnetic, and optoelectronic applications. However, because of the increase of technological needs, it is essential to identify new functional materials and improve the properties of existing ones. The objective of this Viewpoint is to examine the state of the art of atomic-scale simulative and experimental protocols aimed to the design of novel functional nanostructured materials, and to present new perspectives in the relative fields. This is the result of the debates of Symposium I "Atomic-scale design protocols towards energy, electronic, catalysis, and sensing applications", which took place within the 2018 European Materials Research Society fall meeting. © 2019 American Chemical Society.
    view abstractdoi: 10.1021/acs.inorgchem.9b01785
  • 2018 • 217 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 • 216 A short perspective of modeling electrode materials in lithium-ion batteries by the ab initio atomistic thermodynamics approach
    Exner, K.S.
    Journal of Solid State Electrochemistry 22 3111-3117 (2018)
    Atomic-scale insights into the performance of electrode materials in lithium-ion batteries require thermodynamic considerations as first step in order to determine potential surface structures that are relevant for subsequent kinetic studies. Within the last 20 years, research in heterogeneous catalysis as well as in electrocatalysis has been spurred by the ab initio atomistic thermodynamics approach, whose application for electrode materials in lithium-ion batteries is eyed and discussed in this perspective article. © 2018, Springer-Verlag GmbH Germany, part of Springer Nature.
    view abstractdoi: 10.1007/s10008-018-4017-9
  • 2018 • 215 Bioelectrocatalytic and electrochemical cascade for phosphate sensing with up to 6 electrons per analyte molecule
    Kopiec, G. and Starzec, K. and Kochana, J. and Kinnunen-Skidmore, T.P. and Schuhmann, W. and Campbell, W.H. and Ruff, A. and Plumeré, N.
    Biosensors and Bioelectronics 117 501-507 (2018)
    Despite the availability of numerous electroanalytical methods for phosphate quantification, practical implementation in point-of-use sensing remains virtually nonexistent because of interferences from sample matrices or from atmospheric O2. In this work, phosphate determination is achieved by the purine nucleoside phosphorylase (PNP) catalyzed reaction of inosine and phosphate to produce hypoxanthine which is subsequently oxidized by xanthine oxidase (XOx), first to xanthine and then to uric acid. Both PNP and XOx are integrated in a redox active Os-complex modified polymer, which not only acts as supporting matrix for the bienzymatic system but also shuttles electrons from the hypoxanthine oxidation reaction to the electrode. The bienzymatic cascade in this second generation phosphate biosensor selectively delivers four electrons for each phosphate molecule present. We introduced an additional electrochemical process involving uric acid oxidation at the underlying electrode. This further enhances the anodic current (signal amplification) by two additional electrons per analyte molecule which mitigates the influence of electrochemical interferences from the sample matrix. Moreover, while the XOx catalyzed reaction is sensitive to O2, the uric acid production and therefore the delivery of electrons through the subsequent electrochemical process are independent of the presence of O2. Consequently, the electrochemical process counterbalances the O2 interferences, especially at low phosphate concentrations. Importantly, the electrochemical uric acid oxidation specifically reports on phosphate concentration since it originates from the product of the bienzymatic reactions. These advantageous properties make this bioelectrochemical-electrochemical cascade particularly promising for point-of-use phosphate measurements. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.bios.2018.06.047
  • 2018 • 214 Catalysis of Carbon Dioxide Photoreduction on Nanosheets: Fundamentals and Challenges
    Sun, Z. and Talreja, N. and Tao, H. and Texter, J. and Muhler, M. and Strunk, J. and Chen, J.
    Angewandte Chemie - International Edition 57 7610-7627 (2018)
    The transformation of CO2 into fuels and chemicals by photocatalysis is a promising strategy to provide a long-term solution to mitigating global warming and energy-supply problems. Achievements in photocatalysis during the last decade have sparked increased interest in using sunlight to reduce CO2. Traditional semiconductors used in photocatalysis (e.g. TiO2) are not suitable for use in natural sunlight and their performance is not sufficient even under UV irradiation. Some two-dimensional (2D) materials have recently been designed for the catalytic reduction of CO2. These materials still require significant modification, which is a challenge when designing a photocatalytic process. An overarching aim of this Review is to summarize the literature on the photocatalytic conversion of CO2 by various 2D materials in the liquid phase, with special attention given to the development of novel 2D photocatalyst materials to provide a basis for improved materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201710509
  • 2018 • 213 Covalent Surface Functionalization of Calcium Phosphate Nanoparticles with Fluorescent Dyes by Copper-Catalysed and by Strain-Promoted Azide-Alkyne Click Chemistry
    Rojas-Sánchez, L. and Sokolova, V. and Riebe, S. and Voskuhl, J. and Epple, M.
    ChemNanoMat (2018)
    Spherical calcium phosphate nanoparticles with a solid core diameter around 90 nm (from scanning electron microscopy, SEM) were coated with a silica shell and then covalently functionalized by azide groups. To these azide groups, all kinds of alkyne-carrying molecules can be covalently attached by copper-catalysed azide-alkyne cycloaddition (CuAAC) and by strain-promoted azide-alkyne cycloaddition (SPAAC) at a very high density. This was demonstrated for a number of dyes (FAM, TAMRA, Cy5, Alexa Fluor™ 488, and an aromatic thioether with aggregation-induced emission (AIE) properties). It was also possible to attach more than one molecule to the surface of one particle by two-step click reaction, permitting the synthesis of multimodal nanoparticles that are stable under biological conditions. The nanoparticles have a hydrodynamic diameter of around 200 nm (from dynamic light scattering, DLS), which makes them suitable for uptake by cells. The strongly fluorescing nanoparticles were easily taken up by cells as demonstrated by fluorescence microscopy, confocal laser scanning microscopy (CLSM), and structured illuminated microscopy (SIM). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cnma.201800509
  • 2018 • 212 Discovery of a Multinary Noble Metal–Free Oxygen Reduction Catalyst
    Löffler, T. and Meyer, H. and Savan, A. and Wilde, P. and Garzón Manjón, A. and Chen, Y.-T. and Ventosa, E. and Scheu, C. and Ludwig, Al. and Schuhmann, W.
    Advanced Energy Materials 8 (2018)
    In the endeavor of discovering new noble metal–free electrocatalysts for the oxygen reduction reaction, noble metal–free multinary transition metal nanoparticle libraries are investigated. The complexity of such multiple principal element alloys provides access to a large variety of different elemental compositions, each with potentially unique properties. The strategy for efficient identification of novel electrocatalytically active systems comprises combinatorial co-sputtering into an ionic liquid followed by potential-assisted immobilization of the formed nanoparticles at a microelectrode which allows the evaluation of their intrinsic electrocatalytic activity in alkaline media. A surprisingly high intrinsic activity is found for the system Cr–Mn–Fe–Co–Ni, which is at least comparable to Pt under the same conditions, an unexpected result based on the typical properties of its constituents. Systematic removal of each element from the quinary alloy system yields a significant drop in activity for all quaternary alloys, indicating the importance of the synergistic combination of all five elements, likely due to formation of a single solid solution phase with altered properties which enables the limitations of the single elements to be overcome. Multinary transition metal alloys as a novel material class in electrocatalysis with basically unlimited possibilities for catalyst design, targeting the replacement of noble metal–based materials, are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/aenm.201802269
  • 2018 • 211 Dual Brønsted-acid Organocatalysis: Cooperative Asymmetric Catalysis with Combined Phosphoric and Carboxylic Acids
    Mitra, R. and Niemeyer, J.
    ChemCatChem (2018)
    How can an assisting Brønsted-acid be beneficial in asymmetric Brønsted-acid catalysis? In this Minireview, we discuss selected examples of chiral organocatalysts that feature two acidic groups working cooperatively by virtue of intra- or intermolecular hydrogen-bonding. In these systems, the assisting Brønsted-acid can play different roles, ranging from simple hydrogen-bond donation, to substrate-binding or even as a nucleophilic reaction partner. By analysis of combined experimental, structural and theoretical data, we aim at developing a better understanding of the reaction mechanisms, which are largely influenced by the underlying intramolecular- and intermolecular catalyst-substrate interactions. This may aid in the future development of more selective dual Brønsted-acid organocatalysts for specific asymmetric transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201701698
  • 2018 • 210 Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen /639/638/77/886 /639/638/161/893 /639/638/675 /120 /128 /140/131 article
    Oughli, A.A. and Ruff, A. and Boralugodage, N.P. and Rodríguez-Maciá, P. and Plumeré, N. and Lubitz, W. and Shaw, W.J. and Schuhmann, W. and Rüdiger, O.
    Nature Communications 9 (2018)
    The Ni(P2N2)2 catalysts are among the most efficient non-noble-metal based molecular catalysts for H2 cycling. However, these catalysts are O2 sensitive and lack long term stability under operating conditions. Here, we show that in a redox silent polymer matrix the catalyst is dispersed into two functionally different reaction layers. Close to the electrode surface is the "active" layer where the catalyst oxidizes H2 and exchanges electrons with the electrode generating a current. At the outer film boundary, insulation of the catalyst from the electrode forms a "protection" layer in which H2 is used by the catalyst to convert O2 to H2O, thereby providing the "active" layer with a barrier against O2. This simple but efficient polymer-based electrode design solves one of the biggest limitations of these otherwise very efficient catalysts enhancing its stability for catalytic H2 oxidation as well as O2 tolerance. © 2018 The Author(s).
    view abstractdoi: 10.1038/s41467-018-03011-7
  • 2018 • 209 Electrocatalytic Nanoparticles That Mimic the Three-Dimensional Geometric Architecture of Enzymes: Nanozymes
    Benedetti, T.M. and Andronescu, C. and Cheong, S. and Wilde, P. and Wordsworth, J. and Kientz, M. and Tilley, R.D. and Schuhmann, W. and Gooding, J.J.
    Journal of the American Chemical Society 140 13449-13455 (2018)
    Enzymes are characterized by an active site that is typically embedded deeply within the protein shell thus creating a nanoconfined reaction volume in which high turnover rates occur. We propose nanoparticles with etched substrate channels as a simplified enzyme mimic, denominated nanozymes, for electrocatalysis. We demonstrate increased electrocatalytic activity for the oxygen reduction reaction using PtNi nanoparticles with isolated substrate channels. The PtNi nanoparticles comprise an oleylamine capping layer that blocks the external surface of the nanoparticles participating in the catalytic reaction. Oxygen reduction mainly occurs within the etched channels providing a nanoconfined reaction volume different from the bulk electrolyte conditions. The oxygen reduction reaction activity normalized by the electrochemically active surface area is enhanced by a factor of 3.3 for the nanozymes compared to the unetched nanoparticles and a factor of 2.1 compared to mesoporous PtNi nanoparticles that possess interconnecting pores. © Copyright 2018 American Chemical Society.
    view abstractdoi: 10.1021/jacs.8b08664
  • 2018 • 208 Evaluation of 3D gold nanodendrite layers obtained by templated galvanic displacement reactions for SERS sensing and heterogeneous catalysis
    Han, W. and Stepula, E. and Philippi, M. and Schlücker, S. and Steinhart, M.
    Nanoscale 10 20671-20680 (2018)
    Dense layers of overlapping three-dimensional (3D) gold nanodendrites characterized by high specific surfaces as well as by abundance of sharp edges and vertices creating high densities of SERS hotspots are promising substrates for SERS-based sensing and catalysis. We have evaluated to what extent structural features of 3D gold nanodendrite layers can be optimized by the initiation of 3D gold nanodendrite growth at gold particles rationally positioned on silicon wafers. For this purpose, galvanic displacement reactions yielding 3D gold nanodendrites were guided by hexagonal arrays of parent gold particles with a lattice constant of 1.5 μm obtained by solid-state dewetting of gold on topographically patterned silicon wafers. Initiation of the growth of dendritic features at the edges of the gold particles resulted in the formation of 3D gold nanodendrites while limitation of dendritic growth to the substrate plane was prevented. The regular arrangement of the parent gold particles supported the formation of dense layers of overlapping 3D gold nanodendrites that were sufficiently homogeneous within the resolution limits of Raman microscopy. Consequently, SERS mapping experiments revealed a reasonable degree of uniformity. The proposed preparation algorithm comprises only bottom-up process steps that can be carried out without the use of costly instrumentation. © 2018 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c8nr07164k
  • 2018 • 207 From Enzymes to Functional Materials—Towards Activation of Small Molecules
    Möller, F. and Piontek, S. and Miller, R.G. and Apfel, U.-P.
    Chemistry - A European Journal 24 1471-1493 (2018)
    The design of non-noble metal-containing heterogeneous catalysts for the activation of small molecules is of utmost importance for our society. While nature possesses very sophisticated machineries to perform such conversions, rationally designed catalytic materials are rare. Herein, we aim to raise the awareness of the overall common design and working principles of catalysts incorporating aspects of biology, chemistry, and material sciences. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201703451
  • 2018 • 206 Maximally resolved anharmonic OH vibrational spectrum of the water/ZnO(10 1 0) interface from a high-dimensional neural network potential
    Quaranta, V. and Hellström, M. and Behler, J. and Kullgren, J. and Mitev, P.D. and Hermansson, K.
    Journal of Chemical Physics 148 (2018)
    Unraveling the atomistic details of solid/liquid interfaces, e.g., by means of vibrational spectroscopy, is of vital importance in numerous applications, from electrochemistry to heterogeneous catalysis. Water-oxide interfaces represent a formidable challenge because a large variety of molecular and dissociated water species are present at the surface. Here, we present a comprehensive theoretical analysis of the anharmonic OH stretching vibrations at the water/ZnO(1010) interface as a prototypical case. Molecular dynamics simulations employing a reactive high-dimensional neural network potential based on density functional theory calculations have been used to sample the interfacial structures. In the second step, one-dimensional potential energy curves have been generated for a large number of configurations to solve the nuclear Schrödinger equation. We find that (i) the ZnO surface gives rise to OH frequency shifts up to a distance of about 4 Å from the surface; (ii) the spectrum contains a number of overlapping signals arising from different chemical species, with the frequencies decreasing in the order ν(adsorbed hydroxide) > ν(non-adsorbed water) > ν(surface hydroxide) > ν(adsorbed water); (iii) stretching frequencies are strongly influenced by the hydrogen bond pattern of these interfacial species. Finally, we have been able to identify substantial correlations between the stretching frequencies and hydrogen bond lengths for all species. © 2018 Author(s).
    view abstractdoi: 10.1063/1.5012980
  • 2018 • 205 On-surface nickel porphyrin mimics the reactive center of an enzyme cofactor
    Zamborlini, G. and Jugovac, M. and Cossaro, A. and Verdini, A. and Floreano, L. and Lüftner, D. and Puschnig, P. and Feyer, V. and Schneider, C.M.
    Chemical Communications 54 13423-13426 (2018)
    Metal-containing enzyme cofactors achieve their unusual reactivity by stabilizing uncommon metal oxidation states with structurally complex ligands. In particular, the specific cofactor promoting both methanogenesis and anaerobic methane oxidation is a porphyrinoid chelated to a nickel(i) atom via a multi-step biosynthetic path, where nickel reduction is achieved through extensive molecular hydrogenation. Here, we demonstrate an alternative route to porphyrin reduction by charge transfer from a selected copper substrate to commercially available 5,10,15,20-tetraphenyl-porphyrin nickel(ii). X-ray absorption measurements at the Ni L3-edge unequivocally show that NiTPP species adsorbed on Cu(100) are stabilized in the highly reactive Ni(i) oxidation state by electron transfer to the molecular orbitals. Our approach highlights how some fundamental properties of synthetically inaccessible biological cofactors may be reproduced by hybridization of simple metalloporphyrins with metal surfaces, with implications towards novel approaches to heterogenous catalysis. © 2018 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c8cc06739b
  • 2018 • 204 Oxygen Evolution Catalysis with Mössbauerite—A Trivalent Iron-Only Layered Double Hydroxide
    Ertl, M. and Andronescu, C. and Moir, J. and Zobel, M. and Wagner, F.E. and Barwe, S. and Ozin, G. and Schuhmann, W. and Breu, J.
    Chemistry - A European Journal 24 9004-9008 (2018)
    Mössbauerite is investigated for the first time as an “iron-only” mineral for the electrocatalytic oxygen evolution reaction in alkaline media. The synthesis proceeds via intermediate mixed-valence green rust that is rapidly oxidized in situ while conserving the layered double hydroxide structure. The material catalyzes the oxygen evolution reaction on a glassy carbon electrode with a current density of 10 mA cm−2 at 1.63 V versus the reversible hydrogen electrode. Stability measurements, as well as post-electrolysis characterization are presented. This work demonstrates the applicability of iron-only layered double hydroxides as earth-abundant oxygen evolution electrocatalysts. Mössbauerite is of fundamental importance since as an all Fe3+ material its performance has no contributions from unknown synergistic effects as encountered for mixed valence Co/Ni/Fe LDH. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201801938
  • 2018 • 203 Prediction and Experimental Validation of Co-Solvent Influence on Michaelis Constants: A Thermodynamic Activity-Based Approach
    Wangler, A. and Böttcher, D. and Hüser, A. and Sadowski, G. and Held, C.
    Chemistry - A European Journal 24 16418-16425 (2018)
    Co-solvents are known to influence the Michaelis constant KM of enzyme-catalyzed reactions. In the literature, co-solvent effects on KM are usually explained by interactions between enzyme and co-solvent. Very recent works replaced substrate concentrations with thermodynamic activities to separate enzyme–co-solvent from substrate–co-solvent interactions This yields the thermodynamic-activity-based Michalis constant Ka M. In this work, this approach was extended to alcohol dehydrogenase (ADH)-catalyzed reduction of acetophenone (ACP), a two-substrate reaction. It was experimentally found that polyethylene glycol (PEG) 6000 increased KM of ACP and decreased KM of nicotinamide adenine dinucleotide (NADH). To predict Ka M values, non-covalent interactions between substrates and reaction media were taken into account by electrolyte perturbed-chain statistical associating fluid theory (ePC-SAFT) modelling. In contrast to experimental KM values, their activity-based pendants Ka M were independent of co-solvent. To further verify the approach, the reduction of 2-pentanone catalyzed by the same ADH was investigated. Interestingly, the addition of PEG caused a decrease of both KM of 2-pentanone and KM of NADH. Based on Ka M values obtained from in co-solvent-free conditions and activity coefficients from ePC-SAFT, the influence of the co-solvent on KM was quantitatively predicted. Thus, the approach known for pseudo one-substrate reactions was successfully transferred to two-substrate reactions. Furthermore, the advantage of thermodynamic activities over concentrations in the field of enzyme kinetics is highlighted. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201803573
  • 2018 • 202 Proof of Equivalent Catalytic Functionality upon Photon-Induced and Thermal Activation of Supported Isolated Vanadia Species in Methanol Oxidation
    Kortewille, B. and Wachs, I.E. and Cibura, N. and Pfingsten, O. and Bacher, G. and Muhler, M. and Strunk, J.
    ChemCatChem 10 2360-2364 (2018)
    In this study, evidence is provided that isolated surface vanadia (VO4) species on SiO2 can similarly act as a thermal heterogeneous catalyst and as a heterogeneous photocatalyst. Structurally identical surface VO4 species catalyze the selective oxidation of methanol both by thermal activation and by UV-light induction. Selectivity to formaldehyde appears to be unity. For the photocatalytic reaction at room temperature, formaldehyde desorption is rate limiting. With larger agglomerates or V2O5 nanoparticles, on the contrary, only the thermal reaction is feasible. This is tentatively attributed to the different positions of electronic states (HOMO/LUMO, valence/conduction band) on the electrochemical energy scale owing to the quantum size effect. Besides providing new fundamental insight into the mode of action of nanosized photocatalysts, our results demonstrate that tuning the photocatalytic reactivity of supported transition-metal oxides by adjusting the degree of agglomeration is feasible. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201800311
  • 2018 • 201 Rechargeable, flexible and mediator-free biosupercapacitor based on transparent ITO nanoparticle modified electrodes acting in µM glucose containing buffers
    Bobrowski, T. and González Arribas, E. and Ludwig, R. and Toscano, M.D. and Shleev, S. and Schuhmann, W.
    Biosensors and Bioelectronics 101 84-89 (2018)
    We present a transparent and flexible self-charging biosupercapacitor based on an optimised mediator- and membrane-free enzymatic glucose/oxygen biofuel cell. Indium tin oxide (ITO) nanoparticles were spray-coated on transparent conducting ITO supports resulting in a flocculent, porous and nanostructured electrode surface. By this, high capacitive currents caused by an increased electrochemical double layer as well as enhanced catalytic currents due to a higher number of immobilised enzyme molecules were obtained. After a chemical pre-treatment with a silane derivative, bilirubin oxidase from Myrothecium verrucaria was immobilized onto the ITO nanostructured electrode surface under formation of a biocathode, while bioanodes were obtained by either immobilisation of cellobiose dehydrogenase from Corynascus thermophilus or soluble PQQ-dependent glucose dehydrogenase from Acinetobacter calcoaceticus. The latter showed a lower apparent KM value for glucose conversion and higher catalytic currents at µM glucose concentrations. Applying the optimised device as a biosupercapacitor in a discontinuous charge/discharge mode led to a generated power output of 0.030 mW/cm2 at 50 µM glucose, simulating the glucose concentration in human tears. This represents an enhancement by a factor of 350 compared to the power density obtained from the continuously operating biofuel cell with a maximum power output of 0.086 µW/cm2 under the same conditions. After 17 h of charging/discharging cycles a remarkable current enhancement was still measured. The entire device was transferred to flexible materials and applied for powering a flexible display showing its potential applicability as an intermittent power source in smart contact lenses. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.bios.2017.10.016
  • 2018 • 200 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 • 199 Spectroscopical investigations on the redox chemistry of [FeFe]-hydrogenases in the presence of carbon monoxide
    Laun, K. and Mebs, S. and Duan, J. and Wittkamp, F. and Apfel, U.-P. and Happe, T. and Winkler, M. and Haumann, M. and Stripp, S.T.
    Molecules 23 1-13 (2018)
    [FeFe]-hydrogenases efficiently catalyzes hydrogen conversion at a unique [4Fe–4S]-[FeFe] cofactor, the so-called H-cluster. The catalytic reaction occurs at the diiron site, while the [4Fe–4S] cluster functions as a redox shuttle. In the oxidized resting state (Hox), the iron ions of the diiron site bind one cyanide (CN−) and carbon monoxide (CO) ligand each and a third carbonyl can be found in the Fe–Fe bridging position (µCO). In the presence of exogenous CO, A fourth CO ligand binds at the diiron site to form the oxidized, CO-inhibited H-cluster (Hox-CO). We investigated the reduced, CO-inhibited H-cluster (Hred´-CO) in this work. The stretching vibrations of the diatomic ligands were monitored by attenuated total reflection Fourier-transform infrared spectroscopy (ATR FTIR). Density functional theory (DFT) at the TPSSh/TZVP level was employed to analyze the cofactor geometry, as well as the redox and protonation state of the H-cluster. Selective 13CO isotope editing, spectro-electrochemistry, and correlation analysis of IR data identified a one-electron reduced, protonated [4Fe–4S] cluster and an apical CN− ligand at the diiron site in Hred´-CO. The reduced, CO-inhibited H-cluster forms independently of the sequence of CO binding and cofactor reduction, which implies that the ligand rearrangement at the diiron site upon CO inhibition is independent of the redox and protonation state of the [4Fe–4S] cluster. The relation of coordination dynamics to cofactor redox and protonation changes in hydrogen conversion catalysis and inhibition is discussed. © 2018 by the authors.
    view abstractdoi: 10.3390/molecules23071669
  • 2018 • 198 Synthesis of Furan-Annelated BINOL Derivatives: Acid-Catalyzed Cyclization Induces Partial Racemization
    Octa-Smolin, F. and Van Der Vight, F. and Yadav, R. and Bhangu, J. and Soloviova, K. and Wölper, C. and Daniliuc, C.G. and Strassert, C.A. and Somnitz, H. and Jansen, G. and Niemeyer, J.
    Journal of Organic Chemistry 83 14568-14587 (2018)
    In this account, we describe the synthesis of a series of BINOL-based bis- and trisphosphoric acids 11d/e/f, which commonly feature an unusual phosphoric acid monoester motif. This motif is generated by an acid-catalyzed 5-endo-dig cyclization of the 3-alkynyl-substituted BINOL precursors to give the corresponding Furan-annelated derivatives, followed by phosphorylation of the remaining phenolic alcohols. In the cyclization reaction, we observed an unexpected partial racemization in the bis- and tris-BINOL scaffolds, leading to mixtures of diastereomers that were separated and characterized spectroscopically and by X-ray crystal structure analyses. The cyclization and racemization processes were investigated both experimentally and by DFT-calculations, showing that although the cyclization proceeds faster, the barrier for the acid-catalyzed binaphthyl-racemization is only slightly higher. © 2018 American Chemical Society.
    view abstractdoi: 10.1021/acs.joc.8b02353
  • 2018 • 197 The Role of Composition of Uniform and Highly Dispersed Cobalt Vanadium Iron Spinel Nanocrystals for Oxygen Electrocatalysis
    Chakrapani, K. and Bendt, G. and Hajiyani, H. and Lunkenbein, T. and Greiner, M.T. and Masliuk, L. and Salamon, S. and Landers, J. and Schlögl, R. and Wende, H. and Pentcheva, R. and Schulz, S. and Behrens, M.
    ACS Catalysis 8 1259-1267 (2018)
    Cation substitution in transition-metal oxides is an important approach to improve electrocatalysts by the optimization of their composition. Herein, we report on phase-pure spinel-type CoV2-xFexO4 nanoparticles with 0 ≤ x ≤ 2 as a new class of bifunctional catalysts for the oxygen evolution (OER) and oxygen reduction reactions (ORR). The mixed-metal oxide catalysts exhibit high catalytic activity for both OER and ORR that strongly depends on the V and Fe content. CoV2O4 is known to exhibit a high conductivity, while in CoFe2O4 the cobalt cation distribution is expected to change due to the inversion of the spinel structure. The optimized catalyst, CoV1.5Fe0.5O4, shows an overpotential for the OER of â300 mV for 10 mA cm-2 with a Tafel slope of 38 mV dec-1 in alkaline electrolyte. DFT+U+SOC calculations on cation ordering confirm the tendency toward the inverse spinel structure with increasing Fe concentration in CoV2-xFexO4 that starts to dominate already at low Fe contents. The theoretical results also show that the variations of oxidation states are related to the surface region, where the redox activity was found experimentally to be manifested in the transformation of V3+ ↠V2+. The high catalytic activity, facile synthesis, and low cost of the CoV2-xFexO4 nanoparticles render them very promising for application in bifunctional electrocatalysis. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.7b03529
  • 2017 • 196 Black Magic in Gray Titania: Noble-Metal-Free Photocatalytic H2 Evolution from Hydrogenated Anatase
    Liu, N. and Zhou, X. and Nguyen, N.T. and Peters, K. and Zoller, F. and Hwang, I. and Schneider, C. and Miehlich, M.E. and Freitag, D. and Meyer, K. and Fattakhova-Rohlfing, D. and Schmuki, P.
    ChemSusChem 10 62-67 (2017)
    ‘Black’ TiO2—in the widest sense, TiO2 reduced by various treatments—has attracted tremendous scientific interest in recent years because of some outstanding properties; most remarkably in photocatalysis. While the material effects visible light absorption (the blacker, the better), black titania produced by high pressure hydrogenation was recently reported to show another highly interesting feature; noble-metal-free photocatalytic H2 generation. In a systematic investigation of high-temperature hydrogen treatments of anatase nanoparticles, TEM, XRD, EPR, XPS, and photoelectrochemistry are used to characterize different degrees of surface hydrogenation, surface termination, electrical conductivity, and structural defects in the differently treated materials. The materials’ intrinsic activity for photocatalytic hydrogen evolution is coupled neither with their visible light absorption behavior nor the formation of amorphous material, but rather must be ascribed to optimized and specific defect formation (gray is better than black). This finding is further confirmed by using a mesoporous anatase matrix as a hydrogenation precursor, which, after conversion to the gray state, even further enhances the overall photocatalytic hydrogen evolution activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201601264
  • 2017 • 195 Chemoenzymatic one-pot reaction of noncompatible catalysts: Combining enzymatic ester hydrolysis with Cu(i)/bipyridine catalyzed oxidation in aqueous medium
    Sand, H. and Weberskirch, R.
    RSC Advances 7 33614-33626 (2017)
    The combination of chemical catalysts and biocatalysts in a one-pot reaction has attracted considerable interest in the past years. However, since each catalyst requires very different reaction conditions, chemoenzymatic one-pot reactions in aqueous media remain challenging and are limited today to metal-catalysts that display high activity in aqueous media. Here, we report the first combination of two incompatible catalytic systems, a lipase based ester hydrolysis with a water-sensitive Cu/bipyridine catalyzed oxidation reaction, in a one-pot reaction in aqueous medium (PBS buffer). Key to the solution was the compartmentalization of the Cu/bipyridine catalyst in a core-shell like nanoparticle. We show the synthesis and characterization of the Cu/bipyridine functionalized nanoparticles and the application in the oxidation of allylic and benzylic alcohols in aqueous media. Furthermore, the work demonstrates the implementation of a one-pot reaction process with optimized reaction conditions involving a lipase (CAL-B) to hydrolyze various acetate ester substrates in the first step, followed by oxidation of the resulting alcohols to the corresponding aldehydes under aerobic conditions in aqueous media. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7ra05451c
  • 2017 • 194 Constrained Ab Initio Thermodynamics: Transferring the Concept of Surface Pourbaix Diagrams in Electrocatalysis to Electrode Materials in Lithium-Ion Batteries
    Exner, K.S.
    ChemElectroChem 4 3231-3237 (2017)
    DFT-based ab initio Pourbaix diagrams represent a powerful tool to resolve the stable surface structure of an electrocatalyst under different environmental parameters such as the applied electrode potential and pH. Herein, a general approach for anode and cathode materials in lithium-ion batteries (LIBs) is presented that enables to transfer the concept of surface Pourbaix diagrams from electrocatalysis to electrode materials employed in LIBs. This novel approach is exemplified at the example of the (111) facet for a single-crystalline spinel lithium titanate (LTO) model electrode by combining constrained thermodynamics and density functional theory calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201700754
  • 2017 • 193 Decoupling the Effects of High Crystallinity and Surface Area on the Photocatalytic Overall Water Splitting over β-Ga2O3 Nanoparticles by Chemical Vapor Synthesis
    Lukic, S. and Menze, J. and Weide, P. and Busser, G.W. and Winterer, M. and Muhler, M.
    ChemSusChem 10 4190-4197 (2017)
    Chemical vapor synthesis (CVS) is a unique method to prepare well-defined photocatalyst materials with both large specific surface area and a high degree of crystallinity. The obtained β-Ga2O3 nanoparticles were optimized for photocatalysis by reductive photodeposition of the Rh/CrOx co-catalyst system. The influence of the degree of crystallinity and the specific surface area on photocatalytic aqueous methanol reforming and overall water splitting (OWS) was investigated by synthesizing β-Ga2O3 samples in the temperature range from 1000 °C to 1500 °C. With increasing temperature, the specific surface area and the microstrain were found to decrease, whereas the degree of crystallinity and the crystallite size increased. Whereas the photocatalyst with the highest specific surface area showed the highest aqueous methanol reforming activity, the highest OWS activity was that for the sample with an optimum ratio between high degree of crystallinity and specific surface area. Thus, it was possible to show that the facile aqueous methanol reforming and the demanding OWS have different requirements for high photocatalytic activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201701309
  • 2017 • 192 Electrified Interfaces (ICEI 2016): 14th International Conference, 3-8 July 2016, Singapore
    Hoster, H. and Toghill, K. and Xu, Z.J.
    Electrochimica Acta 249 241-242 (2017)
    The special issue of Electrochimica Acta celebrates the 14th International Conference on Electrified Interfaces (ICEI 2016) that was held in Singapore, from 3rd to 8th July 2016. Lancaster University (UK), in collaboration with Nanyang Technological University (Singapore). Five companies presented their lab technologies at booths in the coffee and lunch break area: SPECS, TriTech, Ametek, Princeton/Solartron, and Metrohm. Metrohm also kindly helped us sponsoring the refresh- ments at the Poster Session through an extra contribution. The oral presentations were divided into 10 consecutive sessions, In-situ spectroscopy, Atomic Scale Imaging and Diffraction, Fundamentals of Electrocatalysis, Applied Electrochemistry, Electrocatalysis towards OER and ORR, New Electrocatalytic Materials, Fundamental Electrochemistry, Nanostructures and Nanomaterials, Batteries. The Poster Session on day 2 was initiated by 90-minutes of a poster-pitch session in the afternoon. All submitted manuscripts underwent a rigorous standard review process, which was overseen by Professor Sergio Trasatti.
    view abstractdoi: 10.1016/j.electacta.2017.08.008
  • 2017 • 191 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 • 190 Experimental and Theoretical Understanding of Nitrogen-Doping-Induced Strong Metal-Support Interactions in Pd/TiO2 Catalysts for Nitrobenzene Hydrogenation
    Chen, P. and Khetan, A. and Yang, F. and Migunov, V. and Weide, P. and Stürmer, S.P. and Guo, P. and Kähler, K. and Xia, W. and Mayer, J. and Pitsch, H. and Simon, U. and Muhler, M.
    ACS Catalysis 7 1197-1206 (2017)
    By doping the TiO2 support with nitrogen, strong metal-support interactions (SMSI) in Pd/TiO2 catalysts can be tailored to obtain high-performance supported Pd nanoparticles (NPs) in nitrobenzene (NB) hydrogenation catalysis. According to the comparative studies by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance CO FTIR (CO-DRIFTS), N-doping induced a structural promoting effect, which is beneficial for the dispersion of Pd species on TiO2. High-angle annular dark-field scanning transmission electron microscopy study of Pd on N-doped TiO2 confirmed a predominant presence of sub-2 nm Pd NPs, which are stable under the applied hydrogenation conditions. XPS and CO-DRIFTS revealed the formation of strongly coupled Pd-N species in Pd/TiO2 with N-doped TiO2 as support. Density functional theory (DFT) calculations over model systems with Pdn (n = 1, 5, or 10) clusters deposited on TiO2(101) surface were performed to verify and supplement the experimental observations. In hydrogenation catalysis using NB as a model molecule, Pd NPs on N-doped TiO2 outperformed those on N-free TiO2 in terms of both catalytic activity and stability, which can be attributed to the presence of highly dispersed Pd NPs providing more active sites, and to the formation of Pd-N species favoring the dissociative adsorption of the reactant NB and the easier desorption of the product aniline. (Figure Presented). © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.6b02963
  • 2017 • 189 Exploiting micro-scale structural and chemical observations in real time for understanding chemical conversion: LEEM/PEEM studies over CeOx–Cu(111)
    Duchoň, T. and Hackl, J. and Höcker, J. and Veltruská, K. and Matolín, V. and Falta, J. and Cramm, S. and Nemšák, S. and Schneider, C.M. and Flege, J.I. and Senanayake, S.D.
    Ultramicroscopy 183 1339-1351 (2017)
    Proper consideration of length-scales is critical for elucidating active sites/phases in heterogeneous catalysis, revealing chemical function of surfaces and identifying fundamental steps of chemical reactions. Using the example of ceria thin films deposited on the Cu(111) surface, we demonstrate the benefits of multi length-scale experimental framework for understanding chemical conversion. Specifically, exploiting the tunable sampling and spatial resolution of photoemission electron microscopy, we reveal crystal defect mediated structures of inhomogeneous copper–ceria mixed phase that grow during preparation of ceria/Cu(111) model systems. The density of the microsized structures is such that they are relevant to the chemistry, but unlikely to be found during investigation at the nanoscale or with atomic level investigations. Our findings highlight the importance of accessing micro-scale when considering chemical pathways over heteroepitaxially grown model systems. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2017.05.003
  • 2017 • 188 Functional Mechanically Interlocked Molecules: Asymmetric Organocatalysis with a Catenated Bifunctional Brønsted Acid
    Mitra, R. and Zhu, H. and Grimme, S. and Niemeyer, J.
    Angewandte Chemie - International Edition 56 11456-11459 (2017)
    Interlocked molecules, such as catenanes, rotaxanes, and molecular knots, have become interesting candidates for the development of sophisticated chemical catalysts. Herein, we report the first application of a catenane-based catalyst in asymmetric organocatalysis, revealing that the catenated catalyst shows dramatically increased stereoselectivities (up to 98 % ee) in comparison to its non-interlocked analogues. A mechanistic rationale for the observed differences was developed by DFT studies, suggesting that the involvement of two catalytically active groups in the stereodetermining reaction step is responsible for the superior selectivity of the interlocked catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201704647
  • 2017 • 187 German Catalysis Society (GeCatS)
    Muhler, M.
    ChemCatChem 9 525-526 (2017)
    The German Catalysis Society (GeCatS) is the platform for the entire German catalysis community both in basic and applied research with about 1100 members from industry and academia. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201700117
  • 2017 • 186 Influence of Natural Solutes and Ionic Liquids on the Yield of Enzyme-Catalyzed Reactions: Measurements and Predictions
    Voges, M. and Fischer, C. and Wolff, D. and Held, C.
    Organic Process Research and Development 21 1059-1068 (2017)
    The maximum yield of enzyme-catalyzed reactions is often limited by thermodynamic equilibrium. The knowledge of influencing factors on limitations of reactions is essential for process optimization to increase yields and to reduce solvent and energy consumption. In this work the effect of solvents/cosolvents [e.g., ionic liquid (IL)] and natural solutes on thermodynamic yield limitations of two enzyme-catalyzed model reactions were investigated, namely, an alcohol dehydrogenase (ADH) reaction (acetophenone + 2-propanol ⇌ 1-phenylethanol + acetone) and an alanine aminotransferase reaction (l-alanine + 2-oxoglutarate ⇌ pyruvate + l-glutamate). Experimental results showed that the equilibrium position and the equilibrium product yield of both reactions in aqueous single-phase systems strongly depend on the type and molality of the present natural solute/IL that were present as additives in the reaction mixture. In addition, the ADH reaction was investigated in pure IL and in an IL/buffer two-phase system. Compared to the aqueous reaction mixtures, the reactant solubility could be increased significantly, but at the cost of a lower product yield. Finally, thermodynamic modeling by means of ePC-SAFT was used to predict the equilibrium product yield of both reactions at different reaction conditions (natural solute/IL type and molality) in the aqueous mixtures as well as in the IL. Experimental and predicted results were in good agreement, showing that ePC-SAFT is a promising tool for predicting yield limitations in different reaction media. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acs.oprd.7b00178
  • 2017 • 185 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 • 184 Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis
    Marzun, G. and Levish, A. and Mackert, V. and Kallio, T. and Barcikowski, S. and Wagener, P.
    Journal of Colloid and Interface Science 489 57-67 (2017)
    Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys. © 2016 Elsevier Inc.
    view abstractdoi: 10.1016/j.jcis.2016.09.014
  • 2017 • 183 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 • 182 Poly(2-oxazoline)-Antibiotic Conjugates with Penicillins
    Schmidt, M. and Bast, L.K. and Lanfer, F. and Richter, L. and Hennes, E. and Seymen, R. and Krumm, C. and Tiller, J.C.
    Bioconjugate Chemistry 28 2440-2451 (2017)
    The conjugation of antibiotics with polymers is rarely done, but it might be a promising alternative to low-molecular-weight derivatization. The two penicillins penicillin G (PenG) and penicillin V (PenV) were attached to the end groups of different water-soluble poly(2-oxazoline)s (POx) via their carboxylic acid function. This ester group was shown to be more stable against hydrolysis than the β-lactam ring of the penicillins. The conjugates are still antimicrobially active and up to 20 times more stable against penicillinase catalyzed hydrolysis. The antibiotic activity of the conjugates against Staphylococcus aureus in the presence of penicillinase is up to 350 times higher compared with the free antibiotics. Conjugates with a second antimicrobial function, a dodecyltrimethylammonium group (DDA-X), at the starting end of the PenG and PenV POx conjugates are more antimicrobially active than the conjugates without DDA-X and show high activity in the presence of penicillinase. For example, the conjugates DDA-X-PEtOx-PenG and DDA-X-PEtOx-PenV are 200 to 350 times more active against S. aureus in the presence of penicillinase and almost as effective as the penicillinase stable cloxacollin (Clox) under these conditions. These conjugates show even greater activity compared to cloxacollin without this enzyme present. Further, both conjugates kill Escherichia coli more effectively than PenG and Clox. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acs.bioconjchem.7b00424
  • 2017 • 181 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 • 180 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 • 179 Proton-Coupled Reduction of the Catalytic [4Fe-4S] Cluster in [FeFe]-Hydrogenases
    Senger, M. and Laun, K. and Wittkamp, F. and Duan, J. and Haumann, M. and Happe, T. and Winkler, M. and Apfel, U.-P. and Stripp, S.T.
    Angewandte Chemie - International Edition 56 16503-16506 (2017)
    In nature, [FeFe]-hydrogenases catalyze the uptake and release of molecular hydrogen (H2) at a unique iron-sulfur cofactor. The absence of an electrochemical overpotential in the H2 release reaction makes [FeFe]-hydrogenases a prime example of efficient biocatalysis. However, the molecular details of hydrogen turnover are not yet fully understood. Herein, we characterize the initial one-electron reduction of [FeFe]-hydrogenases by infrared spectroscopy and electrochemistry and present evidence for proton-coupled electron transport during the formation of the reduced state Hred′. Charge compensation stabilizes the excess electron at the [4Fe-4S] cluster and maintains a conservative configuration of the diiron site. The role of Hred′ in hydrogen turnover and possible implications on the catalytic mechanism are discussed. We propose that regulation of the electronic properties in the periphery of metal cofactors is key to orchestrating multielectron processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201709910
  • 2017 • 178 Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction
    Chakrapani, K. and Bendt, G. and Hajiyani, H. and Schwarzrock, I. and Lunkenbein, T. and Salamon, S. and Landers, J. and Wende, H. and Schlögl, R. and Pentcheva, R. and Behrens, M. and Schulz, S.
    ChemCatChem 9 2988-2995 (2017)
    Sub-10 nm CoFe2O4 nanoparticles with different sizes and various compositions obtained by (partial) substitution of Co with Ni cations have been synthesized by using a one-pot method from organic solutions by the decomposition of metal acetylacetonates in the presence of oleylamine. The electrocatalytic activity of CoFe2O4 towards the oxygen evolution reaction (OER) is clearly enhanced with a smaller size (3.1 nm) of the CoFe2O4 nanoparticles (compared with 4.5 and 5.9 nm). In addition, the catalytic activity is improved by partial substitution of Co with Ni, which also leads to a higher degree of inversion of the spinel structure. Theoretical calculations attribute the positive catalytic effect of Ni owing to the lower binding energy differences between adsorbed O and OH compared with pure cobalt or nickel ferrites, resulting in higher OER activity. Co0.5Ni0.5Fe2O4 exhibited a low overpotential of approximately 340 mV at 10 mA cm−2, a smaller Tafel slope of 51 mV dec−1, and stability over 30 h. The unique tunability of these CoFe2O4 nanocrystals provides great potential for their application as an efficient and competitive anode material in the field of electrochemical water splitting as well as for systematic fundamental studies aiming at understanding the correlation of composition and structure with performance in electrocatalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cctc.201700376
  • 2017 • 177 Selective glycerol oxidation over ordered mesoporous copper aluminum oxide catalysts
    Schünemann, S. and Schüth, F. and Tüysüz, H.
    Catalysis Science and Technology 7 5614-5624 (2017)
    Glycerol is a major by-product of the biodiesel production and is therefore produced in high quantities. While currently there are limited possible applications for this highly functionalized molecule, glycerol can be a cheap and abundant feedstock for value-added products that are accessible by selective oxidation. Usually, the selective oxidation of glycerol utilizes expensive noble metal catalysts, such as Au, Pt, and Pd. Here we report the selective oxidation of glycerol in basic media, using ordered mesoporous Cu-Al2O3 catalysts with various Cu loadings prepared by a facile soft-templating method. The materials were characterized in detail by nitrogen physisorption, vis-NIR spectroscopy, EDX, low- and wide-angle XRD, XPS, and TEM. Subsequently the reaction conditions for glycerol oxidation were optimized. The catalytic oxidation of glycerol yields C3 products, such as glyceric acid and tartronic acid, and also C2 and C1 products, such as glycolic acid, oxalic acid, and formic acid. Moreover, the role of the solvent on the catalytic reaction was investigated, and the addition of various co-solvents to the aqueous reaction mixture was found to increase the initial reaction rate up to a factor of three. The trends of the initial reaction rates correlate well with the polarity of the water/co-solvent mixtures. The prepared Cu-Al2O3 catalysts are a more cost-efficient and environmentally viable alternative to the reported noble metal catalysts. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7cy01451a
  • 2017 • 176 Self-Diffusion of Surface Defects at Copper-Water Interfaces
    Kondati Natarajan, S. and Behler, J.
    Journal of Physical Chemistry C 121 4368-4383 (2017)
    Solid-liquid interfaces play an important role in many fields like electrochemistry, corrosion, and heterogeneous catalysis. For understanding the related processes, detailed insights into the elementary steps at the atomic level are mandatory. Here we unravel the properties of prototypical surface-defects like adatoms and vacancies at a number of copper-water interfaces including the low-index Cu(111), Cu(100), and Cu(110), as well as the stepped Cu(211) and Cu(311) surfaces. Using a first-principles quality neural network potential constructed from density functional theory reference data in combination with molecular dynamics and metadynamics simulations, we investigate the defect diffusion mechanisms and the associated free energy barriers. Further, the solvent structure and the mobility of the interfacial water molecules close to the defects are analyzed and compared to the defect-free surfaces. We find that, like at the copper-vacuum interface, hopping mechanisms are preferred compared to exchange mechanisms, while the associated barriers for hopping are reduced in the presence of liquid water. The water structure close to adatoms and vacancies exhibits pronounced local features and differs strongly from the structure at the ideal low-index surfaces. Moreover, in particular at Cu(111) the adatoms are very mobile and hopping events along the surface are more frequent than the exchange of coordinating water molecules in their local environment. Consequently, adatom self-diffusion processes at Cu(111) involve entities of adatoms and their associated solvation shells. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.6b12657
  • 2017 • 175 Synergistic Effect of Cobalt and Iron in Layered Double Hydroxide Catalysts for the Oxygen Evolution Reaction
    Yang, F. and Sliozberg, K. and Sinev, I. and Antoni, H. and Bähr, A. and Ollegott, K. and Xia, W. and Masa, J. and Grünert, W. and Cuenya, B.R. and Schuhmann, W. and Muhler, M.
    ChemSusChem 10 156-165 (2017)
    Co-based layered double hydroxide (LDH) catalysts with Fe and Al contents in the range of 15 to 45 at % were synthesized by an efficient coprecipitation method. In these catalysts, Fe3+ or Al3+ ions play an essential role as trivalent species to stabilize the LDH structure. The obtained catalysts were characterized by a comprehensive combination of surface- and bulk-sensitive techniques and were evaluated for the oxygen evolution reaction (OER) on rotating disk electrodes. The OER activity decreased upon increasing the Al content for the Co- and Al-based LDH catalysts, whereas a synergistic effect in Co- and Fe-based LDHs was observed, which resulted in an optimal Fe content of 35 at %. This catalyst was spray-coated on Ni foam electrodes and showed very good stability in a flow-through cell with a potential of approximately 1.53 V at 10 mA cm−2 in 1 m KOH for at least 48 h. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/cssc.201601272
  • 2017 • 174 Thermodynamics of enzyme-catalyzed esterifications: II. Levulinic acid esterification with short-chain alcohols
    Altuntepe, E. and Emel’yanenko, V.N. and Forster-Rotgers, M. and Sadowski, G. and Verevkin, S.P. and Held, C.
    Applied Microbiology and Biotechnology 101 7509-7521 (2017)
    Levulinic acid was esterified with methanol, ethanol, and 1-butanol with the final goal to predict the maximum yield of these equilibrium-limited reactions as function of medium composition. In a first step, standard reaction data (standard Gibbs energy of reaction ΔRg0) were determined from experimental formation properties. Unexpectedly, these ΔRg0 values strongly deviated from data obtained with classical group contribution methods that are typically used if experimental standard data is not available. In a second step, reaction equilibrium concentrations obtained from esterification catalyzed by Novozym 435 at 323.15 K were measured, and the corresponding activity coefficients of the reacting agents were predicted with perturbed-chain statistical associating fluid theory (PC-SAFT). The so-obtained thermodynamic activities were used to determine ΔRg0 at 323.15 K. These results could be used to cross-validate ΔRg0 from experimental formation data. In a third step, reaction-equilibrium experiments showed that equilibrium position of the reactions under consideration depends strongly on the concentration of water and on the ratio of levulinic acid: alcohol in the initial reaction mixtures. The maximum yield of the esters was calculated using ΔRg0 data from this work and activity coefficients of the reacting agents predicted with PC-SAFT for varying feed composition of the reaction mixtures. The use of the new ΔRg0 data combined with PC-SAFT allowed good agreement to the measured yields, while predictions based on ΔRg0 values obtained with group contribution methods showed high deviations to experimental yields. © 2017, Springer-Verlag GmbH Germany.
    view abstractdoi: 10.1007/s00253-017-8481-4
  • 2017 • 173 Topotactic Synthesis of Porous Cobalt Ferrite Platelets from a Layered Double Hydroxide Precursor and Their Application in Oxidation Catalysis
    Ortega, K.F. and Anke, S. and Salamon, S. and Özcan, F. and Heese, J. and Andronescu, C. and Landers, J. and Wende, H. and Schuhmann, W. and Muhler, M. and Lunkenbein, T. and Behrens, M.
    Chemistry - A European Journal (2017)
    Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe2O4, can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe2+, Co2+, and Fe3+ during co-precipitation, a mixture of LDH, (FeIICoII)2/3FeIII 1/3(OH)2(CO3)1/6mH2O, and the target spinel CoFe2O4 can be obtained in the precursor. During calcination, the remaining FeII fraction of the LDH is oxidized to FeIII leading to an overall Co2+:Fe3+ ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111]Spinel∥[001]LDH. Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201702248
  • 2016 • 172 Bridging the Time Gap: A Copper/Zinc Oxide/Aluminum Oxide Catalyst for Methanol Synthesis Studied under Industrially Relevant Conditions and Time Scales
    Lunkenbein, T. and Girgsdies, F. and Kandemir, T. and Thomas, N. and Behrens, M. and Schlögl, R. and Frei, E.
    Angewandte Chemie - International Edition 55 12708-12712 (2016)
    Long-term stability of catalysts is an important factor in the chemical industry. This factor is often underestimated in academic testing methods, which may lead to a time gap in the field of catalytic research. The deactivation behavior of an industrially relevant Cu/ZnO/Al2O3 catalyst for the synthesis of methanol is reported over a period of 148 days time-on-stream (TOS). The process was investigated by a combination of quasi in situ and ex situ analysis techniques. The results show that ZnO is the most dynamic species in the catalyst, whereas only slight changes can be observed in the Cu nanoparticles. Thus, the deactivation of this catalyst is driven by the changes in the ZnO moieties. Our findings indicate that methanol synthesis is an interfacially mediated process between Cu and ZnO. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201603368
  • 2016 • 171 Electrocatalysis and bioelectrocatalysis – Distinction without a difference
    Masa, J. and Schuhmann, W.
    Nano Energy 29 466-475 (2016)
    Nature's subtle systems drive essential reactions responsible for sustenance of our existence “reactions of life” through sophisticated mechanisms of charge transfer, energy harvest and conversion. The interconnectedness between living nature and technologically relevant electrochemical reactions, for example, oxygen reduction and evolution catalyzed by cytochrome c oxidases and photosystem II respectively, and hydrogen oxidation and evolution catalyzed by hydrogenases, does not only intrigue but also inspires us. To what extent therefore can our present understanding of electrocatalysis guide us to decipher nature's sophistication, or rather, can bioinspired electrocatalysis succeed to replicate and supersede nature's perfection “the exemplar paragon”? Herein, we present a harmonized perspective of the principle factors which govern electrocatalysis and bioelectrocatalysis featuring examples of technologically important electrochemical reactions catalyzed by both enzymes and inorganic electrocatalysts. Sound knowledge of the inter-relationships linking electrocatalysis and bioelectrocatalysis is essential for enabling a deeper understanding of nature's bioelectrochemical reactions, and for insightful design of functional catalysts inspired by models from living nature. © 2016 Elsevier Ltd
    view abstractdoi: 10.1016/j.nanoen.2016.04.007
  • 2016 • 170 Experimental investigation of anion-π interactions - Applications and biochemical relevance
    Giese, M. and Albrecht, M. and Rissanen, K.
    Chemical Communications 52 1778-1795 (2016)
    Anion-π interactions, intuitively repulsive forces, turned from controversial to a well-established non-covalent interaction over the past quarter of a century. Within this time frame the question "Anion-π interactions. Do they exist?" could be answered and even more importantly its functional relevance was proven. The present feature article summarizes the experimental findings of anion-π studies in the gas phase, solution and in the solid state and highlights the application of anion-π interactions in anion recognition, sensing and transport as well as in catalysis. Moreover, the biochemical relevance of this weak intermolecular force is comprehensively reviewed. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c5cc09072e
  • 2016 • 169 Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2(110) Model Electrode
    Exner, K.S. and Anton, J. and Jacob, T. and Over, H.
    Angewandte Chemie - International Edition 55 7501-7504 (2016)
    Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2(110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201511804
  • 2016 • 168 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 • 167 Hollow Nano- and Microstructures as Catalysts
    Prieto, G. and Tüysüz, H. and Duyckaerts, N. and Knossalla, J. and Wang, G.-H. and Schüth, F.
    Chemical Reviews 116 14056-14119 (2016)
    Catalysis is at the core of almost every established and emerging chemical process and also plays a central role in the quest for novel technologies for the sustainable production and conversion of energy. Particularly since the early 2000s, a great surge of interest exists in the design and application of micro- and nanometer-sized materials with hollow interiors as solid catalysts. This review provides an updated and critical survey of the ever-expanding material architectures and applications of hollow structures in all branches of catalysis, including bio-, electro-, and photocatalysis. First, the main synthesis strategies toward hollow materials are succinctly summarized, with emphasis on the (regioselective) incorporation of various types of catalytic functionalities within their different subunits. The principles underlying the scientific and technological interest in hollow materials as solid catalysts, or catalyst carriers, are then comprehensively reviewed. Aspects covered include the stabilization of catalysts by encapsulation, the introduction of molecular sieving or stimuli-responsive "auxiliary" functionalities, as well as the single-particle, spatial compartmentalization of various catalytic functions to create multifunctional (bio)catalysts. Examples are also given on the applications which hollow structures find in the emerging fields of electro- and photocatalysis, particularly in the context of the sustainable production of chemical energy carriers. Finally, a critical perspective is provided on the plausible evolution lines for this thriving scientific field, as well as the main practical challenges relevant to the reproducible and scalable synthesis and utilization of hollow micro- and nanostructures as solid catalysts. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemrev.6b00374
  • 2016 • 166 Homogeneously catalyzed hydroamination in a Taylor–Couette reactor using a thermormorphic multicomponent solvent system
    Färber, T. and Riechert, O. and Zeiner, T. and Sadowski, G. and Behr, A. and Vorholt, A.J.
    Chemical Engineering Research and Design 112 263-273 (2016)
    In order to design an innovative continuous process for the conversion of the renewable β-myrcene, three methodical steps are shown in this paper to find a setup for the demanding homogeneously catalyzed hydroamination. First step is the theoretical and practical design of a suitable thermomorphic multicomponent solvent (TMS)-systems for recycling the catalyst system. The necessary phase equilibria were successfully investigated by modelling using the Perturbed Chain – Statistical Associating Fluid Theory (PC-SAFT) and measuring liquid–liquid equilibria of the ternary systems substrates/solvents mixtures at the separation temperature. In the next step the promising TMS-system was subsequently used to investigate the recycling of the catalyst in continuous operation. A Taylor–Couette reactor (TCR) was developed and modified for the application in homogeneous transition metal catalysis. The reactor was integrated in a miniplant setup and a continuous recycling of the catalyst phase as well as an efficient synthesis of the desired terpenyl amines is achieved in 3 complete cycles. The results show that the TCR is suitable for the hydroamination and generates high conversion and yields (XMyr = 82%, YHA = 80%). Recycling experiments were conducted successfully in the miniplant setup to show the long-term operation in a period of 24 h. © 2016 Institution of Chemical Engineers
    view abstractdoi: 10.1016/j.cherd.2016.06.022
  • 2016 • 165 In Situ Investigations of Laser-Generated Ligand-Free Platinum Nanoparticles by X-ray Absorption Spectroscopy: How Does the Immediate Environment Influence the Particle Surface?
    Fischer, M. and Hormes, J. and Marzun, G. and Wagener, P. and Hagemann, U. and Barcikowski, S.
    Langmuir 32 8793-8802 (2016)
    Pulsed laser ablation in liquid (PLAL) has proven its usefulness as a nanoparticle (NP) synthesis method alternative to traditional chemical reduction methods, where the absence of any molecular ligands or residual reactants makes laser-generated nanoparticles ideal reference materials for charge-transfer experiments. We synthesized additive-free platinum nanoparticles by PLAL and in-situ characterized their interaction with H2O, sodium phosphate buffer, and sodium citrate as well as a TiO2 support by X-ray absorption fine structure (XAFS), i.e., X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Differences in the white-line intensity among the colloidal particles in the three liquids indicate that the respective NP-solvent interaction varies in strength. The ions added ex situ diffuse through the particles' electric double layer and interact electrostatically with the Stern plane. Consequently, these ions weaken the interaction of the functional OH groups that are bound to the partially oxidized platinum surfaces and cause their partial reduction. Comparing XAFS spectra of laser-generated Pt NPs in citrate with wet-chemically synthesized ones (both ligand-covered) indicates different types of Pt-O bonds: a Pt(IV)O2 type in the case of wet-chemical NPs and a Pt(II)O type in the case of laser-generated NPs. A comparison of unsupported laser-generated platinum NPs in H2O with TiO2-supported ones shows no white-line intensity differences and also an identical number of Pt-O bonds in both cases. This suggests that in the deposition process at least part of the double-layer coating stays intact and that the ligand-free Pt particle properties are preserved in the TiO2-supported Pt particles, relevant for heterogeneous catalysis. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.langmuir.6b00685
  • 2016 • 164 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 • 163 Local Platinum Environments in a Solid Analogue of the Molecular Periana Catalyst
    Soorholtz, M. and Jones, L.C. and Samuelis, D. and Weidenthaler, C. and White, R.J. and Titirici, M.-M. and Cullen, D.A. and Zimmermann, T. and Antonietti, M. and Maier, J. and Palkovits, R. and Chmelka, B.F. and Schüth, F.
    ACS Catalysis 6 2332-2340 (2016)
    Combining advantages of homogeneous and heterogeneous catalysis by incorporating active species on a solid support is often an effective strategy for improving overall catalyst performance, although the influences of the support are generally challenging to establish, especially at a molecular level. Here, we report the local compositions, and structures of platinum species incorporated into covalent triazine framework (Pt-CTF) materials, a solid analogue of the molecular Periana catalyst, Pt(bpym)Cl2, both of which are active for the selective oxidation of methane in the presence of concentrated sulfuric acid. By using a combination of solid-state 195Pt nuclear magnetic resonance (NMR) spectroscopy, aberration-corrected scanning transmission electron microscopy (AC-STEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), important similarities and differences are observed between the Pt-CTF and Periana catalysts, which are likely related to their respective macroscopic reaction properties. In particular, wide-line solid-state 195Pt NMR spectra enable direct measurement, identification, and quantification of distinct platinum species in as-synthesized and used Pt-CTF catalysts. The results indicate that locally ordered and disordered Pt sites are present in as-synthesized Pt-CTF, with the former being similar to one of the two crystallographically distinct Pt sites in crystalline Pt(bpym)Cl2. A distribution of relatively disordered Pt moieties is also present in the used catalyst, among which are the principal active sites. Similarly XAS shows good agreement between the measured data of Pt-CTF and a theoretical model based on Pt(bpym)Cl2. Analyses of the absorption spectra of Pt-CTF used for methane oxidation suggests ligand exchange, as predicted for the molecular catalyst. XPS analyses of Pt(bpym)Cl2, Pt-CTF, as well as the unmodified ligands, further corroborate platinum coordination by pyridinic N atoms. Aberration-corrected high-angle annular dark-field STEM proves that Pt atoms are distributed within Pt-CTF before and after catalysis. The overall results establish the close similarities of Pt-CTF and the molecular Periana catalyst Pt(bpym)Cl2, along with differences that account for their respective properties. (Figure Presented). © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.5b02305
  • 2016 • 162 Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster
    Tymoczko, J. and Calle-Vallejo, F. and Schuhmann, W. and Bandarenka, A.S.
    Nature Communications 7 (2016)
    Although the hydrogen evolution reaction (HER) is one of the fastest electrocatalytic reactions, modern polymer electrolyte membrane (PEM) electrolysers require larger platinum loadings (∼0.5-1.0 mg cm-2) than those in PEM fuel cell anodes and cathodes altogether (∼0.5 mg cm-2). Thus, catalyst optimization would help in substantially reducing the costs for hydrogen production using this technology. Here we show that the activity of platinum(111) electrodes towards HER is significantly enhanced with just monolayer amounts of copper. Positioning copper atoms into the subsurface layer of platinum weakens the surface binding of adsorbed H-intermediates and provides a twofold activity increase, surpassing the highest specific HER activities reported for acidic media under similar conditions, to the best of our knowledge. These improvements are rationalized using a simple model based on structure-sensitive hydrogen adsorption at platinum and copper-modified platinum surfaces. This model also solves a long-lasting puzzle in electrocatalysis, namely why polycrystalline platinum electrodes are more active than platinum(111) for the HER.
    view abstractdoi: 10.1038/ncomms10990
  • 2016 • 161 Metal Nanoparticle-Catalyzed Reduction Using Borohydride in Aqueous Media: A Kinetic Analysis of the Surface Reaction by Microfluidic SERS
    Xie, W. and Grzeschik, R. and Schlücker, S.
    Angewandte Chemie - International Edition 55 13729-13733 (2016)
    Hydrides are widely used in reduction reactions. In protic solvents, their hydrolysis generates molecular hydrogen as a second reducing agent. The competition between these two parallel reduction pathways has been overlooked so far since both typically yield the same product. We investigated the platinum-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol in aqueous sodium borohydride solution as a prominent model reaction, by using label-free SERS monitoring in a microfluidic reactor. Kinetic analysis revealed a strong pH dependence. Surprisingly, only at pH>13 the reduction is driven exclusively by sodium borohydride. This study demonstrates the potential of microfluidics-based kinetic SERS monitoring of heterogeneous catalysis in colloidal suspension. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/anie.201605776
  • 2016 • 160 Nanocasting Design and Spatially Selective Sulfonation of Polystyrene-Based Polymer Networks as Solid Acid Catalysts
    Richter, F.H. and Sahraoui, L. and Schüth, F.
    Chemistry - A European Journal 22 13563-13574 (2016)
    Nanocasting is a general and widely applied method in the generation of porous materials during which a sacrificial solid template is used as a mold on the nanoscale. Ideally, the resulting structure is the inverse of the template. However, replication is not always as direct as anticipated, so the influences of the degree of pore filling and of potential restructuring processes after removal of the template need to be considered. These apparent limitations give rise to opportunities in the synthesis of poly(styrene-co-divinylbenzene) (PSD) polymer networks of widely varying porosities (BET surface area=63–562 m2g−1; Vtot=0.18–1.05 cm3g−1) by applying a single synthesis methodology. In addition, spatially selective sulfonation on the nanoscale seems possible. Together, nanocasting and sulfonation enable rational catalyst design. The highly porous nanocast and predominantly surface-sulfonated PSD networks approach the activity of the corresponding molecular catalyst, para-toluenesulfonic acid, and exceed those of commercial ion-exchange polymers in the depolymerization of macromolecular inulin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201603069
  • 2016 • 159 Nanoelectrodes reveal the electrochemistry of single nickelhydroxide nanoparticles
    Clausmeyer, J. and Masa, J. and Ventosa, E. and Öhl, D. and Schuhmann, W.
    Chemical Communications 52 2408-2411 (2016)
    Individual Ni(OH)2 nanoparticles deposited on carbon nanoelectrodes are investigated in non-ensemble measurements with respect to their energy storage properties and electrocatalysis for the oxygen evolution reaction (OER). Charging by oxidation of Ni(OH)2 is limited by the diffusion of protons into the particle bulk and the OER activity is independent of the particle size. © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5cc08796a
  • 2016 • 158 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 • 157 Optimization of and Mechanistic Considerations for the Enantioselective Dihydroxylation of Styrene Catalyzed by Osmate-Laccase-Poly(2-Methyloxazoline) in Organic Solvents
    Leurs, M. and Spiekermann, P.S. and Tiller, J.C.
    ChemCatChem 8 593-599 (2016)
    The Sharpless dihydroxylation of styrene with the artificial metalloenzyme osmate-laccase-poly(2-methyloxazoline) was investigated to find reaction conditions that allow this unique catalyst to reveal its full potential. After changing the co-oxidizing agent to tert-butyl hydroperoxide and optimizing the osmate/enzyme ratio, the turnover frequency and the turnover number could be increased by an order of magnitude, showing that the catalyst can compete with classical organometallic catalysts. Varying the metal in the active center showed that osmate is by far the most active catalytic center, but the reaction can also be realized with permanganate and iron(II) salts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201501083
  • 2016 • 156 Pilot-scale synthesis of metal nanoparticles by high-speed pulsed laser ablation in liquids
    Streubel, R. and Bendt, G. and Gökce, B.
    Nanotechnology 27 (2016)
    The synthesis of catalysis-relevant nanoparticles such as platinum and gold is demonstrated with productivities of 4 g h-1 for pulsed laser ablation in liquids (PLAL). The major drawback of low productivity of PLAL is overcome by utilizing a novel ultrafast high-repetition rate laser system combined with a polygon scanner that reaches scanning speeds up to 500 m s-1. This high scanning speed is exploited to spatially bypass the laser-induced cavitation bubbles at MHz-repetition rates resulting in an increase of the applicable, ablation-effective, repetition rate for PLAL by two orders of magnitude. The particle size, morphology and oxidation state of fully automated synthesized colloids are analyzed while the ablation mechanisms are studied for different laser fluences, repetition rates, interpulse distances, ablation times, volumetric flow rates and focus positions. It is found that at high scanning speeds and high repetition rate PLAL the ablation process is stable in crystallite size and decoupled from shielding and liquid effects that conventionally occur during low-speed PLAL. © 2016 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0957-4484/27/20/205602
  • 2016 • 155 Plasmonic Au/TiO2 nanostructures for glycerol oxidation
    Dodekatos, G. and Tüysüz, H.
    Catalysis Science and Technology 6 7307-7315 (2016)
    Au nanoparticles supported on P25 TiO2 (Au/TiO2) were prepared by a facile deposition-precipitation method with urea and investigated for surface plasmon-assisted glycerol oxidation under base-free conditions. Au/TiO2 samples were characterized in detail by X-ray diffraction, UV-vis spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The adopted synthetic methodology permits deposition of Au nanoparticles with similar mean particle sizes up to 12.5 wt% loading that allows for the evaluation of the influence of the Au amount (without changing the particle size) on its photocatalytic performance for glycerol oxidation. The reaction conditions were optimized by carrying out a systematic study with different Au loadings on TiO2, reaction times, temperatures, catalyst amounts, O2 pressures and Au particle sizes for photocatalytic reactions as well as traditional heterogeneous catalysis. It has been shown that visible light irradiation during the reaction has a beneficial effect on the conversion of glycerol where the best catalytic results were observed for 7.5 wt% Au loading with an average particle size of around 3 nm. The main product observed, with selectivities up to 63%, was high-value dihydroxyacetone that has important industrial applications, particularly in the cosmetic industry. © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6cy01192f
  • 2016 • 154 Radical perfluoroalkylation - Easy access to 2-perfluoroalkylindol-3-imines-via electron catalysis
    Leifert, D. and Artiukhin, D.G. and Neugebauer, J. and Galstyan, A. and Strassert, C.A. and Studer, A.
    Chemical Communications 52 5997-6000 (2016)
    Arylisonitriles (2 equivalents) react with alkyl and perfluoroalkyl radicals to form 2-alkylated indole-3-imines via two sequential additions to the isonitrile moiety followed by homolytic aromatic substitution. The three component reaction comprises three C-C bond formations. The endocyclic imine functionality in the products is more reactive in follow up chemistry and hydrolysis of the exocyclic imine leads to 3-oxindoles that show fluorescence properties. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c6cc02284g
  • 2016 • 153 Resonant laser processing of nanoparticulate Au/TiO2 films on glass supports: Photothermal modification of a photocatalytic nanomaterial
    Schade, L. and Franzka, S. and Thomas, M. and Hagemann, U. and Hartmann, N.
    Surface Science 650 57-63 (2016)
    Resonant laser processing at λ = 532 nm is used to modify thin Au/TiO2 nanoparticle films on soda lime glass plates. A microfocused continuous-wave laser is employed for local patterning at distinct laser powers. In conjunction with microscopic techniques this approach allows for reproducible high-throughput screening of laser-induced material modifications. Optical microscopy and microspectroscopy reveal laser darkening, i.e. a significantly increased optical absorbance. Scanning electron microscopy and X-ray photoelectron spectroscopy show laser-induced film growth and roughening along with the integration of SiO2 from the glass supports. Raman spectroscopy displays a phase transition from anatase to rutile. Au evaporation and/or integration only takes place at high laser powers. All these modifications provide promising perspectives in view of photocatalytic applications. Data from complementary laser experiments with unblended pure TiO2 coatings at λ = 532 nm and λ = 355 nm point to a photothermal process, in which the optical energy is selectively deposited in the Au nanoparticles and transformed into heat. As a result, thermally activated modifications take place. General prospects of laser processing in targeted modification of nanomaterials for photocatalysis are emphasized. © 2016 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.susc.2016.01.006
  • 2016 • 152 Ruthenium Metal–Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties
    Zhang, W. and Kauer, M. and Halbherr, O. and Epp, K. and Guo, P. and Gonzalez, M.I. and Xiao, D.J. and Wiktor, C. and LIabrés i Xamena, F.X. and Wöll, C. and Wang, Y. and Muhler, M. and Fischer, R.A.
    Chemistry - A European Journal 22 14297-14307 (2016)
    By employing the mixed-component, solid-solution approach, various functionalized ditopic isophthalate (ip) defect-generating linkers denoted 5-X-ipH2, where X=OH (1), H (2), NH2(3), Br (4), were introduced into the mixed-valent ruthenium analogue of [Cu3(btc)2]n(HKUST-1, btc=benzene-1,3,5-tricarboxylate) to yield Ru-DEMOFs (defect-engineered metal–organic frameworks) of the general empirical formula [Ru3(btc)2−x(5-X-ip)xYy]n. Framework incorporation of 5-X-ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh-vacuum IR spectroscopy, thermogravimetric analysis,1H NMR spectroscopy, N2sorption, and X-ray absorption near edge structure. Interestingly, Ru-DEMOF 1 c with 32 % framework incorporation of 5-OH-ip shows the highest BET surface area (≈1300 m2g−1, N2adsorption, 77 K) among all materials (including the parent framework [Ru3(btc)2Yy]n). The characterization data are consistent with two kinds of structural defects induced by framework incorporation of 5-X-ip: modified paddlewheel nodes featuring reduced ruthenium sites (Ruδ+, 0< δ< 2, type A) and missing nodes leading to enhanced porosity (type B). Their relative abundances depend on the choice of the functional group X in the defect linkers. Defects A and B also appeared to play a key role in sorption of small molecules (i.e., CO2, CO, H2) and the catalytic properties of the materials (i.e., ethylene dimerization and the Paal–Knorr reaction). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201602641
  • 2016 • 151 Self-supporting hierarchical porous PtAg alloy nanotubular aerogels as highly active and durable electrocatalysts
    Liu, W. and Haubold, D. and Rutkowski, B. and Oschatz, M. and Hübner, R. and Werheid, M. and Ziegler, C. and Sonntag, L. and Liu, S. and Zheng, Z. and Herrmann, A.-K. and Geiger, D. and Terlan, B. and Gemming, T. and Borchardt, L...
    Chemistry of Materials 28 6477-6483 (2016)
    Developing electrocatalysts with low cost, high activity, and good durability is urgently demanded for the wide commercialization of fuel cells. By taking advantage of nanostructure engineering, we fabricated PtAg nanotubular aerogels (NTAGs) with high electrocatalytic activity and good durability via a simple galvanic replacement reaction between the in situ spontaneously gelated Ag hydrogel and the Pt precursor. The PtAg NTAGs have hierarchical porous network features with primary networks and pores from the interconnected nanotubes of the aerogel and secondary networks and pores from the interconnected thin nanowires on the nanotube surface, and they show very high porosities and large specific surface areas. Due to the unique structure, the PtAg NTAGs exhibit greatly enhanced electrocatalytic activity toward formic acid oxidation, reaching 19 times higher metal-based mass current density as compared to the commercial Pt black. Furthermore, the PtAg NTAGs show outstanding structural stability and electrochemical durability during the electrocatalysis. Noble metal-based NTAGs are promising candidates for applications in electrocatalysis not only for fuel cells, but also for other energy-related systems. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemmater.6b01394
  • 2016 • 150 Single Nanoparticle Voltammetry: Contact Modulation of the Mediated Current
    Li, X. and Batchelor-Mcauley, C. and Whitby, S.A.I. and Tschulik, K. and Shao, L. and Compton, R.G.
    Angewandte Chemie - International Edition 55 4296-4299 (2016)
    The cyclic voltammetric responses of individual palladium-coated carbon nanotubes are reported. Upon impact - from the solution phase - with the electrified interface, the nanoparticles act as individual nanoelectrodes catalyzing the hydrogen-oxidation reaction. At high overpotentials the current is shown to reach a quasi-steady-state diffusion limit, allowing determination of the tube length. The electrochemical response of the individual nanotubes also reveals the system to be modulated by the electrical contact between the electrode and carbon nanotube. This modulation presents itself as fluctuations in the recorded Faradaic current. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201509017
  • 2016 • 149 Textile Catalysts - An unconventional approach towards heterogeneous catalysis
    Mayer-Gall, T. and Lee, J.-W. and Opwis, K. and List, B. and Gutmann, J.S.
    ChemCatChem 8 1428-1436 (2016)
    Textile catalysts are a new approach utilizing immobilization of different classes of catalysts onto textile materials such as polyethylene terephthalate and polyamide. Robust, inexpensive fibrous materials are chosen because they are available in many variations. By a photochemical approach a series of different supported organocatalysts (organotextile catalysts) has been prepared, showing high catalytic activity and good reusability. The aim of this concept article is to present the scope, limits and open questions of our innovative approach. The working principle of the immobilization and its control parameters will be explained and the scope of useable catalysts is shown. Therefore we will show the significant influence of the anchoring group on loading and more importantly on catalyst activity. This concept is also applicable to organometallic catalysts and enzymes. Understanding the different phenomena allows us to develop "textile catalysts" as a new powerful tool for heterogeneous catalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201501252
  • 2016 • 148 Thermodynamics of Bioreactions
    Held, C. and Sadowski, G.
    Annual Review of Chemical and Biomolecular Engineering 7 395-414 (2016)
    Thermodynamic principles have been applied to enzyme-catalyzed reactions since the beginning of the 1930s in an attempt to understand metabolic pathways. Currently, thermodynamics is also applied to the design and analysis of biotechnological processes. The key thermodynamic quantity is the Gibbs energy of reaction, which must be negative for a reaction to occur spontaneously. However, the application of thermodynamic feasibility studies sometimes yields positive Gibbs energies of reaction even for reactions that are known to occur spontaneously, such as glycolysis. This article reviews the application of thermodynamics in enzyme-catalyzed reactions. It summarizes the basic thermodynamic relationships used for describing the Gibbs energy of reaction and also refers to the nonuniform application of these relationships in the literature. The review summarizes state-of-the-art approaches that describe the influence of temperature, pH, electrolytes, solvents, and concentrations of reacting agents on the Gibbs energy of reaction and, therefore, on the feasibility and yield of biological reactions. Copyright © 2016 by Annual Reviews. All rights reserved.
    view abstractdoi: 10.1146/annurev-chembioeng-080615-034704
  • 2016 • 147 Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions
    Mistry, H. and Behafarid, F. and Reske, R. and Varela, A.S. and Strasser, P. and Roldan Cuenya, B.
    ACS Catalysis 6 1075-1080 (2016)
    The selectivity of heterogeneously catalyzed chemical reactions is well-known to be dependent on nanoscale determinants, such as surface atomic geometry and composition. However, principles to control the selectivity of nanoparticle (NP) catalysts by means of mesoscopic descriptors, such as the interparticle distance, have remained largely unexplored. We used well-defined copper catalysts to deconvolute the effect of NP size and distance on product selectivity during CO2 electroreduction. Corroborated by reaction-diffusion modeling, our results reveal that mesoscale phenomena such as interparticle reactant diffusion and readsorption of intermediates play a defining role in product selectivity. More importantly, this study uncovers general principles of tailoring NP activity and selectivity by carefully engineering size and distance. These principles provide guidance for the rational design of mesoscopic catalyst architectures in order to enhance the production of desired reaction products. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.5b02202
  • 2016 • 146 Ultrahigh vacuum and electrocatalysis – The powers of quantitative surface imaging
    P. Mercer, M. and E. Hoster, H.
    Nano Energy 29 394-413 (2016)
    We highlight the impact of Ultrahigh Vacuum (UHV)-born surface science on modern electrocatalysis. The microscopic, atomic level picture of surface adsorption and reaction, which was developed in the surface science community in decades of systematic research on single crystals in UHV, has meanwhile become state-of-the-art also in electrochemistry. For the example of CO on Pt(111) single crystals, which has been extensively studied at the solid/gas and the solid/liquid interface using atomic resolution scanning tunnelling microscopy (STM), we highlight how both interfaces may have even more in common than often assumed. We then illustrate how planar model surfaces such as mono- and bimetallic single crystals and surface alloys, prepared and thoroughly analysed in UHV, enabled a systematic search for improved electrocatalysts. Surface alloys, thermodynamically more stable than foreign metal islands, are a particularly important sub-group of model surfaces, which so far have only been fabricated in UHV. We also flag that model surfaces may not always assume the structure anticipated for the respective experiment, regardless of their preparation in UHV or by electrochemical methods. “Accidental” surface alloying may be more common than often assumed, leading to misinterpretations of the structure-property relationships targeted in many model studies. We highlight that controlled surface alloy formation should be a key step in any model study looking at bimetallic systems in order to get an idea what the effect of unintended alloying could possibly be, and to cross-check whether alloyed surfaces may potentially be the better electrocatalysts in the first place. © 2016
    view abstractdoi: 10.1016/j.nanoen.2016.04.015
  • 2016 • 145 ZnPd/ZnO Aerogels as Potential Catalytic Materials
    Ziegler, C. and Klosz, S. and Borchardt, L. and Oschatz, M. and Kaskel, S. and Friedrich, M. and Kriegel, R. and Keilhauer, T. and Armbrüster, M. and Eychmüller, A.
    Advanced Functional Materials 26 1014-1020 (2016)
    Many different aerogel materials are known to be accessible via the controlled destabilization of the respective nanoparticle suspensions. Especially for applications in heterogeneous catalysis such materials with high specific surface areas are highly desirable. Here, a facile method to obtain a mixed ZnPd/ZnO aerogel via a reductive treatment of a preformed Pd/ZnO aerogel is presented. Different morphologies of the Pd/ZnO aerogels could be achieved by controlling the destabilization of the ZnO sol. All aerogels show a high CO2 selectivity of up to 96% and a very good activity in methanol steam reforming that delivers hydrogen, which is one of the most important fuels for future energy concepts. The method presented is promising for different transition metal/metal oxide systems and hence opens a path to a huge variety of materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adfm.201503000
  • 2015 • 144 A Redox Hydrogel Protects the O2-Sensitive [FeFe]-Hydrogenase from Chlamydomonas reinhardtii from Oxidative Damage
    Oughli, A.A. and Conzuelo, F. and Winkler, M. and Happe, T. and Lubitz, W. and Schuhmann, W. and Rüdiger, O. and Plumeré, N.
    Angewandte Chemie - International Edition 54 12329-12333 (2015)
    The integration of sensitive catalysts in redox matrices opens up the possibility for their protection from deactivating molecules such as O2. [FeFe]-hydrogenases are enzymes catalyzing H2 oxidation/production which are irreversibly deactivated by O2. Therefore, their use under aerobic conditions has never been achieved. Integration of such hydrogenases in viologen-modified hydrogel films allows the enzyme to maintain catalytic current for H2 oxidation in the presence of O2, demonstrating a protection mechanism independent of reactivation processes. Within the hydrogel, electrons from the hydrogenase-catalyzed H2 oxidation are shuttled to the hydrogel-solution interface for O2 reduction. Hence, the harmful O2 molecules do not reach the hydrogenase. We illustrate the potential applications of this protection concept with a biofuel cell under H2/O2 mixed feed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201502776
  • 2015 • 143 Bimetallic Zn and Hf on silica catalysts for the conversion of ethanol to 1,3-butadiene
    De Baerdemaeker, T. and Feyen, M. and Müller, U. and Yilmaz, B. and Xiao, F.-S. and Zhang, W. and Yokoi, T. and Bao, X. and Gies, H. and De Vos, D.E.
    ACS Catalysis 5 3393-3397 (2015)
    Silica-supported catalysts for the conversion of ethanol to 1,3-butadiene were investigated. The combination of Hf(IV) and Zn(II) resulted in a stable, active, and selective catalyst in which the Zn(II) effectively suppressed the dehydration activity of Hf(IV); the catalyst preparation method plays a crucial role. Using the crystalline Zn-silicate hemimorphite as an alternative Zn(II) source proved to be even more successful in suppressing ethanol dehydration. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.5b00376
  • 2015 • 142 Combined experiment and theory approach in surface chemistry: Stairway to heaven?
    Exner, K.S. and Heß, F. and Over, H. and Seitsonen, A.P.
    Surface Science 640 165-180 (2015)
    In this perspective we discuss how an intimate interaction of experiments with theory is able to deepen our insight into the catalytic reaction system on the molecular level. This strategy is illustrated by discussing various examples from our own research of surface chemistry and model catalysis. The particular examples were carefully chosen to balance the specific strength of both approaches - theory and experiment - and emphasize the benefit of this combined approach. We start with the determination of complex surface structures, where diffraction techniques in combination with theory are clear-cut. The promoter action of alkali metals in heterogeneous catalysis is rationalized with theory and experiment for the case of CO coadsorption. Predictive power of theory is limited as demonstrated with the apparent activity of chlorinated TiO2(110) in the oxidation of HCl: Even if we know all elementary reaction steps of a catalytic reaction mechanism, the overall kinetics may remain elusive and require the application kinetic Monte Carlo simulations. Catalysts are not always stable under reaction conditions and may chemically transform as discussed for the CO oxidation reaction over ruthenium. Under oxidizing reaction conditions ruthenium transforms into RuO2, a process which is hardly understood on the molecular level. Lastly we focus on electrochemical reactions. Here theory is clearly ahead since spectroscopic methods are not available to resolve the processes at the electrode surface. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.susc.2015.01.006
  • 2015 • 141 Different recycling concepts in the homogeneously catalysed synthesis of terpenyl amines
    Färber, T. and Schulz, R. and Riechert, O. and Zeiner, T. and Górak, A. and Sadowski, G. and Behr, A.
    Chemical Engineering and Processing: Process Intensification 98 22-31 (2015)
    The homogeneously catalysed hydroamination reaction of β-myrcene with morpholine to terpenyl amines was investigated. Two different techniques to avoid catalyst losses from the liquid phase were applied: Thermomorphic Multicomponent Solvent (TMS)-systems, in which the temperature-sensitivity of the binodal curve is exploited and Liquid-Liquid Two-Phase (LLTP)-systems, in which the reaction happens at the phase interface. The highest β-myrcene conversion of more than 90% and a product yield of more than 80% was measured in a TMS-system consisting of n-heptane and acetonitrile. The same conversion was reached in a LLTP-system consisting of water and β-myrcene, whereas a product yield of 55% was achieved. Experimental data of the liquid-liquid phase equilibria resulted in thermodynamic fundamentals for the design of chemical reactors for the production of amines. Theoretical prediction of equilibrium compositions using PC-SAFT equation of state agree excellent with measured values. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.cep.2015.09.016
  • 2015 • 140 Fast and Reproducible Testing of Cu-Co-Based Catalysts Applied in the Conversion of Synthesis Gas to Ethanol and Higher Alcohols
    Anton, J. and Ruland, H. and Kaluza, S. and Muhler, M.
    Catalysis Letters 145 1374-1381 (2015)
    A test procedure for alkali-free Cu-Co-based catalysts synthesized by co-precipitation was established allowing the fast assessment and screening of their catalytic properties in the synthesis of higher alcohols by online GC analysis. Due to precisely controlled initial deactivation of the catalysts at 280 °C long-term measurements were avoided and steady-state conditions at 260 °C were reached within a short period of time. Temperatures up to 300 °C were found to favor the formation of methanol, whereas the product distribution was not affected at lower space velocities. Even traces of alkali ions present due to insufficient washing were found to strongly affect the catalytic properties. (Graph Presented). © Springer Science+Business Media 2015
    view abstractdoi: 10.1007/s10562-015-1543-2
  • 2015 • 139 Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors
    Calle-Vallejo, F. and Tymoczko, J. and Colic, V. and Vu, Q.H. and Pohl, M.D. and Morgenstern, K. and Loffreda, D. and Sautet, P. and Schuhmann, W. and Bandarenka, A.S.
    Science 350 185-189 (2015)
    A good heterogeneous catalyst for a given chemical reaction very often has only one specific type of surface site that is catalytically active. Widespread methodologies such as Sabatier-type activity plots determine optimal adsorption energies to maximize catalytic activity, but these are difficult to use as guidelines to devise new catalysts. We introduce "coordination-activity plots" that predict the geometric structure of optimal active sites. The method is illustrated on the oxygen reduction reaction catalyzed by platinum. Sites with the same number of first-nearest neighbors as (111) terraces but with an increased number of second-nearest neighbors are predicted to have superior catalytic activity. We used this rationale to create highly active sites on platinum (111), without alloying and using three different affordable experimental methods.
    view abstractdoi: 10.1126/science.aab3501
  • 2015 • 138 Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al2O3 Catalysts Induced by Strong Metal-Support Interactions
    Lunkenbein, T. and Schumann, J. and Behrens, M. and Schlögl, R. and Willinger, M.G.
    Angewandte Chemie - International Edition 54 4544-4548 (2015)
    In industrially relevant Cu/ZnO/Al<inf>2</inf>O<inf>3</inf> catalysts for methanol synthesis, the strong metal support interaction between Cu and ZnO is known to play a key role. Here we report a detailed chemical transmission electron microscopy study on the nanostructural consequences of the strong metal support interaction in an activated high-performance catalyst. For the first time, clear evidence for the formation of metastable "graphite-like" ZnO layers during reductive activation is provided. The description of this metastable layer might contribute to the understanding of synergistic effects between the components of the Cu/ZnO/Al<inf>2</inf>O<inf>3</inf> catalysts. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201411581
  • 2015 • 137 General Method for the Synthesis of Hollow Mesoporous Carbon Spheres with Tunable Textural Properties
    Mezzavilla, S. and Baldizzone, C. and Mayrhofer, K.J.J. and Schüth, F.
    ACS Applied Materials and Interfaces 7 12914-12922 (2015)
    A versatile synthetic procedure to prepare hollow mesoporous carbon spheres (HMCS) is presented here. This approach is based on the deposition of a homogeneous hybrid polymer/silica composite shell on the outer surface of silica spheres through the surfactant-assisted simultaneous polycondensation of silica and polymer precursors in a colloidal suspension. Such composite materials can be further processed to give hollow mesoporous carbon spheres. The flexibility of this method allows for independent control of the morphological (i.e., core diameter and shell thickness) and textural features of the carbon spheres. In particular, it is demonstrated that the size of the pores within the mesoporous shell can be precisely tailored over an extended range (2-20 nm) by simply adjusting the reaction conditions. In a similar fashion, also the specific carbon surface area as well as the total shell porosity can be tuned. Most importantly, the textural features can be adjusted without affecting the dimension or the morphology of the spheres. The possibility to directly modify the shell textural properties by varying the synthetic parameters in a scalable process represents a distinct asset over the multistep hard-templating (nanocasting) routes. As an exemplary application, Pt nanoparticles were encapsulated in the mesoporous shell of HMCS. The resulting Pt@HMCS catalyst showed an enhanced stability during the oxygen reduction reaction, one of the most important reactions in electrocatalysis. This new synthetic procedure could allow the expansion, perhaps even beyond the lab-scale, of advanced carbon nanostructured supports for applications in catalysis. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsami.5b02580
  • 2015 • 136 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 • 135 Hot electron-induced reduction of small molecules on photorecycling metal surfaces
    Xie, W. and Schlücker, S.
    Nature Communications 6 (2015)
    Noble metals are important photocatalysts due to their ability to convert light into chemical energy. Hot electrons, generated via the non-radiative decay of localized surface plasmons, can be transferred to reactants on the metal surface. Unfortunately, the number of hot electrons per molecule is limited due to charge-carrier recombination. In addition to the reduction half-reaction with hot electrons, also the corresponding oxidation counter-half-reaction must take place since otherwise the overall redox reaction cannot proceed. Here we report on the conceptual importance of promoting the oxidation counter-half-reaction in plasmon-mediated catalysis by photorecycling in order to overcome this general limitation. A six-electron photocatalytic reaction occurs even in the absence of conventional chemical reducing agents due to the photoinduced recycling of Ag atoms from hot holes in the oxidation half-reaction. This concept of multi-electron, counter-half-reaction-promoted photocatalysis provides exciting new opportunities for driving efficient light-to-energy conversion processes. © 2015 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/ncomms8570
  • 2015 • 134 Hybridization of an Aβ-specific antibody fragment with aminopyrazole-based β-sheet ligands displays striking enhancement of target affinity
    Hellmert, M. and Müller-Schiffmann, A. and Peters, M.S. and Korth, C. and Schrader, T.
    Organic and Biomolecular Chemistry 13 2974-2979 (2015)
    Determining Aβ levels in body fluids remains a powerful tool in the diagnostics of Alzheimer's disease. This report delineates a new supramolecular strategy which increases the affinity of antibodies towards Aβ to make diagnostic procedures more sensitive. A monoclonal antibody IC16 was generated to an N-terminal epitope of Aβ and the variable regions of the heavy and light chains were cloned as a recombinant protein (scFv). A 6 × histidine tag was fused to the C-terminus of IC16-scFv allowing hybridization with a small organic β-sheet binder via Ni-NTA complexation. On the other hand, a multivalent nitrilotriacetic acid (NTA)-equipped trimeric aminopyrazole (AP) derivative was synthesized based on a cyclam platform; and experimental evidence was obtained for efficient Ni2+-mediated complex formation with the histidine-tagged antibody species. In a proof of principle experiment the hybrid molecule showed a strong increase in affinity towards Aβ. Thus, the specific binding power of recombinant antibody fragments to their β-sheet rich targets can be conveniently enhanced by non-covalent hybridization with small organic β-sheet binders. © 2015 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c4ob02411g
  • 2015 • 133 In Situ X-ray Diffraction Study of Co-Al Nanocomposites as Catalysts for Ammonia Decomposition
    Gu, Y.-Q. and Fu, X.-P. and Du, P.-P. and Gu, D. and Jin, Z. and Huang, Y.-Y. and Si, R. and Zheng, L.-Q. and Song, Q.-S. and Jia, C.-J. and Weidenthaler, C.
    Journal of Physical Chemistry C 119 17102-17110 (2015)
    Co-Al nanocomposite materials as active and stable catalysts for ammonia decomposition have been synthesized by a one-pot evaporation-induced self-assembly method. The catalysts were characterized by various techniques including powder X-ray diffraction (XRD), X-ray absorption fine structure (XAFS), X-ray photoelectron spectroscopy (XPS), N<inf>2</inf> adsorption/desorption, and transmission/scanning electron microscopy (TEM/SEM). Especially, in situ XRD under catalytic reaction conditions was performed, and metallic Co with a cubic structure was identified to be most probably the active crystalline phase for the decomposition of ammonia; also, contribution of CoO to the catalytic activity cannot be excluded. Most importantly, the introduction of alumina can significantly suppress the agglomeration of the active metallic Co phase and thus maintain the high activity of the cobalt catalyst. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.5b02932
  • 2015 • 132 Kinetics enhancement, reaction pathway change, and mechanism clarification in LiBH4 with Ti-catalyzed nanocrystalline MgH2 composite
    Shao, H. and Felderhoff, M. and Weidenthaler, C.
    Journal of Physical Chemistry C 119 2341-2348 (2015)
    A composite of 2LiBH4 + nano-MgH2* (Ti-catalyzed) shows significantly enhanced desorption kinetics compared to a conventional mixture of 2LiBH4 + MgH2. The desorption mechanism was studied in the temperature range between 304 and 383 °C and under different pressure conditions. Desorption temperatures are 50-70 °C lower compared to conventional 2LiBH4 + MgH2 mixtures. During the hydrogen release from a mixture of 2LiBH4 + nano-MgH2* at a hydrogen back-pressure of 0.4 MPa, MgB2 is formed and three different plateaus of equilibrium were detected. The reaction pathway is changed at 360 °C for the 2LiBH4 + MgH2 system when the nano-MgH2* is used. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/jp511479d
  • 2015 • 131 Kinetics of deactivation on Cu/ZnO/Al2O3 methanol synthesis catalysts
    Fichtl, M.B. and Schlereth, D. and Jacobsen, N. and Kasatkin, I. and Schumann, J. and Behrens, M. and Schlögl, R. and Hinrichsen, O.
    Applied Catalysis A: General 502 262-270 (2015)
    Deactivation behavior is an important topic in catalyst development. In case of methanol synthesis the conventional Cu/ZnO/Al<inf>2</inf>O<inf>3</inf> system is commonly known to be prone to sintering, however, information about the structural development during deactivation or the sintering mechanism(s) are scarce. We present a systematic deactivation study on three different Cu/ZnO/Al<inf>2</inf>O<inf>3</inf> catalysts which are aged under constant conditions and periodically analyzed using kinetic measurements and N<inf>2</inf>O chemisorption. A power law model for the catalyst activity with time on stream is derived. Furthermore it is found, that the presence of water provokes a steep loss in active surface area and specific activity. Also, the TEM particle size distributions generated during the aging treatment are evaluated and discussed. © 2015 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.apcata.2015.06.014
  • 2015 • 130 Ligand Effects and Their Impact on Electrocatalytic Processes Exemplified with the Oxygen Evolution Reaction (OER) on RuO2(110)
    Exner, K.S. and Anton, J. and Jacob, T. and Over, H.
    ChemElectroChem 2 707-713 (2015)
    By using the abinitio atomistic thermodynamics approach guided by a DFT-derived volcano curve, we demonstrate that the thermodynamic part of the reaction barrier to the oxygen evolution reaction (OER) over RuO2(110) can be significantly reduced when moderately lowering the free adsorption energy of oxygen to the catalytically active Ru center (Rucus). With the selective replacement of metal sites in the second coordination shell of Rucus, the free oxygen adsorption energy is reduced by about 0.8 and 1.0eV for Cr and Ir, respectively. The weakening of Rucus and oxygen-on-top (RucusOot) bonding results in a substantial decrease in the thermodynamic part of the reaction barrier (Gibbs free-energy loss) by 180meV for Cr and 150meV for Ir. The presented strategy is motivated by homogeneous metal catalysis where dedicated modifications of the ligands are able to tune the catalytic performance of the active metal center. Pick′n′Mix: Based on homogeneous metal catalysis, in which dedicated modifications of the ligands are able to tune the catalytic performance of the active metal center, DFT calculations are used to demonstrate that the thermodynamic part of the reaction barrier (Gibbs free-energy loss) to the oxygen evolution reaction over RuO2(110) can be significantly reduced by selectively substituting the metal sites in the second coordination shell of the active center. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/celc.201402430
  • 2015 • 129 Ligand-free Gold Nanoparticles as a Reference Material for Kinetic Modelling of Catalytic Reduction of 4-Nitrophenol
    Gu, S. and Kaiser, J. and Marzun, G. and Ott, A. and Lu, Y. and Ballauff, M. and Zaccone, A. and Barcikowski, S. and Wagener, P.
    Catalysis Letters 145 1105-1112 (2015)
    The reduction of 4-nitrophenol by sodium borohydride is a common model reaction to test the catalytic activity of metal nanoparticles. As all reaction steps proceed solely on the surface of the metal nanoparticles (Langmuir-Hinshelwood model), ligand-coverage of metal nanoparticles impedes the merging of theory and experiment. Therefore we analyzed the catalytic activity of bare gold nanoparticles prepared by laser ablation in liquid without any stabilizers or ligands. The catalytic reaction is characterized by a full kinetic analysis including 4-hydroxylaminophenol as an intermediate species. Excellent agreement between theory and experiment is found. Moreover, the suspension of the nanoparticles remains stable. Hence, ligand-free nanoparticles can be used as a reference material for mechanistic studies of catalytic reactions. In addition, the analysis shows that gold nanoparticles synthesized by laser ablation are among the most active catalysts for this reaction. (Graph Presented). © 2015 Springer Science+Business Media.
    view abstractdoi: 10.1007/s10562-015-1514-7
  • 2015 • 128 Mechanism of protection of catalysts supported in redox hydrogel films
    Fourmond, V. and Stapf, S. and Li, H. and Buesen, D. and Birrell, J. and Rüdiger, O. and Lubitz, W. and Schuhmann, W. and Plumeré, N. and Léger, C.
    Journal of the American Chemical Society 137 5494-5505 (2015)
    The use of synthetic inorganic complexes as supported catalysts is a key route in energy production and in industrial synthesis. However, their intrinsic oxygen sensitivity is sometimes an issue. Some of us have recently demonstrated that hydrogenases, the fragile but very efficient biological catalysts of H<inf>2</inf> oxidation, can be protected from O<inf>2</inf> damage upon integration into a film of a specifically designed redox polymer. Catalytic oxidation of H<inf>2</inf> produces electrons which reduce oxygen near the film/solution interface, thus providing a self-activated protection from oxygen [Plumeré et al., Nat Chem. 2014, 6, 822-827]. Here, we rationalize this protection mechanism by examining the time-dependent distribution of species in the hydrogenase/polymer film, using measured or estimated values of all relevant parameters and the numerical and analytical solutions of a realistic reaction-diffusion scheme. Our investigation sets the stage for optimizing the design of hydrogenase-polymer films, and for expanding this strategy to other fragile catalysts. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/jacs.5b01194
  • 2015 • 127 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 • 126 Process boundaries of irreversible scCO2-assisted phase separation in biphasic whole-cell biocatalysis
    Brandenbusch, C. and Glonke, S. and Collins, J. and Hoffrogge, R. and Grunwald, K. and Bühler, B. and Schmid, A. and Sadowski, G.
    Biotechnology and Bioengineering 112 2316-2323 (2015)
    The formation of stable emulsions in biphasic biotransformations catalyzed by microbial cells turned out to be a major hurdle for industrial implementation. Recently, a cost-effective and efficient downstream processing approach, using supercritical carbon dioxide (scCO2) for both irreversible emulsion destabilization (enabling complete phase separation within minutes of emulsion treatment) and product purification via extraction has been proposed by Brandenbusch et al. (2010). One of the key factors for a further development and scale-up of the approach is the understanding of the mechanism underlying scCO2-assisted phase separation. A systematic approach was applied within this work to investigate the various factors influencing phase separation during scCO2 treatment (that is pressure, exposure of the cells to CO2, and changes of cell surface properties). It was shown that cell toxification and cell disrupture are not responsible for emulsion destabilization. Proteins from the aqueous phase partially adsorb to cells present at the aqueous-organic interface, causing hydrophobic cell surface characteristics, and thus contribute to emulsion stabilization. By investigating the change in cell-surface hydrophobicity of these cells during CO2 treatment, it was found that a combination of catastrophic phase inversion and desorption of proteins from the cell surface is responsible for irreversible scCO2 mediated phase separation. These findings are essential for the definition of process windows for scCO2-assisted phase separation in biphasic whole-cell biocatalysis. © 2015 Wiley Periodicals, Inc.
    view abstractdoi: 10.1002/bit.25655
  • 2015 • 125 Scalability and feasibility of photoelectrochemical H2 evolution: the ultimate limit of Pt nanoparticle as an HER catalyst
    Kemppainen, E. and Bodin, A. and Sebok, B. and Pedersen, T. and Seger, B. and Mei, B. and Bae, D. and Vesborg, P.C.K. and Halme, J. and Hansen, O. and Lund, P.D. and Chorkendorff, I.
    Energy and Environmental Science 8 2991-2999 (2015)
    The recent surge in investigating electrocatalysts for the H2 evolution reaction is based on finding a cheap alternative to Pt. However platinum's excellent catalytic activity means very little catalyst needs to be used. The present study combines model experiments with numerical modeling to determine exactly how little catalyst is needed. Specifically we investigate ultra-low Pt loadings for use in photoelectrochemical H2 evolution using TiO2-Ti-pn+Si photocathodes. At a current density of 10 mA cm-2, we photocathodically evolve H2 at +465, +450, +350 and +270 mV vs., RHE at Pt loadings of 1000, 200, 50, and 10 ng cm-2 corresponding to HER overpotentials of η1000ng = 32 mV, η200ng = 46 mV, η50ng = 142 mV, and η10ng = 231 mV. To put this in perspective, if 30% of the world's current annual Pt production was used for H2 evolution catalysis, using a loading of 100 ng cm-2 and a current of 10 mA cm-2 would produce 1 TWaverage of H2. The photoelectrochemical data matched the modeling calculations implying that we were near the fundamental maximum in performance for our system. Furthermore modeling indicated that the overpotentials were dominated by mass transfer effects, rather than catalysis unless catalyst loadings were less than 1000 ng cm-2. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5ee02188j
  • 2015 • 124 Size control and supporting of palladium nanoparticles made by laser ablation in saline solution as a facile route to heterogeneous catalysts
    Marzun, G. and Nakamura, J. and Zhang, X. and Barcikowski, S. and Wagener, P.
    Applied Surface Science 348 75-84 (2015)
    In the literature many investigations on colloidal stability and size control of gold nanoparticles are shown but less for ligand-free palladium nanoparticles, which can be promising materials in various applications. Palladium nanoparticles are perspective materials for a manifold of energy application like photo- and electrocatalysis or hydrogen storage. For this purpose, size-controlled nanoparticles with clean surfaces and facile immobilization on catalyst supports are wanted. Laser ablation in saline solution yields ligand-free, charged colloidal palladium nanoparticles that are supported by titania and graphene nanosheets as model systems for photo- and electrocatalysis, respectively. By adjusting the ionic strength during laser ablation in liquid, it is possible to control stability and particle size without compromising subsequent nanoparticle adsorption of supporting materials. A quantitative deposition of nearly 100% yield with up to 18 wt% nanoparticle load was achieved. The average size of the laser-generated nanoparticles remains the same after immobilization on a support material, in contrast to other preparation methods of catalysts. The characterization by X-ray photoelectron spectroscopy reveals a redox reaction between the immobilized nanoparticles and the graphene support. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2015.01.108
  • 2015 • 123 Structural stability and Lewis acidity of tetravalent Ti, Sn, or Zr-linked interlayer-expanded zeolite COE-4: A DFT study
    Li, H. and Wang, J. and Zhou, D. and Tian, D. and Shi, C. and Müller, U. and Feyen, M. and Gies, H. and Xiao, F.-S. and De Vos, D. and Yokoi, T. and Bao, X. and Zhang, W.
    Microporous and Mesoporous Materials 218 160-166 (2015)
    Density functional theory (DFT) has been performed to characterize the structural stability and Lewis acidic properties of the T-COE-4 zeolites, in which the linked site between the layers is isomorphously substituted by the tetravalent Ti-, Sn-, or Zr- heteroatom. The effects of substitution energy and equilibrium geometry parameters on the stability of T-COE-4 are investigated. The computed Fukui function values and the adsorption of ammonia, pyridine, water and trimethylphosphine oxide molecules have been employed to predict the Lewis acid strength of the T-COE-4 zeolites. It is found that the smaller the O1-T-O2 bond angle is, the more difficult is to form the regular tetrahedral unit. The substitution energies at the linker position increase in the following sequence: Ti-COE-4 < Sn-COE-4 < Zr-COE-4. The incorporation of Ti-, Sn-, or Zr-heteroatom enhances the Lewis acidity of COE-4 zeolite. It is predicted that the Lewis acid strength increases in the order of Ti-COE-4 < Zr-COE-4 & Sn-COE-4 by the adsorption of different base molecules. Six O-T-O bond angles are divided into different extent to form the analogous trigonal bipyramid structures in the optimized ligand adsorbed complexes. These findings could be beneficial for the structural design and catalytic function modification of the interlayer-expanded zeolites. © 2015 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.micromeso.2015.07.020
  • 2015 • 122 The Interaction of Formic Acid with Zinc Oxide: A Combined Experimental and Theoretical Study on Single Crystal and Powder Samples
    Buchholz, M. and Li, Q. and Noei, H. and Nefedov, A. and Wang, Y. and Muhler, M. and Fink, K. and Wöll, C.
    Topics in Catalysis 58 174-183 (2015)
    We present azimuth- and polarization-dependent infrared spectroscopy results obtained under ultra-high vacuum conditions on surface species formed by the interaction of formic acid with the mixed-terminated ZnO(101¯0) surface. Since there are no previous IRRAS data for formic-acid derived species on any ZnO single crystal surfaces, we have carried out calculations using density function theory to aid the interpretation of the results. From our combined experimental and theoretical data we conclude that two different formate species are formed. The more strongly bound species is a bidentate with the formate molecular plane oriented along the [12¯10] direction. The less strongly bound species is a quasi-bidentate with its molecular plane oriented along the [0001] direction. This second species is characterized by a strong hydrogen bond between a surface OH species and the formate. In addition, IR data were recorded for the same molecule adsorbed on commercial ZnO nanoparticles. The different bands of the powder IR-data are assigned on the basis of the experimental and theoretical results obtained for the single crystal surface. This study demonstrates the importance of the Surface Science approach to heterogeneous catalysis also for ZnO, an important catalyst for the conversion of syngas to methanol. © 2014 Springer Science+Business Media.
    view abstractdoi: 10.1007/s11244-014-0356-7
  • 2015 • 121 The Yin and Yang in the development of catalytic processes: Catalysis research and reaction engineering
    Prieto, G. and Schüth, F.
    Angewandte Chemie - International Edition 54 3222-3239 (2015)
    A synergetic interplay: Catalysis is a key research field within BASF. Successful industrial chemistry is always the result of a combination of catalyst and process development. The interplay of catalyst chemistry and reaction engineering is discussed for processes such as the sulfuric acid production, ammonia synthesis, methanol synthesis, fluid catalytic cracking, and direct epoxidation of propylene. (Figure Presented). © 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/anie.201409885
  • 2015 • 120 Three-dimensional Cu foam-supported single crystalline mesoporous Cu2O nanothorn arrays for ultra-highly sensitive and efficient nonenzymatic detection of glucose
    Dong, C. and Zhong, H. and Kou, T. and Frenzel, J. and Eggeler, G. and Zhang, Z.
    ACS Applied Materials and Interfaces 7 20215-20223 (2015)
    Highly sensitive and efficient biosensors play a crucial role in clinical, environmental, industrial, and agricultural applications, and tremendous efforts have been dedicated to advanced electrode materials with superior electrochemical activities and low cost. Here, we report a three-dimensional binder-free Cu foam-supported Cu<inf>2</inf>O nanothorn array electrode developed via facile electrochemistry. The nanothorns growing in situ along the specific direction of <011> have single crystalline features and a mesoporous surface. When being used as a potential biosensor for nonenzyme glucose detection, the hybrid electrode exhibits multistage linear detection ranges with ultrahigh sensitivities (maximum of 97.9 mA mM-1 cm-2) and an ultralow detection limit of 5 nM. Furthermore, the electrode presents outstanding selectivity and stability toward glucose detection. The distinguished performances endow this novel electrode with powerful reliability for analyzing human serum samples. These unprecedented sensing characteristics could be ascribed to the synergistic action of superior electrochemical catalytic activity of nanothorn arrays with dramatically enhanced surface area and intimate contact between the active material (Cu<inf>2</inf>O) and current collector (Cu foam), concurrently supplying good conductivity for electron/ion transport during glucose biosensing. Significantly, our findings could guide the fabrication of new metal oxide nanostructures with well-organized morphologies and unique properties as well as low materials cost. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsami.5b05738
  • 2015 • 119 Using cavity microelectrodes for electrochemical noise studies of oxygen-evolving catalysts
    Rincón, R.A. and Battistel, A. and Ventosa, E. and Chen, X. and Nebel, M. and Schuhmann, W.
    ChemSusChem 8 560-566 (2015)
    Cavity microelectrodes were used as a binder-free platform to evaluate oxygen evolution reaction (OER) electrocatalysts with respect to gas bubble formation and departure. Electrochemical noise measurements were performed by using RuO2 as a benchmark catalyst and the perovskite La0.58Sr0.4Fe0.8Co0.2O3 as a non-noble metal OER catalyst with lower intrinsic conductivity. Changes in the current during the OER originate from variations in electrolyte resistance during the formation of the gas phase and partial coverage of the active area. Fluctuations observed in current and conductance transients were used to establish the contribution from the ohmic overpotential and to determine the characteristic frequency of oxygen evolution. The proposed quantitative determination of gas bubble growth and departure opens up the route for a rational interface design by considering gas bubble growth and departure as a main contributing factor to the overall electrocatalytic activity at high current densities. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201402855
  • 2014 • 118 A molecular iron catalyst for the acceptorless dehydrogenation and hydrogenation of N-heterocycles
    Chakraborty, S. and Brennessel, W.W. and Jones, W.D.
    Journal of the American Chemical Society 136 8564-8567 (2014)
    A well-defined iron complex (3) supported by a bis(phosphino)amine pincer ligand efficiently catalyzes both acceptorless dehydrogenation and hydrogenation of N-heterocycles. The products from these reactions are isolated in good yields. Complex 3, the active catalytic species in the dehydrogenation reaction, is independently synthesized and characterized, and its structure is confirmed by X-ray crystallography. A trans-dihydride intermediate (4) is proposed to be involved in the hydrogenation reaction, and its existence is verified by NMR and trapping experiments. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/ja504523b
  • 2014 • 117 A polyphenylene support for pd catalysts with exceptional catalytic activity
    Wang, F. and Mielby, J. and Richter, F.H. and Wang, G. and Prieto, G. and Kasama, T. and Weidenthaler, C. and Bongard, H.-J. and Kegnæs, S. and Fürstner, A. and Schüth, F.
    Angewandte Chemie - International Edition 53 8645-8648 (2014)
    We describe a solid polyphenylene support that serves as an excellent platform for metal-catalyzed reactions that are normally carried out under homogeneous conditions. The catalyst is synthesized by palladium-catalyzed Suzuki coupling which directly results in formation of palladium nanoparticles confined to a porous polyphenylene network. The composite solid is in turn highly active for further Suzuki coupling reactions, including non-activated substrates that are challenging even for molecular catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201404912
  • 2014 • 116 A special thematic compilation/special issue crossover with biochemistry, journal of medicinal chemistry, and ACS medicinal chemistry letters focused on kinases
    Rauh, D.
    ACS Chemical Biology 9 579-580 (2014)
    doi: 10.1021/cb500150d
  • 2014 • 115 Control of solid catalysts down to the atomic scale: Where is the limit?
    Schüth, F.
    Angewandte Chemie - International Edition 53 8599-8604 (2014)
    Down to the last detail: Nanostructured solid catalysts were already known in the early 20th century, but their exact structure was unclear. Nowadays, the arrangement of atoms and particles in solids can be manipulated and analyzed down to the atomic scale (see image). The use of specific highly active catalysts enables industrially relevant reactions to be performed at room temperature. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201402251
  • 2014 • 114 Counting of oxygen defects versus metal surface sites in methanol synthesis catalysts by different probe molecules
    Fichtl, M.B. and Schumann, J. and Kasatkin, I. and Jacobsen, N. and Behrens, M. and Schlögl, R. and Muhler, M. and Hinrichsen, O.
    Angewandte Chemie - International Edition 53 7043-7047 (2014)
    Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N2O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N2O, temperature programmed desorption of H2, and kinetic experiments. The presence of ZnO dramatically influences the N2O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu-ZnO interface and can be used to easily quantify the intensity of Cu-Zn interaction. N2O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H2. A combination of N2O reactive frontal chromatography and H2 temperature-programmed desorption is used to analyze the interplay of copper and zinc oxide in methanol synthesis catalysts. This method provides an easy in situ approach to quantify the direct copper-zinc interaction (SMSI effect) and offers an important possibility to rational catalyst design also for other supported metal catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201400575
  • 2014 • 113 Cu-based catalyst resulting from a Cu,Zn,Al hydrotalcite-like compound: A microstructural, thermoanalytical, and in situ XAS study
    Kühl, S. and Tarasov, A. and Zander, S. and Kasatkin, I. and Behrens, M.
    Chemistry - A European Journal 20 3782-3792 (2014)
    A Cu-based methanol synthesis catalyst was obtained from a phase pure Cu,Zn,Al hydrotalcite-like precursor, which was prepared by co-precipitation. This sample was intrinsically more active than a conventionally prepared Cu/ZnO/Al2O3 catalyst. Upon thermal decomposition in air, the [(Cu0.5Zn0.17Al0.33)(OH) 2(CO3)0.17]×mH2O precursor is transferred into a carbonate-modified, amorphous mixed oxide. The calcined catalyst can be described as well-dispersed "CuO" within ZnAl 2O4 still containing stabilizing carbonate with a strong interaction of Cu2+ ions with the Zn-Al matrix. The reduction of this material was carefully analyzed by complementary temperature-programmed reduction (TPR) and near-edge X-ray absorption fine structure (NEXAFS) measurements. The results fully describe the reduction mechanism with a kinetic model that can be used to predict the oxidation state of Cu at given reduction conditions. The reaction proceeds in two steps through a kinetically stabilized CuI intermediate. With reduction, a nanostructured catalyst evolves with metallic Cu particles dispersed in a ZnAl2O4 spinel-like matrix. Due to the strong interaction of Cu and the oxide matrix, the small Cu particles (7 nm) of this catalyst are partially embedded leading to lower absolute activity in comparison with a catalyst comprised of less-embedded particles. Interestingly, the exposed Cu surface area exhibits a superior intrinsic activity, which is related to a positive effect of the interface contact of Cu and its surroundings. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201302599
  • 2014 • 112 Design and demonstration of an ethanol fuel processor for HT-PEM fuel cell applications
    Gardemann, U. and Steffen, M. and Heinzel, A.
    International Journal of Hydrogen Energy 39 18135-18145 (2014)
    This work describes the development of a compact ethanol fuel processor for small scale high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) systems with 200-500 W electrical power output. Promising markets for reformer fuel cell systems based on ethanol are mobile or portable leisure and security power supply applications as well as small scale stationary off grid power supply and backup power. Main components of the fuel processor to be developed were the reformer reactor, the shift converter, a catalytic burner and heat exchangers. Development focused in particular on the homogeneous evaporation of the liquid reactants ethanol and water for the reformer and burner and on the development of an efficient and autarkic start-up method, respectively. Theoretical as well as experimental work has been carried out for all main components separately including for example catalyst screening and evaporator performance tests in a first project period. Afterwards all components have been assembled to a complete fuel processor which has been qualified with various operation parameter set-ups. A theoretically defined basic operation point could practically be confirmed. The overall start-up time to receive reformate gas with appropriate quality to feed an HT-PEMFC (xCO < 2%) takes around 30 min. At steady state operation the hydrogen power output is around 900 W with H2 and CO fractions of 41.2% and 1.5%, respectively. © 2014 Hydrogen Energy Publications, LLC.
    view abstractdoi: 10.1016/j.ijhydene.2014.05.027
  • 2014 • 111 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 • 110 Interaction of cobalt nanoparticles with oxygen- and nitrogen- functionalized carbon nanotubes and impact on nitrobenzene hydrogenation catalysis
    Chen, P. and Yang, F. and Kostka, A. and Xia, W.
    ACS Catalysis 4 1478-1486 (2014)
    The type and the amount of functional groups on the surface of carbon nanotubes (CNTs) were tuned to improve the activity of supported Co nanoparticles in hydrogenation catalysis. Surface nitrogen species on CNTs significantly promoted the decomposition of the cobalt precursor and the reduction of cobalt oxide, and improved the resistance of metallic Co against oxidation in ambient atmosphere. In the selective hydrogenation of nitrobenzene in the gas phase, Co supported on CNTs with the highest surface nitrogen content showed the highest activity, which is ascribed to the higher reducibility and the lower oxidation state of the Co nanoparticles under reaction conditions. For Co nanoparticles supported on CNTs with a smaller amount of surface nitrogen groups, a repeated reduction at 350 °C was essential to achieve a comparable high catalytic activity reaching 90% conversion at 250 °C, pointing to the importance of nitrogen species for the supported Co nanoparticles in nitrobenzene hydrogenation. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/cs500173t
  • 2014 • 109 Iron-based catalysts for the hydrogenation of esters to alcohols
    Chakraborty, S. and Dai, H. and Bhattacharya, P. and Fairweather, N.T. and Gibson, M.S. and Krause, J.A. and Guan, H.
    Journal of the American Chemical Society 136 7869-7872 (2014)
    Hydrogenation of esters is vital to the chemical industry for the production of alcohols, especially fatty alcohols that find broad applications in consumer products. Current technologies for ester hydrogenation rely on either heterogeneous catalysts operating under extreme temperatures and pressures or homogeneous catalysts containing precious metals such as ruthenium and osmium. Here, we report the hydrogenation of esters under relatively mild conditions by employing an iron-based catalyst bearing a PNP-pincer ligand. This catalytic system is also effective for the conversion of coconut oil derived fatty acid methyl esters to detergent alcohols without adding any solvent. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/ja504034q
  • 2014 • 108 Local visualization of catalytic activity at gas evolving electrodes using frequency-dependent scanning electrochemical microscopy
    Chen, X. and Maljusch, A. and Rincón, R.A. and Battistel, A. and Bandarenka, A.S. and Schuhmann, W.
    Chemical Communications 50 13250-13253 (2014)
    A new concept for the localized characterization of gas evolving electrodes based on scanning electrochemical microscopy (SECM) is suggested. It offers information about the spatial distribution of the predominant locations, which represent the most active catalytic sites, and dynamic characteristics of gas-bubble departure. The knowledge about gas-bubble departure is critical for the assessment and development of new electrode materials for energy applications. This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cc06100d
  • 2014 • 107 Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: Sorption and catalytic properties
    Kozachuk, O. and Luz, I. and Llabrés I Xamena, F.X. and Noei, H. and Kauer, M. and Albada, H.B. and Bloch, E.D. and Marler, B. and Wang, Y. and Muhler, M. and Fischer, R.A.
    Angewandte Chemie - International Edition 53 7058-7062 (2014)
    A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru II/III structural analogue of the well-known MOF family [M 3 II,II(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the "defective" variants in the dissociative chemisorption of CO 2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins. The defect engineering in Ru-based metal-organic frameworks (MOFs) at coordinatively unsaturated metal centers (CUS) induces partial reduction of the metal nodes and leads to properties that are absent for the parent MOF, such as dissociative chemisorption of CO2 and enhanced sorption capacity of CO. The modified MOFs offer new perspectives as multifunctional materials whose performance is controlled by design of the defects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201311128
  • 2014 • 106 Multimetallic aerogels by template-free self-assembly of Au, Ag, Pt, and Pd nanoparticles
    Herrmann, A.-K. and Formanek, P. and Borchardt, L. and Klose, M. and Giebeler, L. and Eckert, J. and Kaskel, S. and Gaponik, N. and Eychmüller, A.
    Chemistry of Materials 26 1074-1083 (2014)
    Nanostructured, porous metals are of great interest for material scientists since they combine high surface area, gas permeability, electrical conductivity, plasmonic behavior, and size-enhanced catalytic reactivity. Here we present the formation of multimetallic porous three-dimensional networks by a template-free self-assembly process. Nanochains are formed by the controlled coalescence of Au, Ag, Pt, and Pd nanoparticles in aqueous media, and their interconnection and interpenetration leads to the formation of a self-supporting network. The resulting noble-metal-gels are transformed into solid aerogels by the supercritical drying technique. Compared to previously reported results, the technique is facilitated by exclusion of additional destabilizers. Moreover, temperature control is demonstrated as a powerful tool, allowing acceleration of the gelation process as well as improvement of its reproducibility and applicability. Electron microscopy shows the nanostructuring of the network and its high porosity. XRD and EDX STEM are used to investigate the alloying behavior of the bimetallic aerogels and prove the control of the alloying state by temperature induced phase modifications. Furthermore, the resulting multimetallic aerogels show an extremely low relative density (&lt;0.2%) and a very high surface area (&gt;50 m2/g) compared to porous noble metals obtained by other approaches. Electrically conductive thin films as well as hybrid materials with organic polymers are depicted to underline the processability of the materials, which is a key factor regarding handling of the fragile structures and integration into device architectures. Owing to their exceptional and tunable properties, multimetallic aerogels are very promising materials for applications in heterogeneous catalysis and electrocatalysis, hydrogen storage, and sensor systems but also in surface enhanced Raman spectroscopy (SERS) and the preparation of transparent conductive substrates. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/cm4033258
  • 2014 • 105 Nanojunction-mediated photocatalytic enhancement in heterostructured CdS/ZnO, CdSe/ZnO, and CdTe/ZnO nanocrystals
    Eley, C. and Li, T. and Liao, F. and Fairclough, S.M. and Smith, J.M. and Smith, G. and Tsang, S.C.E.
    Angewandte Chemie - International Edition 53 7838-7842 (2014)
    A series of highly efficient semiconductor nanocrystal (NC) photocatalysts have been synthesized by growing wurtzite-ZnO tetrahedrons around pre-formed CdS, CdSe, and CdTe quantum dots (QDs). The resulting contact between two small but high-quality crystals creates novel CdX/ZnO heterostructured semiconductor nanocrystals (HSNCs) with extensive type-II nanojunctions that exhibit more efficient photocatalytic decomposition of aqueous organic molecules under UV irradiation. Catalytic testing and characterization indicate that catalytic activity increases as a result of a combination of both the intrinsic chemistry of the chalcogenide anions and the heterojunction structure. Atomic probe tomography (APT) is employed for the first time to probe the spatial characteristics of the nanojunction between cadmium chalcogenide and ZnO crystalline phases, which reveals various degrees of ion exchange between the two crystals to relax large lattice mismatches. In the most extreme case, total encapsulation of CdTe by ZnO as a result of interfacial alloying is observed, with the expected advantage of facilitating hole transport for enhanced exciton separation during catalysis. That's a (quantum dot) wrap! A series of highly active semiconductor photocatalysts have been synthesized by growing wurtzite-ZnO tetrahedrons around pre-formed CdS, CdSe, and CdTe quantum dots. The resulting heterostructured CdX/ZnO nanocrystals with extensive type-II nanojunctions exhibit rapid photocatalytic decomposition of organic molecules in aqueous media. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201404481
  • 2014 • 104 One-step synthesis of bismuth molybdate catalysts via flame spray pyrolysis for the selective oxidation of propylene to acrolein
    Schuh, K. and Kleist, W. and Høj, M. and Trouillet, V. and Jensen, A.D. and Grunwaldt, J.-D.
    Chemical Communications 50 15404-15406 (2014)
    Flame spray pyrolysis (FSP) of Bi(iii)- and Mo(vi)-2-ethylhexanoate dissolved in xylene resulted in various nanocrystalline bismuth molybdate phases depending on the Bi/Mo ratio. Besides α-Bi2Mo3O12 and γ-Bi2MoO6, FSP gave direct access to the metastable β-Bi2Mo2O9 phase with high surface area (19 m2 g-1). This phase is normally only obtained at high calcination temperatures (&gt;560 °C) resulting in lower surface areas. The β-phase was stable up to 400 °C and showed superior catalytic performance compared to α- and γ-phases in selective oxidation of propylene to acrolein at temperatures relevant for industrial applications (360 °C). This journal is © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c4cc07527g
  • 2014 • 103 Oxidation of bioethanol using zeolite-encapsulated gold nanoparticles
    Mielby, J. and Abildstrøm, J.O. and Wang, F. and Kasama, T. and Weidenthaler, C. and Kegnæs, S.
    Angewandte Chemie - International Edition 53 12513-12516 (2014)
    With the ongoing developments in biomass conversion, the oxidation of bioethanol to acetaldehyde may become a favorable and green alternative to the preparation from ethylene. Here, a simple and effective method to encapsulate gold nanoparticles in zeolite silicalite-1 is reported and their high activity and selectivity for the catalytic gas-phase oxidation of ethanol are demonstrated. The zeolites are modified by a recrystallization process, which creates intraparticle voids and mesopores that facilitate the formation of small and disperse nanoparticles upon simple impregnation. The individual zeolite crystals comprise a broad range of mesopores and contain up to several hundred gold nanoparticles with a diameter of 2-3 nm that are distributed inside the zeolites rather than on the outer surface. The encapsulated nanoparticles have good stability and result in 50%conversion of ethanol with 98% selectivity toward acetaldehyde at 200°C, which (under the given reaction conditions) corresponds to 606 mol acetaldehyde/mol Au hour-1. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
    view abstractdoi: 10.1002/anie.201406354
  • 2014 • 102 Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles
    Reske, R. and Mistry, H. and Behafarid, F. and Roldan Cuenya, B. and Strasser, P.
    Journal of the American Chemical Society 136 6978-6986 (2014)
    A study of particle size effects during the catalytic CO2 electroreduction on size-controlled Cu nanoparticles (NPs) is presented. Cu NP catalysts in the 2-15 nm mean size range were prepared, and their catalytic activity and selectivity during CO2 electroreduction were analyzed and compared to a bulk Cu electrode. A dramatic increase in the catalytic activity and selectivity for H2 and CO was observed with decreasing Cu particle size, in particular, for NPs below 5 nm. Hydrocarbon (methane and ethylene) selectivity was increasingly suppressed for nanoscale Cu surfaces. The size dependence of the surface atomic coordination of model spherical Cu particles was used to rationalize the experimental results. Changes in the population of low-coordinated surface sites and their stronger chemisorption were linked to surging H2 and CO selectivities, higher catalytic activity, and smaller hydrocarbon selectivity. The presented activity-selectivity-size relations provide novel insights in the CO2 electroreduction reaction on nanoscale surfaces. Our smallest nanoparticles (∼2 nm) enter the ab initio computationally accessible size regime, and therefore, the results obtained lend themselves well to density functional theory (DFT) evaluation and reaction mechanism verification. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/ja500328k
  • 2014 • 101 Photodeposition of copper and chromia on gallium oxide: The role of co-catalysts in photocatalytic water splitting
    Busser, G.W. and Mei, B. and Pougin, A. and Strunk, J. and Gutkowski, R. and Schuhmann, W. and Willinger, M.-G. and Schlögl, R. and Muhler, M.
    ChemSusChem 7 1030-1034 (2014)
    Split second: The photocatalytic activity of gallium oxide (β-Ga 2O3) depends strongly on the co-catalysts CuOx and chromia, which can be efficiently deposited in a stepwise manner by photoreduction of Cu2+ and CrO42-. The water-splitting activity can be tuned by varying the Cu loading in the range 0.025-1.5 wt %, whereas the Cr loading is not affecting the rate as long as small amounts (such as 0.05 wt %) are present. Chromia is identified as highly efficient co-catalyst in the presence of CuOx: it is essential for the oxidation of water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201301065
  • 2014 • 100 Rediscovering zeolite mechanochemistry-A pathway beyond current synthesis and modification boundaries
    Majano, G. and Borchardt, L. and Mitchell, S. and Valtchev, V. and Pérez-Ramírez, J.
    Microporous and Mesoporous Materials 194 106-114 (2014)
    The search for new and improved methods to synthesize and modify zeolites remains a topic of central academic and industrial relevance. The current reliance on solvent-based methods imposes several drawbacks, including the need for subsequent workup steps and the copious generation of liquid waste. Providing a solvent-and process-efficient, but also a mechanistically-distinct route, mechanochemistry has been postulated as a scalable, one-step approach to overcome these limitations. Uniting essential studies in the field, this perspective explores the potential of mechanochemical methods to contribute to zeolite and zeotype material research. Particular emphasis is given to framework interactions associated with post-synthetic modifications. In addition to the archetypal crystal/particle size reduction, these include the introduction of functionalities by framework activation or ion exchange as well as the moderation of the type, density, and accessibility of active sites by controlled amorphization. The interesting prospects for zeolite catalysis are also discussed. We devise directions to construct a basic understanding of the underlying mechanisms in zeolite-related mechanochemistry, which we expect will broaden its applicability and facilitate the laboratory-to-industry transition. © 2014 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.micromeso.2014.04.006
  • 2014 • 99 Revealing onset potentials using electrochemical microscopy to assess the catalytic activity of gas-evolving electrodes
    Maljusch, A. and Ventosa, E. and Rincón, R.A. and Bandarenka, A.S. and Schuhmann, W.
    Electrochemistry Communications 38 142-145 (2014)
    Determination of the so-called onset potentials, i.e. the lowest (for the anodic reactions) or the highest (for the cathodic reactions) potentials at which a reaction product is formed at a given electrode and at defined conditions, is very important for the evaluation of the catalytic activity and even more for the comparison of different catalysts. We present an approach for the determination of the onset potentials based on scanning electrochemical microscopy (SECM) using the "substrate generation-tip collection" mode. In the proposed method, the potential applied to the catalyst sample is changed stepwise. A micro-electrode serving as SECM tip is positioned in known close proximity to the catalyst surface and is used to detect the onset of the formation of the product of the catalytic reaction, specifically gas generation at the sample surface. The oxygen evolution reaction (OER) at model RuO 2 and perovskite catalyst surfaces is used to evaluate the approach. The suggested method is supposed to provide a clearer and sensitive means for the detection of the onset potentials of electrolytic gas evolution reactions as compared to conventional procedures which mainly use cyclic voltammetry on stationary or rotating (ring) disk electrodes. Moreover, the detection of the reaction product at the SECM tip allows distinguishing between parasitic reactions at the catalyst surface and the true formation of the anticipated reaction product. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.elecom.2013.11.024
  • 2014 • 98 Sequential growth of zinc oxide nanorod arrays at room temperature via a corrosion process: Application in visible light photocatalysis
    Iqbal, D. and Kostka, A. and Bashir, A. and Sarfraz, A. and Chen, Y. and Wieck, A.D. and Erbe, A.
    ACS Applied Materials and Interfaces 6 18728-18734 (2014)
    Many photocatalyst systems catalyze chemical reactions under ultraviolet (UV) illumination, because of its high photon energies. Activating inexpensive, widely available materials as photocatalyst using the intense visible part of the solar spectrum is more challenging. Here, nanorod arrays of the wide-band-gap semiconductor zinc oxide have been shown to act as photocatalysts for the aerobic photo-oxidation of organic dye Methyl Orange under illumination with red light, which is normally accessible only to narrow-band semiconductors. The homogeneous, 800-1000-nm-thick ZnO nanorod arrays show substantial light absorption (absorbances >1) throughout the visible spectral range. This absorption is caused by defect levels inside the band gap. Multiple scattering processes by the rods make the nanorods appear black. The dominantly crystalline ZnO nanorod structures grow in the (0001) direction, i.e., with the c-axis perpendicular to the surface of polycrystalline zinc. The room-temperature preparation route relies on controlled cathodic delamination of a weakly bound polymer coating from metallic zinc, an industrially produced and cheaply available substrate. Cathodic delamination is a sequential synthesis process, because it involves the propagation of a delamination front over the base material. Consequently, arbitrarily large sample surfaces can be nanostructured using this approach. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/am504299v
  • 2014 • 97 Strong metal-support interactions between palladium and iron oxide and their effect on CO oxidation
    Naumann D'Alnoncourt, R. and Friedrich, M. and Kunkes, E. and Rosenthal, D. and Girgsdies, F. and Zhang, B. and Shao, L. and Schuster, M. and Behrens, M. and Schlögl, R.
    Journal of Catalysis 317 220-228 (2014)
    Pd/FeOx catalysts were prepared by co-precipitation and characterized before and after reduction using X-ray powder diffraction, thermal analysis, CO chemisorption, electron microscopy, and X-ray photoelectron spectroscopy. Results give evidence for the encapsulation of palladium particles by iron oxide after reduction at high temperatures (523 K). Oxidation of carbon monoxide was applied as test reaction to characterize catalyst samples in different states. Strong metal-support interactions significantly enhance catalytic activity for oxidation of carbon monoxide. However, this state is not stable under the applied reaction conditions. Catalyst deactivation occurs in two ways: (1) via changes in the oxidation state of iron species and (2) due to sintering of palladium particles. © 2014 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2014.06.019
  • 2014 • 96 Surface termination of the metal-organic framework HKUST-1: A theoretical investigation
    Amirjalayer, S. and Tafipolsky, M. and Schmid, R.
    Journal of Physical Chemistry Letters 5 3206-3210 (2014)
    The surface morphology and termination of metal-organic frameworks (MOF) is of critical importance in many applications, but the surface properties of these soft materials are conceptually different from those of other materials like metal or oxide surfaces. Up to now, experimental investigations are scarce and theoretical simulations have focused on the bulk properties. The possible surface structure of the archetypal MOF HKUST-1 is investigated by a first-principles derived force field in combination with DFT calculations of model systems. The computed surface energies correctly predict the [111] surface to be most stable and allow us to obtain an unprecedented atomistic picture of the surface termination. Entropic factors are identified to determine the preferred surface termination and to be the driving force for the MOF growth. On the basis of this, reported strategies like employing "modulators" during the synthesis to tailor the crystal morphology are discussed. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/jz5012065
  • 2014 • 95 Synthesis of 7-pentafluorophenyl-1 H -indole: An anion receptor for anion-π interactions
    Sun, Z.-H. and Albrecht, M. and Giese, M. and Pan, F. and Rissanen, K.
    Synlett 25 2075-2077 (2014)
    7-Pentafluorophenyl-1H-indole has the potential to be a key compound for the investigation of anion-π interactions in solution. Unfortunately, it was not possible to obtain it by aryl-aryl coupling reaction. Finally, it has been prepared by Bartoli indole synthesis. The key compound as well as analogues were submitted to preliminary studies of anion binding. Single crystals of two key receptors were obtained. © Georg Thieme Verlag Stuttgart New York.
    view abstractdoi: 10.1055/s-0034-1378449
  • 2013 • 94 A new catalyst platform: Zeolite Beta from template-free synthesis
    Yilmaz, B. and Müller, U. and Feyen, M. and Maurer, S. and Zhang, H. and Meng, X. and Xiao, F.-S. and Bao, X. and Zhang, W. and Imai, H. and Yokoi, T. and Tatsumi, T. and Gies, H. and De Baerdemaeker, T. and De Vos, D.
    Catalysis Science and Technology 3 2580-2586 (2013)
    Structural analysis and catalytic testing revealed that zeolite Beta from template-free synthesis introduces new possibilities in catalysis, as a result of its unprecedentedly high density of active sites with exceptional stability and distinctively ordered nature. Highly active and selective catalysts were obtained either by using it in the Al-rich form (e.g. alkylation) or after post-synthesis treatments (e.g. acylation). Such versatility made possible by this novel synthesis route constitutes a new toolbox for catalysis. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3cy00073g
  • 2013 • 93 A robust nickel catalyst for cyanomethylation of aldehydes: Activation of acetonitrile under base-free conditions
    Chakraborty, S. and Patel, Y.J. and Krause, J.A. and Guan, H.
    Angewandte Chemie - International Edition 52 7523-7526 (2013)
    Nick of time: The nickel cyanomethyl complex 1 catalyzes the room temperature coupling of aldehydes with acetonitrile under base-free conditions. The catalytic system is long-lived and remarkably efficient with high turnover numbers (TONs) and turnover frequencies (TOFs) achieved. The mild reaction conditions allow a wide variety of aldehydes, including base-sensitive ones, to catalytically react with acetonitrile. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201302613
  • 2013 • 92 Advanced nanoparticle generation and excitation by lasers in liquids
    Barcikowski, S. and Compagnini, G.
    Physical Chemistry Chemical Physics 15 3022-3026 (2013)
    Today, nanoparticles are widely implemented as functional elements onto surfaces, into volumes and as nano-hybrids, resulting for example in bioactive composites and biomolecule conjugates. However, only limited varieties of materials compatible for integration into advanced functional materials are available: nanoparticles synthesized using conventional gas phase processes are often agglomerated into micro powders that are hard to re-disperse into functional matrices. Chemical synthesis methods often lead to impurities of the nanoparticle colloids caused by additives and precursor reaction products. In the last decade, laser ablation and nanoparticle generation in liquids has proven to be a unique and efficient technique to generate, excite, fragment, and conjugate a large variety of nanostructures in a scalable and clean manner. This editorial briefly highlights selected recent advancements and critical aspects in the field of pulsed laser-based nanoparticle generation and manipulation, including exemplary strategies to harvest the unique properties of the laser-generated nanomaterials in the field of biomedicine and catalysis. The presented critical aspects address future assignments such as size control and scale-up. This journal is © 2013 the Owner Societies.
    view abstractdoi: 10.1039/c2cp90132c
  • 2013 • 91 An orders-of-magnitude increase in the rate of the solid-catalyzed co oxidation by in situ ball milling
    Immohr, S. and Felderhoff, M. and Weidenthaler, C. and Schüth, F.
    Angewandte Chemie - International Edition 52 12688-12691 (2013)
    Shaken, not stirred: CO oxidation was carried out continuously in a shaker ball mill. During milling, the reaction rate increases dramatically, but drops rapidly to zero when the mill is stopped. Compared to a conventional experiment in a plug-flow reactor, the rate of a ball-mill reaction catalyzed by Cr 2O3 is three orders of magnitude higher at room temperature and one order of magnitude higher at 100°C. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201305992
  • 2013 • 90 Atomic engineering of platinum alloy surfaces
    Li, T. and Bagot, P.A.J. and Marquis, E.A. and Edman Tsang, S.C. and Smith, G.D.W.
    Ultramicroscopy 132 205-211 (2013)
    A major practical challenge in heterogeneous catalysis is to minimize the loading of expensive platinum group metals (PGMs) without degrading the overall catalytic efficiency. Gaining a thorough atomic-scale understanding of the chemical/structural changes occurring during catalyst manufacture/operation could potentially enable the design and production of "nano-engineered" catalysts, optimized for cost, stability and performance. In the present study, the oxidation behavior of a Pt-31 at% Pd alloy between 673-1073. K is investigated using atom probe tomography (APT). Over this range of temperatures, three markedly different chemical structures are observed near the surface of the alloy. At 673. K, the surface oxide formed is enriched with Pd, the concentration of which rises further following oxidation at 773. K. During oxidation at 873. K, a thick, stable oxide layer is formed on the surface with a stoichiometry of PdO, beneath which a Pd-depleted (Pt-rich) layer exists. Above 873. K, the surface composition switches to enrichment in Pt, with the Pt content increasing further with increasing oxidation temperature. This treatment suggests a route for tuning the surfaces of Pt-Pd nanoparticles to be either Pd-rich or Pt-rich, simply by adjusting the oxidation temperatures in order to form two different types of core-shell structures. In addition, comparison of the oxidation behavior of Pt-Pd with Pt-Rh and Pd-Rh alloys demonstrates markedly different trends under the same conditions for these three binary alloys. © 2012.
    view abstractdoi: 10.1016/j.ultramic.2012.10.012
  • 2013 • 89 Biomimetic assembly of the [FeFe] hydrogenase: Synthetic mimics in a biological shell
    Apfel, U.-P. and Weigand, W.
    ChemBioChem 14 2237-2238 (2013)
    Combining synthetic chemistry and biology: A new method that allows the incorporation of synthetic [FeFe] hydrogenase mimics into the apo-hydrogenase is highlighted. Azadithiolato-functionalized model complexes showed similar activity to wild-type enzymes when implemented into the protein. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cbic.201300523
  • 2013 • 88 Chemical activity of thin oxide layers: Strong interactions with the support yield a new thin-film phase of zno
    Schott, V. and Oberhofer, H. and Birkner, A. and Xu, M. and Wang, Y. and Muhler, M. and Reuter, K. and Wöll, C.
    Angewandte Chemie - International Edition 52 11925-11929 (2013)
    Influential support: Metal substrates affect the chemical properties of ZnO layers, which are important catalyst materials for the industrial production of methanol through the oxidation of CO. Interactions with the substrate lead to the formation of a new, planar ZnO thin-film phase, in which less highly oxidized Zn atoms bind CO more strongly than the Zn atoms in the normal wurtzite modification. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201302315
  • 2013 • 87 Colloidal deposition as method to study the influence of the support on the activity of gold catalysts in CO-oxidation
    Schüth, F.
    Physica Status Solidi (B) Basic Research 250 1142-1151 (2013)
    The strong influence of the support properties on the activity of gold catalysts has been observed in many publications. The most studied reaction in this respect seems to be CO-oxidation, for which gold catalysts have outstanding activity. However, since in most studies the support properties are also important in influencing the nature of the gold particles deposited on them by co-precipitation or deposition-precipitation, it is difficult to study the support effect alone. We have in a series of studies used colloidal impregnation of preformed gold particles approximately 3nm in size on different supports in order to decouple the gold particle formation from the deposition process, in order to isolate the support effect. Even for such similarly prepared catalysts very strong differences between different supports were observed. The analysis of the data, also in the light of literature data, suggests that there is no unique factor explaining the high activity of gold catalysts, but rather a combination of effects, which act in different proportion for different catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssb.201248499
  • 2013 • 86 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 • 85 Experimental and theoretical investigation of molybdenum carbide and nitride as catalysts for ammonia decomposition
    Zheng, W. and Cotter, T.P. and Kaghazchi, P. and Jacob, T. and Frank, B. and Schlichte, K. and Zhang, W. and Su, D.S. and Schüth, F. and Schlögl, R.
    Journal of the American Chemical Society 135 3458-3464 (2013)
    Constant COx-free H2 production from the catalytic decomposition of ammonia could be achieved over a high-surface-area molybdenum carbide catalyst prepared by a temperature-programmed reduction-carburization method. The fresh and used catalyst was characterized by N2 adsorption/desorption, powder X-ray diffraction, scanning and transmission electron microscopy, and electron energy-loss spectroscopy at different stages. Observed deactivation (in the first 15 h) of the high-surface-area carbide during the reaction was ascribed to considerable reduction of the specific surface area due to nitridation of the carbide under the reaction conditions. Theoretical calculations confirm that the N atoms tend to occupy subsurface sites, leading to the formation of nitride under an NH3 atmosphere. The relatively high rate of reaction (30 mmol/((g of cat.) min)) observed for the catalytic decomposition of NH3 is ascribed to highly energetic sites (twin boundaries, stacking faults, steps, and defects) which are observed in both the molybdenum carbide and nitride samples. The prevalence of such sites in the as-synthesized material results in a much higher H2 production rate in comparison with that for previously reported Mo-based catalysts. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/ja309734u
  • 2013 • 84 Fundamental studies on the electrocatalytic properties of metal macrocyclics and other complexes for the electroreduction of O2
    Masa, J. and Ozoemena, K.I. and Schuhmann, W. and Zagal, J.H.
    Lecture Notes in Energy 9 157-212 (2013)
    The high prospects of exploiting the oxygen reduction reaction (ORR) for lucrative technologies, for example, in the fuel cells industry, chlor-alkali electrolysis, and metal-air batteries, to name but a few, have prompted enormous research interest in the search for cost-effective and abundant catalysts for the electrocatalytic reduction of oxygen. This chapter describes and discusses the electrocatalysis of oxygen reduction by metallomacrocyclic complexes and the prospect of their potential to be used in fuel cells. Since the main interest of most researchers in this field is to design catalysts which can achieve facile reduction of O2 at a high thermodynamic efficiency, this chapter aims to bring to light the research frontiers uncovering important milestones towards the synthesis and design of promising metallomacrocyclic catalysts which can accomplish the four-electron reduction of O2 at low overpotential and to draw attention to the fundamental requirements for synthesis of improved catalysts. Particular attention has been paid to discussion of the common properties which cut across these complexes and how they may be aptly manipulated for tailored catalyst synthesis. Therefore, besides discussion of the progress attained with regard to synthesis and design of catalysts with high selectivity towards the four-electron reduction of O2, a major part of this chapter highlights quantitative structure-activity relationships (QSAR) which govern the activity and stability of these complexes, which when well understood, refined, and carefully implemented should lead to rational design of better catalysts. A brief discussion about nonmacrocyclic copper (I) complexes, particularly Cu(I) phenanthrolines, and those with a laccase-like structure which exhibit promising activity for ORR has been included in a separate section at the end. © Springer-Verlag London 2013.
    view abstractdoi: 10.1007/978-1-4471-4911-8_7
  • 2013 • 83 Highly enantioselective catalytic synthesis of neurite growth-promoting secoyohimbanes
    Antonchick, A.P. and López-Tosco, S. and Parga, J. and Sievers, S. and Schürmann, M. and Preut, H. and Höing, S. and Schöler, H.R. and Sterneckert, J. and Rauh, D. and Waldmann, H.
    Chemistry and Biology 20 500-509 (2013)
    Natural products endowed with neuromodulatory activity and their underlying structural scaffolds may inspire the synthesis of novel neurotrophic compound classes. The spirocyclic secoyohimbane alkaloid rhynchophylline is the major component of the extracts of Uncaria species used in Chinese traditional medicine for treatment of disorders of the central nervous system. Based on the structure of rhynchophylline, a highly enantioselective and efficient organocatalyzed synthesis method was developed that gives access to the tetracyclic secoyohimbane scaffold, embodying a quaternary and three tertiary stereogenic centers in a one-pot multistep reaction sequence. Investigation of a collection of the secoyohimbanes in primary rat hippocampal neurons and embryonal stem cell-derived motor neurons led to discovery of compounds that promote neurite outgrowth and influence the complexity of neuronal network formation. © 2013 Elsevier Ltd.
    view abstractdoi: 10.1016/j.chembiol.2013.03.011
  • 2013 • 82 Influence of the precipitation method on acid-base-catalyzed reactions over Mg-Zr mixed oxides
    Kozlowski, J.T. and Behrens, M. and Schlögl, R. and Davis, R.J.
    ChemCatChem 5 1989-1997 (2013)
    To examine the promotional effect that zirconia has on magnesia in catalysis, mixed oxides were prepared by coprecipitation under controlled-pH conditions or rising-pH conditions. The resulting mixed oxides were characterized by using NH3 and CO2 adsorption microcalorimetry, X-ray diffraction, and scanning electron microscopy. The samples were also tested as catalysts for transesterification of tributyrin with methanol, coupling of acetone, and conversion of ethanol to ethene, ethanal, and butanol. Zirconia promoted the activity of MgO for both transesterification and acetone coupling reactions, presumably by exposing new acid-base pairs at the surface. During ethanol conversion, however, zirconia promoted the dehydration reactions. Characterization and reactivity results suggest that a Mg-Zr sample prepared by controlled-pH precipitation exposes more ZrO2 than a sample prepared by the rising-pH method. © 2013 WILEY-VCH Verlag GmbH & Co.
    view abstractdoi: 10.1002/cctc.201200833
  • 2013 • 81 InSitu study of catalytic processes: Neutron diffraction of a methanol synthesis catalyst at industrially relevant pressure
    Kandemir, T. and Girgsdies, F. and Hansen, T.C. and Liss, K.-D. and Kasatkin, I. and Kunkes, E.L. and Wowsnick, G. and Jacobsen, N. and Schlögl, R. and Behrens, M.
    Angewandte Chemie - International Edition 52 5166-5170 (2013)
    Studying the workplace: An industrial methanol synthesis catalyst operating at high pressure was studied by insitu neutron diffraction. The peculiar microstructure of Cu/ZnO/Al2O3 nanocatalysts was found to be stable under reaction conditions. Stacking fault annealing and brass formation was only observed at temperatures higher than used in the methanol synthesis process, providing support for active role of defects in this catalyst system. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201209539
  • 2013 • 80 Interface defects and impurities at the growth zone of Au-catalyzed GaAs nanowire from first principles
    Sakong, S. and Du, Y.A. and Kratzer, P.
    Physica Status Solidi - Rapid Research Letters 7 882-885 (2013)
    The defects and impurities at the interface of a Au-catalyzed GaAs nanowire have been studied by the first-principles method. The interface is modeled by Au layers on the ${\rm GaAs}(\bar 1\bar 1\bar 1)$ substrate with both Ga- and As-terminations. From the energetics of interface defects and impurities, we find that a highly ordered As-terminated interface is expected under As-rich growth, but mixed Ga- and As-terminations are expected under Ga-rich growth. Comparing the interface defects and impurities to their bulk species, we expect the interface to be a sink for Au impurities in the GaAs nanowire. Based on DFT results, we estimate that materials transport by impurity diffusion through a liquid nanoparticle is sufficient for sustained GaAs growth. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssr.201307210
  • 2013 • 79 Label-free SERS monitoring of chemical reactions catalyzed by small gold nanoparticles using 3D plasmonic superstructures
    Xie, W. and Walkenfort, B. and Schlücker, S.
    Journal of the American Chemical Society 135 1657-1660 (2013)
    Label-free in situ surface-enhanced Raman scattering (SERS) monitoring of reactions catalyzed by small gold nanoparticles using rationally designed plasmonic superstructures is presented. Catalytic and SERS activities are integrated into a single bifunctional 3D superstructure comprising small gold satellites self-assembled onto a large shell-isolated gold core, which eliminates photocatalytic side reactions. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ja309074a
  • 2013 • 78 Mechanocatalytic depolymerization of cellulose combined with hydrogenolysis as a highly efficient pathway to sugar alcohols
    Hilgert, J. and Meine, N. and Rinaldi, R. and Schüth, F.
    Energy and Environmental Science 6 92-96 (2013)
    Cellulose is both insoluble in water and resistant against hydrolysis. These features pose major problems for its conversion into platform chemicals. Herein, we demonstrate that mechanocatalytic, solid-state depolymerization combined with hydrogenolysis, in the presence of Ru/C in water, provides a highly efficient pathway for the production of sugar alcohols. This novel approach leads to yields of hexitols up to 94% at 150 °C in an overall process time of 4 h. © The Royal Society of Chemistry 2013.
    view abstractdoi: 10.1039/c2ee23057g
  • 2013 • 77 N-doped carbon synthesized from N-containing polymers as metal-free catalysts for the oxygen reduction under alkaline conditions
    Zhao, A. and Masa, J. and Muhler, M. and Schuhmann, W. and Xia, W.
    Electrochimica Acta 98 139-145 (2013)
    Nitrogen-doped carbon materials were synthesized and used as metal-free electrocatalysts for the oxygen reduction reaction (ORR) under alkaline conditions. The synthesis was achieved by thermal treatment of nitrogen-containing polymers diluted in different carbon materials. Polypyrrole, polyaniline and polyacrylonitrile were used as N precursors. Carbon black and two types of commercial carbon nanotubes were used as carbon matrices. The obtained N contents were in the range of 1-1.8 wt.%. Different N species including pyridinic, pyrrolic and quaternary N were quantitatively determined by X-ray photoelectron spectroscopy. The ORR activities were evaluated in 0.1 M KOH. Rotating disc electrode studies revealed the presence of multiple active centers in all the samples. The sample obtained using polypyrrole and small diameter nanotubes (ca. 15 nm) had the highest onset potential at -0.07 V vs. Ag/AgCl/3 M KCl, which also showed a significantly higher electrochemical stability than the sample from carbon black and polypyrrole. The ORR activity was not correlated to the total nitrogen amount, but to the amount of pyridinic and quaternary N species. For the onset potential and the (Npyridinic + Nquaternary)/Ntotal ratio a quasi-linear relation was found, which points to the substantial role of pyridinic- and quaternary-N species in ORR catalysis. © 2013 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.electacta.2013.03.043
  • 2013 • 76 Neural network potentials for metals and oxides - First applications to copper clusters at zinc oxide
    Artrith, N. and Hiller, B. and Behler, J.
    Physica Status Solidi (B) Basic Research 250 1191-1203 (2013)
    The development of reliable interatomic potentials for large-scale molecular dynamics (MD) simulations of chemical processes at surfaces and interfaces is a formidable challenge because a wide range of atomic environments and very different types of bonding can be present. In recent years interatomic potentials based on artificial neural networks (NNs) have emerged offering an unbiased approach to the construction of potential energy surfaces (PESs) for systems that are difficult to describe by conventional potentials. Here, we review the basic properties of NN potentials and describe their construction for materials like metals and oxides. The accuracy and efficiency are demonstrated using copper and zinc oxide as benchmark systems. First results for a potential of the combined ternary CuZnO system aiming at the description of oxide-supported copper clusters are reported. Model of a copper cluster at the ZnO($10\overline {1} 0$) surface. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssb.201248370
  • 2013 • 75 Organotextile catalysis
    Lee, J.-W. and Mayer-Gall, T. and Opwis, K. and Song, C.E. and Gutmann, J.S. and List, B.
    Science 341 1225-1229 (2013)
    Throughout human history, textiles have been integral to daily life, but their exploration in catalysis has been rare. Herein, we show a facile and permanent immobilization of organocatalysts on the textile nylon using ultraviolet light. The catalyst and the textile material require no chemical modification for the immobilization. All of the prepared textile-immobilized organocatalysts (a Lewis basic, a Brønsted acidic, and a chiral organocatalyst) display excellent stability, activity, and recyclability for various organic transformations. Very good enantioselectivity (>95:5 enantiomeric ratio) can be maintained for more than 250 cycles of asymmetric catalysis. Practical and straightforward applications of textile organocatalysis may be beneficial for various fields by offering inexpensive and accessible functionalized catalytic materials.
    view abstractdoi: 10.1126/science.1242196
  • 2013 • 74 Pincer-ligated nickel hydridoborate complexes: The dormant species in catalytic reduction of carbon dioxide with boranes
    Chakraborty, S. and Zhang, J. and Patel, Y.J. and Krause, J.A. and Guan, H.
    Inorganic Chemistry 52 37-47 (2013)
    Nickel pincer complexes of the type [2,6-(R2PO) 2C6H3]NiH (R = tBu, 1a; R = iPr, 1b; R = cPe, 1c) react with BH3·THF to produce borohydride complexes [2,6-(R2PO)2C 6H3]Ni(η2-BH4) (2a-c), as confirmed by NMR and IR spectroscopy, X-ray crystallography, and elemental analysis. The reactions are irreversible at room temperature but reversible at 60 C. Compound 1a exchanges its hydrogen on the nickel with the borane hydrogen of 9-BBN or HBcat, but does not form any observable adduct. The less bulky hydride complexes 1b and 1c, however, yield nickel dihydridoborate complexes reversibly at room temperature when mixed with 9-BBN and HBcat. The dihydridoborate ligand in these complexes adopts an η2- coordination mode, as suggested by IR spectroscopy and X-ray crystallography. Under the catalytic influence of 1a-c, reduction of CO2 leads to the methoxide level when 9-BBN or HBcat is employed as the reducing agent. The best catalyst, 1a, involves bulky substituents on the phosphorus donor atoms. Catalytic reactions involving 1b and 1c are less efficient because of the formation of dihydridoborate complexes as the dormant species as well as partial decomposition of the catalysts by the boranes. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ic300587b
  • 2013 • 73 Salen-based coordination polymers of manganese and the rare-earth elements: Synthesis and catalytic aerobic epoxidation of olefins
    Bhunia, A. and Gotthardt, M.A. and Yadav, M. and Gamer, M.T. and Eichhöfer, A. and Kleist, W. and Roesky, P.W.
    Chemistry - A European Journal 19 1986-1995 (2013)
    Treatment of N,N'-bis(4carboxysalicylidene)ethylenediamine (H 4L), with MnCl2·(H2O)4, and Ln(NO3)3·(H2O)m (Ln=Nd, Eu, Gd, Dy, Tb), in the presence of N,N-dimethylformamide (DMF)/pyridine at elevated temperature resulted (after work up) in the formation of 1D coordination polymers {[Ln2(MnLCl)2(NO3)2(dmf) 5]·4 DMF}n (1-5). In these coordination polymers the rare earth ions are connected through carboxylate groups from Mn-salen units in a 1D chain structure. Thus, the Mn-salen complex acts as a "metalloligand" with open coordination sites. All compounds were used as catalysts in the liquid-phase epoxidation of trans-stilbene with molecular oxygen, which resulted in the formation of stilbene oxide. Since the choice of the lanthanide had virtually no influence on the performance of the catalyst, only the manganese-gadolinium was studied in detail. The influence of solvent, catalyst concentration, reaction temperature, oxidant, and oxidant flow rate on conversion, yield, and selectivity was analyzed. A conversion of up to 70 %, the formation of 61 % stilbene oxide (88 % selectivity), and a TON of 84 were observed after 24 h. A hot filtration test confirmed that the reaction is mainly catalyzed through a heterogeneous pathway, although a minor contribution of homogeneous species could not be completely excluded. The catalyst could be reused without significant loss of activity. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201203636
  • 2013 • 72 The Haber-Bosch process revisited: On the real structure and stability of "ammonia iron" under working conditions
    Kandemir, T. and Schuster, M.E. and Senyshyn, A. and Behrens, M. and Schlögl, R.
    Angewandte Chemie - International Edition 52 12723-12726 (2013)
    In situ neutron diffraction was used to study the structural properties of an industrial ammonia synthesis catalyst under working conditions similar to those of the Haber-Bosch process. Despite favorable thermodynamics, no indications of reversible bulk nitridation of the iron catalyst was observed in a self-generated ammonia concentration of 12 vol % at 425 °C and 75 bar after 88 h on stream. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201305812
  • 2013 • 71 The intermetallic compound ZnPd and its role in methanol steam reforming
    Armbrüster, M. and Behrens, M. and Föttinger, K. and Friedrich, M. and Gaudry, E. and Matam, S.K. and Sharma, H.R.
    Catalysis Reviews - Science and Engineering 55 289-367 (2013)
    The rich literature about the intermetallic compound ZnPd as well as several ZnPd near-surface intermetallic phases is reviewed. ZnPd is frequently observed in different catalytic reactions triggering this review in order to collect the knowledge about the compound. The review addresses the chemical and physical properties of the compound and relates these comprehensively to the catalytic properties of ZnPd in methanol steam reforming - an interesting reaction to release hydrogen for a future hydrogen-based energy infrastructure from water/methanol mixtures. The broad scope of the review covers experimental work as well as quantum chemical calculations on a variety of Pd-Zn materials, aiming at covering all relevant literature to derive a sound state-of-the-art picture of the understanding gained so far. © 2013 Copyright Taylor and Francis Group, LLC.
    view abstractdoi: 10.1080/01614940.2013.796192
  • 2013 • 70 Towards the understanding of sintering phenomena at the nanoscale: Geometric and environmental effects
    Behafarid, F. and Roldan Cuenya, B.
    Topics in Catalysis 56 1542-1559 (2013)
    One of the technologically most important requirements for the application of supported metal nanoparticles (NPs) to the field of heterogeneous catalysis is the achievement of thermally and chemically stable systems under reaction conditions. For this purpose, a thorough understanding of the different pathways underlying coarsening phenomena is needed. In particular, in depth knowledge must be achieved on the role of the NP synthesis method, geometrical features of the NPs (size and shape), initial NP dispersion on the support (interparticle distance), support pre-treatment (affecting its morphology and chemical state), and reaction environment (gaseous or liquid medium, pressure, temperature). This study provides examples of the stability and sintering behavior of nanoscale systems monitored ex situ, in situ, and under operando conditions via transmission electron microscopy, atomic force microscopy, scanning tunneling microscopy, and X-ray absorption fine-structure spectroscopy. Experimental data corresponding to physical-vapor-deposited and micelle-synthesized metal (Pt, Au) NPs supported on TiO<inf>2</inf>, SiO<inf>2</inf> and Al<inf>2</inf>O <inf>3</inf> will be used to illustrate Ostwald-ripening and diffusion coalescence processes. In addition, the role of the annealing environment (H<inf>2</inf>, O<inf>2</inf>, water vapor) on the stability of NPs will be discussed. © 2013 Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s11244-013-0149-4
  • 2013 • 69 Why silver deposition is so fast: Solving the enigma of metal deposition
    Pinto, L.M.C. and Spohr, E. and Quaino, P. and Santos, E. and Schmickler, W.
    Angewandte Chemie - International Edition 52 7883-7885 (2013)
    A perfect match: Silver deposition is one of the fastest electrochemical reactions, even though the Ag+ ion loses more than 5 eV solvation energy in the process. This phenomenon, an example of the enigma of metal deposition, was investigated by a combination of MD simulations, DFT, and specially developed theory. At the surface, the Ag+ ion experiences a strong interaction with the sp band of silver, which catalyzes the reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201301998
  • 2012 • 68 Aerobic epoxidation of olefins catalyzed by the cobalt-based metal-organic framework STA-12(Co)
    Beier, M.J. and Kleist, W. and Wharmby, M.T. and Kissner, R. and Kimmerle, B. and Wright, P.A. and Grunwaldt, J.-D. and Baiker, A.
    Chemistry - A European Journal 18 887-898 (2012)
    A Co-based metal-organic framework (MOF) was investigated as a catalytic material in the aerobic epoxidation of olefins in DMF and exhibited, based on catalyst mass, a remarkably high catalytic activity compared with the Co-doped zeolite catalysts that are typically used in this reaction. The structure of STA-12(Co) is similar to that of STA-12(Ni), as shown by XRD Rietveld refinement and is stable up to 270 °C. For the epoxidation reaction, significantly different selectivities were obtained depending on the substrate. Although styrene was epoxidized with low selectivity due to oligomerization, (E)-stilbene was converted with high selectivities between 80 and 90%. Leaching of Co was low and the reaction was found to proceed mainly heterogeneously. The catalyst was reusable with only a small loss of activity. The catalytic epoxidation of stilbene with the MOF featured an induction period, which was, interestingly, considerably reduced by styrene/stilbene co-epoxidation. This could be traced back to the formation of benzaldehyde promoting the reaction. Detailed parameter and catalytic studies, including in situ EPR and EXAFS spectroscopy, were performed to obtain an initial insight into the reaction mechanism. Aim for the STAs: The metal-organic framework catalyst STA-12(Co) showed remarkable activity in the aerobic epoxidation of E-stilbene in DMF (see figure) and could be efficiently recycled. High selectivity (80-90%) for stilbene oxide was observed. The induction period of the reaction could be reduced by styrene/stilbene co-epoxidation. Detailed parameter studies combined with spectroscopic investigations were performed to obtain an initial insight into the reaction mechanism. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201101223
  • 2012 • 67 Catalytic reactivity of face centered cubic PdZn α for the steam reforming of methanol
    Halevi, B. and Peterson, E.J. and Roy, A. and Delariva, A. and Jeroro, E. and Gao, F. and Wang, Y. and Vohs, J.M. and Kiefer, B. and Kunkes, E. and Hävecker, M. and Behrens, M. and Schlögl, R. and Datye, A.K.
    Journal of Catalysis 291 44-54 (2012)
    Addition of Zn to Pd changes its catalytic behavior for steam reforming of methanol. Previous work shows that improved catalytic behavior (high selectivity to CO 2) is achieved by the intermetallic, tetragonal L1 0 phase PdZn β1, where the Pd:Zn ratio is near 1:1. The Pd-Zn phase diagram shows a number of other phases, but their steady-state reactivity has not been determined due to the difficulty of precisely controlling composition and phase in supported catalysts. Hence, the role of Zn on Pd has generally been studied only on model single crystals where Zn was deposited on Pd(1 1 1) with techniques such as TPD and TPR of methanol or CO. The role of small amounts of Zn on the steady-state reactivity of Pd-Zn remains unknown. Therefore, in this work, we have synthesized unsupported powders of phase pure PdZn α, a solid solution of Zn in fcc Pd, using a spray pyrolysis technique. The surface composition and chemical state were studied using Ambient Pressure-XPS (AP-XPS) and were found to match the bulk composition and remain so during methanol steam reforming (MSR) (P tot = 0.25 mbar). Unlike the PdZn β11 phase, we find that PdZn α is 100% selective to CO during methanol steam reforming with TOF at 250 °C of 0.12 s -1. Steady-state ambient pressure micro-reactor experiments and vacuum TPD of methanol and CO show that the α phase behaves much like Pd, but Zn addition to Pd improves TOF since it weakens the Pd-CO bond, eliminating the poisoning of Pd by CO during MSR over Pd. The measured selectivity for fcc PdZn α therefore confirms that adding small amounts of Zn to Pd is not enough to modify the selectivity during MSR and that the PdZn β1 tetragonal structure is essential for CO 2 formation during MSR. © 2011 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2012.04.002
  • 2012 • 66 Catalytic role of gold nanoparticle in GaAs nanowire growth: A density functional theory study
    Kratzer, P. and Sakong, S. and Pankoke, V.
    Nano Letters 12 943-948 (2012)
    The energetics of Ga, As, and GaAs species on the Au(111) surface (employed as a model for Au nanoparticles) is investigated by means of density functional calculations. Apart from formation of the compound Au 7Ga 2, Ga is found to form a surface alloy with gold with comparable ΔH ∼ -0.5 eV for both processes. Dissociative adsorption of As 2 is found to be exothermic by more than 2 eV on both clean Au(111) and AuGa surface alloys. The As-Ga species formed by reaction of As with the surface alloy is sufficiently stable to cover the surface of an Au particle in vacuo in contact with a GaAs substrate. The results of the calculations are interpreted in the context of Au-catalyzed growth of GaAs nanowires. We argue that arsenic is supplied to the growth zone of the nanowire mainly by impingement of molecules on the gold particle and identify a regime of temperatures and As 2 partial pressures suitable for Au-catalyzed nanowire growth in molecular beam epitaxy. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/nl204004p
  • 2012 • 65 Comparison of micro- and nanoscale Fe +3-containing (Hematite) particles for their toxicological properties in human lung cells in vitro
    Bhattacharya, K. and Hoffmann, E. and Schins, R.F.P. and Boertz, J. and Prantl, E.-M. and Alink, G.M. and Byrne, H.J. and Kuhlbusch, T.A.J. and Rahman, Q. and Wiggers, H. and Schulz, C. and Dopp, E.
    Toxicological Sciences 126 173-182 (2012)
    The specific properties of nanoscale particles, large surface-to-mass ratios and highly reactive surfaces, have increased their commercial application in many fields. However, the same properties are also important for the interaction and bioaccumulation of the nonbiodegradable nanoscale particles in a biological system and are a cause for concern. Hematite (α-Fe 2O 3), being a mineral form of Fe(III) oxide, is one of the most used iron oxides besides magnetite. The aim of our study was the characterization and comparison of biophysical reactivity and toxicological effects of α-Fe 2O 3 nano- (d < 100 nm) and microscale (d < 5 μm) particles in human lung cells. Our study demonstrates that the surface reactivity of nanoscale α-Fe 2O 3 differs from that of microscale particles with respect to the state of agglomeration, radical formation potential, and cellular toxicity. The presence of proteins in culture medium and agglomeration were found to affect the catalytic properties of the hematite nano- and microscale particles. Both the nano- and microscale α-Fe 2O 3 particles were actively taken up by human lung cells in vitro, although they were not found in the nuclei and mitochondria. Significant genotoxic effects were only found at very high particle concentrations (> 50 μg/ml). The nanoscale particles were slightly more potent in causing cyto- and genotoxicity as compared with their microscale counterparts. Both types of particles induced intracellular generation of reactive oxygen species. This study underlines that α-Fe 2O 3 nanoscale particles trigger different toxicological reaction pathways than microscale particles. However, the immediate environment of the particles (biomolecules, physiological properties of medium) modulates their toxicity on the basis of agglomeration rather than their actual size. © The Author 2012. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved.
    view abstractdoi: 10.1093/toxsci/kfs014
  • 2012 • 64 Copper nanoparticles stabilized on nitrogen-doped carbon nanotubes as efficient and recyclable catalysts for alkyne/aldehyde/cyclic amine A 3-type coupling reactions
    Ramu, V.G. and Bordoloi, A. and Nagaiah, T.C. and Schuhmann, W. and Muhler, M. and Cabrele, C.
    Applied Catalysis A: General 431-432 88-94 (2012)
    Metallic copper nanoparticles have been efficiently dispersed and stabilized on nitrogen-doped carbon nanotubes. They are about 8-10 nm in diameter and highly resistant against bulk oxidation. Their catalytic activity and recyclability have been investigated in A 3-type coupling reactions for the synthesis of propargylamines. It was easily possible to prepare diastereomerically pure derivatives of proline and to efficiently recover and reuse the supported catalyst several times. © 2012 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apcata.2012.04.019
  • 2012 • 63 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 • 62 Enhanced electrocatalytic stability of platinum nanoparticles supported on a nitrogen-doped composite of carbon nanotubes and mesoporous titania under oxygen reduction conditions
    Masa, J. and Bordoloi, A. and Muhler, M. and Schuhmann, W. and Xia, W.
    ChemSusChem 5 523-525 (2012)
    Cheers for titania: An N-doped composite of carbon nanotubes (CNTs) and mesoporous TiO 2 is used as support for Pt nanoparticles applied in the oxygen reduction reaction. The composite Pt/N-TiO 2-CNT shows a higher stability than Pt particles on carbon black or N-doped CNTs, as indicated by accelerated stress tests of up to 2000 cycles. The enhanced stability is attributed to strong interactions between TiO 2 and Pt and a higher corrosion resistance of TiO 2 as well as CNTs. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201100643
  • 2012 • 61 Enhanced performance of surface-modified TiO2 photocatalysts prepared via a visible-light photosynthetic route
    Ramakrishnan, A. and Neubert, S. and Mei, B. and Strunk, J. and Wang, L. and Bledowski, M. and Muhler, M. and Beranek, R.
    Chemical Communications 48 8556-8558 (2012)
    Benzene can be activated by visible light (λ &gt; 455 nm) in the presence of TiO2, which leads to formation of carbonaceous polymeric deposits on the titania surface. These photosynthesized surface-modified materials exhibit enhanced photoactivity in degradation of phenolic compounds, particularly under visible light irradiation. © 2012 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2cc34243j
  • 2012 • 60 Evaluation of the catalytic performance of gas-evolving electrodes using local electrochemical noise measurements
    Zeradjanin, A.R. and Ventosa, E. and Bondarenko, A.S. and Schuhmann, W.
    ChemSusChem 5 1905-1911 (2012)
    Characterization of gas evolution reactions at the electrode/electrolyte boundary is often difficult due to the dynamic behavior of interfacial processes. Electrochemical noise measurements determined by scanning electrochemical microscopy were used to characterize Cl 2 evolution at gas-evolving electrodes (GEEs). Analysis of the electrochemical noise is a powerful method to evaluate the efficiency of the catalyst layer at a GEE. The high sensitivity of the developed measurement system enabled accurate monitoring of the current fluctuations caused by gas-bubble detachment from the electrode surface. Fourier transform analysis of the obtained current responses allows extraction of the characteristic frequency, which is the main parameter of the macrokinetics of GEEs. The characteristic frequency was used as part of a methodology to evaluate the catalyst performance and, in particular, to estimate the fraction of the catalyst layer that is active during the gas evolution reaction. Tip of the iceberg: Positioned scanning electrochemical microscopy tips are used to determine the characteristic frequency of gas-bubble detachment from ruthenium-based dimensionally stable anodes at different applied potentials (see picture). Geometrical factors and optimized microstructures of the electrode surface are essential for improving the overall catalytic activity for industrial applications. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201200262
  • 2012 • 59 Ga-Pd/Ga 2O 3 Catalysts: The Role of Gallia Polymorphs, Intermetallic Compounds, and Pretreatment Conditions on Selectivity and Stability in Different Reactions
    Li, L. and Zhang, B. and Kunkes, E. and Föttinger, K. and Armbrüster, M. and Su, D.S. and Wei, W. and Schlögl, R. and Behrens, M.
    ChemCatChem 4 1764-1775 (2012)
    A series of gallia-supported Pd-Ga catalysts that consist of metallic nanoparticles on three porous polymorphs of Ga 2O 3 (α-, β-, and γ-Ga 2O 3) were synthesized by a controlled co-precipitation of Pd and Ga. The effects of formation of Ga-Pd intermetallic compounds (IMCs) were studied in four catalytic reactions: methanol steam reforming, hydrogenation of acetylene, and methanol synthesis by CO and CO 2 hydrogenation reactions. The IMC Pd 2Ga forms upon reduction of α- and β-Ga 2O 3-supported materials in hydrogen at temperatures of 250 and 310°C, respectively. At higher temperatures, Ga-enrichment of the intermetallic particles is observed, leading to formation of Pd 5Ga 3 before the support itself is reduced at temperatures above 565°C. In the case of Ga-Pd/γ-Ga 2O 3, no information about the metal particles could be obtained owing to their very small size and high dispersion; however, the catalytic results suggest that the IMC Pd 2Ga also forms in this sample. Pd 2Ga/gallia samples show a stable selectivity towards ethylene in acetylene hydrogenation (≈75%), which is higher than for a monometallic Pd reference catalyst. An even higher selectivity of 80% was observed for Pd 5Ga 3 supported on α-Ga 2O 3. In methanol steam reforming, the Ga-Pd/Gallia catalysts showed, in contrast to Pd/Al 2O 3, selectivity towards CO 2 of up to 40%. However, higher selectivities, which have been reported for Pd 2Ga in literature, could not be reproduced in this study, which might be a result of particle size effects. The initially higher selectivity of the Pd 5Ga 3-containing samples was not stable, suggesting superior catalytic properties for this IMC, but that re-oxidation of Ga species and formation of Pd 2Ga occurs under reaction conditions. In methanol synthesis, CO hydrogenation did not occur, but a considerable methanol yield from a CO 2/H 2 feed was observed for Pd 2Ga/α-Ga 2O 3. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201200268
  • 2012 • 58 Hypothesis: Origin of Life in Deep-Reaching Tectonic Faults
    Schreiber, U. and Locker-Grütjen, O. and Mayer, C.
    Origins of Life and Evolution of Biospheres 42 47-54 (2012)
    The worldwide discussion on the origin of life encounters difficulties when it comes to estimate the conditions of the early earth and to define plausible environments for the development of the first complex organic molecules. Until now, the role of the earth's crust has been more or less ignored. In our opinion, deep-reaching open, interconnected tectonic fault systems may provide possible reaction habitats ranging from nano- to centimetre and even larger dimensions for the formation of prebiotic molecules. In addition to the presence of all necessary raw materials including phosphate, as well as variable pressure and temperature conditions, we suggest that supercritical CO 2 as a nonpolar solvent could have played an important role. A hypothetical model for the origin of life is proposed which will be used to design crucial experiments for the model's verification. Because all proposed processes could still occur in tectonic faults at the present time, it may be possible to detect and analyse the formation of prebiotic molecules in order to assess the validity of the proposed hypothesis. © 2012 Springer Science+Business Media B.V.
    view abstractdoi: 10.1007/s11084-012-9267-4
  • 2012 • 57 In situ neutron diffraction under high pressure - Providing an insight into working catalysts
    Kandemir, T. and Wallacher, D. and Hansen, T. and Liss, K.-D. and Naumann Dalnoncourt, R. and Schlögl, R. and Behrens, M.
    Nuclear Instruments and Methods in Physics Research, Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 673 51-55 (2012)
    In the present work the construction and application of a continuous flow cell is presented, from which neutron diffraction data could be obtained during catalytic reactions at high pressure. By coupling an online gas detection system, parallel structure and activity investigations of working catalysts under industrial relevant conditions are possible. The flow cell can be operated with different feed gases in a wide range from room temperature to 603 K. Pressures from ambient up to 6 MPa are applicable. An exchangeable sample positioning system makes the flow cell suitable for several different goniomter types on a variety of instrument beam lines. Complementary operational test measurements were carried out monitoring reduction of and methanol synthesis over a Cu/ZnO/Al 2O 3 catalyst at the high-flux powder diffraction beamline D1B at ILL and high-resolution diffraction beamline Echidna at ANSTO. © 2012 Elsevier B.V.
    view abstractdoi: 10.1016/j.nima.2012.01.019
  • 2012 • 56 Layered precursors for new zeolitic materials: Synthesis and characterization of B-RUB-39 and its condensation product B-RUB-41
    Grünewald-Lüke, A. and Gies, H. and Müller, U. and Yilmaz, B. and Imai, H. and Tatsumi, T. and Xie, B. and Xiao, F.-S. and Bao, X. and Zhang, W. and De Vos, D.
    Microporous and Mesoporous Materials 147 102-109 (2012)
    Condensation of layered silicate precursors leads to new, all silica zeolite frameworks. In order to introduce catalytic functionality, boron has been substituted into the silicate layer of RUB-39 in a single step synthesis process. Condensation of the silicate layer to the zeolite framework of RUB-41, RRO framework structure type, preserved B as constituent of the material. Analysis of structural details obtained from Rietveld analysis of powder diffraction data, 11B and 29Si NMR experiments of the as synthesized precursor as well as of the zeolite condensation product, and crystal chemical reasoning indicates segregation of B on one specific T-site. This T-site is buried in the silicate anionic layer of the precursor shielding the additional negative charge introduced by the trivalent T-atom. © 2011 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.micromeso.2011.05.036
  • 2012 • 55 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 • 54 Microstructural impact of anodic coatings on the electrochemical chlorine evolution reaction
    Chen, R. and Trieu, V. and Zeradjanin, A.R. and Natter, H. and Teschner, D. and Kintrup, J. and Bulan, A. and Schuhmann, W. and Hempelmann, R.
    Physical Chemistry Chemical Physics 14 7392-7399 (2012)
    Sol-gel Ru 0.3Sn 0.7O 2 electrode coatings with crack-free and mud-crack surface morphology deposited onto a Ti-substrate are prepared for a comparative investigation of the microstructural effect on the electrochemical activity for Cl 2 production and the Cl 2 bubble evolution behaviour. For comparison, a state-of-the-art mud-crack commercial Ru 0.3Ti 0.7O 2 coating is used. The compact coating is potentially durable over a long term compared to the mud-crack coating due to the reduced penetration of the electrolyte. Ti L-edge X-ray absorption spectroscopy confirms that a TiO x interlayer is formed between the mud-crack Ru 0.3Sn 0.7O 2 coating and the underlying Ti-substrate due to the attack of the electrolyte. Meanwhile, the compact coating shows enhanced activity in comparison to the commercial coating, benefiting from the nanoparticle-nanoporosity architecture. The dependence of the overall electrode polarization behaviour on the local activity and the bubble evolution behaviour for the Ru 0.3Sn 0.7O 2 coatings with different surface microstructure are evaluated by means of scanning electrochemical microscopy and microscopic bubble imaging. © 2012 the Owner Societies.
    view abstractdoi: 10.1039/c2cp41163f
  • 2012 • 53 Microwave-hydrothermal synthesis and characterization of nanostructured copper substituted ZnM2O4 (M = Al, Ga) spinels as precursors for thermally stable Cu catalysts
    Conrad, F. and Massue, C. and Kühl, S. and Kunkes, E. and Girgsdies, F. and Kasatkin, I. and Zhang, B. and Friedrich, M. and Luo, Y. and Armbrüster, M. and Patzke, G.R. and Behrens, M.
    Nanoscale 4 2018-2028 (2012)
    Nanostructured Cu<inf>x</inf>Zn<inf>1-x</inf>Al<inf>2</inf>O<inf>4</inf> with a Cu:Zn ratio of: has been prepared by a microwave-assisted hydrothermal synthesis at 150°C and used as a precursor for Cu/ZnO/Al<inf>2</inf>O <inf>3</inf>-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m2 g-1). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen and the accessible metallic Cu(0) surface area of the reduced catalyst was 8 m2 g-1. The catalytic performance of the material in CO<inf>2</inf> hydrogenation and methanol steam reforming was compared with conventionally prepared Cu/ZnO/Al<inf>2</inf>O<inf>3</inf> reference catalysts. The observed lower performance of the spinel-based samples is attributed to a lack of synergetic interaction of the Cu nanoparticles with ZnO due to the incorporation of Zn 2+ in the stable spinel lattice. Despite its lower performance, however, the nanostructured nature of the spinel catalyst was stable after thermal treatment up to 500°C in contrast to other Cu-based catalysts. Furthermore, a large fraction of the re-oxidized copper migrates back into the spinel upon calcination of the reduced catalyst, thereby enabling a regeneration of sintered catalysts after prolonged usage at high temperatures. Similarly prepared samples with Ga instead of Al exhibit a more crystalline catalyst with a spinel particle size around 20 nm. The slightly decreased Cu(0) surface area of 3.2 m2 g-1 due to less copper incorporation is not a significant drawback for the methanol steam reforming. © The Royal Society of Chemistry 2012.
    view abstractdoi: 10.1039/c2nr11804a
  • 2012 • 52 Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions
    Busser, G.W. and Mei, B. and Muhler, M.
    ChemSusChem 5 2200-2206 (2012)
    The deposition of hydrogen evolution sites on photocatalysts is a crucial step in the multistep process of synthesizing a catalyst that is active for overall photocatalytic water splitting. An alternative approach to conventional photodeposition was developed, applying the photocatalytic reforming of aqueous methanol solutions to deposit metal particles on semiconductor materials such as Ga2O3 and (Ga0.6Zn0.4)(N 0.6O0.4). The method allows optimizing the loading of the co-catalysts based on the stepwise addition of their precursors and the continuous online monitoring of the evolved hydrogen. Moreover, a synergetic effect between different co-catalysts can be directly established. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201200374
  • 2012 • 51 Role of Water in the Chlorine Evolution Reaction at RuO 2-Based Electrodesa-Understanding Electrocatalysis as a Resonance Phenomenon
    Zeradjanin, A.R. and Menzel, N. and Strasser, P. and Schuhmann, W.
    ChemSusChem 5 1897-1904 (2012)
    The reaction path of the Cl 2 evolution reaction (CER) was investigated by combining electrochemical and spectroscopic methods. It is shown that oxidation and reconstruction of the catalyst surface during CER is a consequence of the interaction between RuO 2 and water. The state of the RuO 2 surface during the electrochemical reaction was analyzed in situ by using Raman spectroscopy to monitor vibrations of the crystal lattice of RuO 2 and changes in the surface concentration of the adsorbed species as a function of the electrode potential. The role of the solvent was recognized as being crucial in the formation of an oxygen-containing hydrophilic layer, which is a key prerequisite for electrocatalytic Cl 2 formation. Water (more precisely the OH adlayer) is understood not just as a medium that allows adsorption of intermediates, but also as an integral part of the intermediate formed during the electrochemical reaction. New insights into the general understanding of electrocatalysis were obtained by utilizing the vibration frequencies of the crystal lattice as a dynamic catalytic descriptor instead of thermodynamic descriptors, such as the adsorption energy of intermediates. Interpretation of the derived "volcano" curve suggests that electrocatalysis is governed by a resonance phenomenon. Water powered! The reaction path of the Cl 2 evolution reaction (CER) is investigated by combining electrochemical and spectroscopic methods. Oxidation and reconstruction of the catalyst surface during CER is a consequence of the interaction between RuO 2 and water. Interpretation of the derived volcano curve suggests that electrocatalysis is governed by a resonance phenomenon (see picture). © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201200193
  • 2012 • 50 Solid-state nuclear magnetic resonance studies delineate the role of the protein in activation of both aromatic rings of thiamin
    Balakrishnan, A. and Paramasivam, S. and Chakraborty, S. and Polenova, T. and Jordan, F.
    Journal of the American Chemical Society 134 665-672 (2012)
    Knowledge of the state of ionization and tautomerization of heteroaromatic cofactors when enzyme-bound is essential for formulating a detailed stepwise mechanism via proton transfers, the most commonly observed contribution to enzyme catalysis. In the bifunctional coenzyme, thiamin diphosphate (ThDP), both aromatic rings participate in catalysis, the thiazolium ring as an electrophilic covalent catalyst and the 4″-aminopyrimidine as acid-base catalyst involving its 1″,4″-iminopyrimidine tautomeric form. Two of four ionization and tautomeric states of ThDP are well characterized via circular dichroism spectral signatures on several ThDP superfamily members. Yet, the method is incapable of providing information about specific proton locations, which in principle may be accessible via NMR studies. To determine the precise ionization/tautomerization states of ThDP during various stages of the catalytic cycle, we report the first application of solid-state NMR spectroscopy to ThDP enzymes, whose large mass (160,000-250,000 Da) precludes solution NMR approaches. Three de novo synthesized analogues, [C2,C6″- 13C 2]ThDP, [C2- 13C]ThDP, and [N4″- 15N]ThDP used with three enzymes revealed that (a) binding to the enzymes activates both the 4″-aminopyrimidine (via pK a elevation) and the thiazolium rings (pK a suppression); (b) detection of a pre-decarboxylation intermediate analogue using [C2,C6″- 13C 2]ThDP, enables both confirmation of covalent bond formation and response in 4″-aminopyrimidine ring's tautomeric state to intermediate formation, supporting the mechanism we postulate; and (c) the chemical shift of bound [N4″- 15N]ThDP provides plausible models for the participation of the 1″,4″-iminopyrimidine tautomer in the mechanism. Unprecedented detail is achieved about proton positions on this bifunctional coenzyme on large enzymes in their active states. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja209856x
  • 2012 • 49 Solvent-Free catalytic depolymerization of cellulose to water-soluble oligosaccharides
    Meine, N. and Rinaldi, R. and Schüth, F.
    ChemSusChem 5 1449-1454 (2012)
    The use of cellulose is hampered by difficulties with breaking up the biopolymer into soluble products. Herein, we show that the impregnation of cellulosic substrates with catalytic amounts of a strong acid (e.g., H 2SO 4, HCl) is a highly effective strategy for minimizing the contact problem commonly experienced in mechanically assisted, solid-state reactions. Milling the acid-impregnated cellulose fully converts the substrate into water-soluble oligosaccharides within 2a H. In aqueous solution, soluble products are easily hydrolyzed at 130°C in 1a H, leading to 91% conversion of the glucan fraction of α-cellulose into glucose, and 96% of the xylans into xylose. Minor products are glucose dimers (8%), 5-hydroxymethylfurfural (1%) and furfural (4%). Milling practical feedstocks (e.g., wood, sugarcane bagasse, and switchgrass) also results to water-soluble products (oligosaccharides and lignin fragments). The integrated approach (solid-state depolymerization in combination with liquid-phase hydrolysis) could well hold the key to a highly efficient "entry process" in biorefinery schemes. Reactive milling: Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201100770
  • 2012 • 48 Stability investigations of electrocatalysts on the nanoscale
    Meier, J.C. and Katsounaros, I. and Galeano, C. and Bongard, H.J. and Topalov, A.A. and Kostka, A. and Karschin, A. and Schüth, F. and Mayrhofer, K.J.J.
    Energy and Environmental Science 5 9319-9330 (2012)
    The search for more stable electrocatalyst materials for electrochemical energy conversion requires a fundamental understanding of the underlying degradation processes. Advanced characterization techniques like identical location transmission electron microscopy (IL-TEM) can provide invaluable insight into the stability of electrode materials on the nanoscale. In this review, the basic principles and the methodology of IL-TEM are described, and its capabilities are revealed by demonstrating the recent progress that has been achieved in research on the stability of fuel cell catalysts. Moreover, we provide future perspectives of the identical location approach towards implementing other electron microscopic and tomographic applications, which will help us to gain an even broader view of the degradation of electrocatalysts. © 2012 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2ee22550f
  • 2012 • 47 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 • 46 The active site of methanol synthesis over Cu/ZnO/Al2O 3 industrial catalysts
    Behrens, M. and Studt, F. and Kasatkin, I. and Kühl, S. and Hävecker, M. and Abild-Pedersen, F. and Zander, S. and Girgsdies, F. and Kurr, P. and Kniep, B.-L. and Tovar, M. and Fischer, R.W. and Nørskov, J.K. and Schlögl, R.
    Science 336 893-897 (2012)
    One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al2O 3methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work.
    view abstractdoi: 10.1126/science.1219831
  • 2012 • 45 The surface science approach for understanding reactions on oxide powders: The importance of IR spectroscopy
    Xu, M. and Noei, H. and Fink, K. and Muhler, M. and Wang, Y. and Wöll, C.
    Angewandte Chemie - International Edition 51 4731-4734 (2012)
    Chemistry at defects: The concentration of defect sites at rutile TiO 2 (r-TiO 2) surfaces of both single crystals and powder particles was determined by UHV-FTIR spectroscopy using CO as a probe molecule (see picture). The potential of this novel approach is demonstrated by unraveling the mechanism of reductive coupling of formaldehyde to give ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201200585
  • 2011 • 44 Al-RUB-41: A shape-selective zeolite catalyst from a layered silicate
    Yilmaz, B. and Müller, U. and Tijsebaert, B. and Vos, D.D. and Xie, B. and Xiao, F.-S. and Gies, H. and Zhang, W. and Bao, X. and Imai, H. and Tatsumi, T.
    Chemical Communications 47 1812-1814 (2011)
    A new zeolite catalyst, Al-RUB-41, was synthesized for the first time. It was tested as a catalyst in methanol amination, and showed a shape-selective performance that results in a highly favorable product distribution. The shape-selective nature was also evidenced by using Pt-Al-RUB-41 as a bifunctional catalyst for decane hydroconversion. With its unique pore architecture and remarkable shape-selective character, Al-RUB-41 presents a significant commercial potential in industrial catalysis. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c0cc03895d
  • 2011 • 43 Atomically smooth p-doped silicon nanowires catalyzed by aluminum at low temperature
    Moutanabbir, O. and Senz, S. and Scholz, R. and Alexe, M. and Kim, Y. and Pippel, E. and Wang, Y. and Wiethoff, C. and Nabbefeld, T. and Meyer zu Heringdorf, F.-J. and Horn-von Hoegen, M.
    ACS Nano 5 1313-1320 (2011)
    Silicon nanowires (SiNWs) are powerful nanotechnological building blocks. To date, a variety of metals have been used to synthesize high-density epitaxial SiNWs through metal-catalyzed vapor phase epitaxy. Understanding the impact of the catalyst on the intrinsic properties of SiNWs is critical for precise manipulation of the emerging SiNW-based devices. Here we demonstrate that SiNWs synthesized at low-temperature by ultrahigh vacuum chemical vapor deposition using Al as a catalyst present distinct morphological properties. In particular, these nanowires are atomically smooth in contrast to rough {112}-type sidewalls characteristic of the intensively investigated Au-catalyzed SiNWs. We show that the stabilizing effect of Al plays the key role in the observed nanowire surface morphology. In fact, unlike Au which induces (111) and (113) facets on the nanowire sidewall surface, Al revokes the reconstruction along the [1̄1̄2] direction leading to equivalent adjacent step edges and flat surfaces. Our finding sets the lower limit of the Al surface density on the nanowire sidewalls at ∼2 atom/nm2. Additionally, despite using temperatures of ca. 110-170 K below the eutectic point, we found that the incorporation of Al into the growing nanowires is sufficient to induce an effective p-type doping of SiNWs. These results demonstrate that the catalyst plays a crucial role is shaping the structural and electrical properties of SiNWs. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/nn1030274
  • 2011 • 42 Bifunctional Aryloxylate Esters as potential oxidatively cleavable linkers
    Czarnecki, P.V. and Kampert, A. and Barbe, S. and Tiller, J.C.
    Tetrahedron Letters 52 3551-3554 (2011)
    Selectively cleavable linkers are essential parts in environmentally responsive materials. Here, we introduce aryl oxalate esters (AOE) as one of the first examples for oxidatively cleavable linkers. To this end a series of novel AOEs was synthesized and explored regarding the H 2O 2-dependent degradation. All AOEs were cleaved selectively at the oxalate group. The degradation rate was clearly dependent on the substituents. Further, it was found that the H 2O 2 based degradation undergoes an autocatalysis mechanism. © 2011 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.tetlet.2011.04.083
  • 2011 • 41 Characterization of oxidation and reduction of a platinum-rhodium alloy by atom-probe tomography
    Li, T. and Marquis, E.A. and Bagot, P.A.J. and Tsang, S.C. and Smith, G.D.W.
    Catalysis Today 175 552-557 (2011)
    An active challenge in heterogeneous catalysis is to minimize the quantities of the expensive platinum group metals used without causing degradation of the overall catalytic efficiency in a chemical reaction. To achieve this goal, a thorough atomic-scale understanding of these materials under reactive conditions is required. This will enable the design and production of "nano-engineered" catalysts, optimised for cost, stability and performance. In this study, the oxidation and reduction behaviour of a Pt-Rh alloy between 873 and 1073K was investigated by atom-probe tomography (APT). Detailed observations of the concentration profiles at the oxide/metal interfaces show that the growth of Rh2O3 oxide is limited by diffusion of Rh in the alloy. By varying the oxidation conditions, it was possible to calculate the activation energy for Rh diffusion in Pt-Rh as 236 ± 41 kJ/mol, together with diffusion coefficients for Rh for a range of temperatures. Reduction of the oxide phase left a thin, almost pure, layer of the most reactive (and expensive) element, Rh, on the surface of the specimen, suggesting a simple route for engineering the formation of the core-shell structure Pt-Rh nanoparticles. © 2011 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.cattod.2011.03.046
  • 2011 • 40 Colloidal metal nanoparticles as a component of designed catalyst
    Jia, C.-J. and Schüth, F.
    Physical Chemistry Chemical Physics 13 2457-2487 (2011)
    Recent advances in the synthesis of collidal metal nanoparticles of controlled sizes and shapes that are relevant for catalyst design are reviewed. Three main methods, based on colloid chemistry techniques in solution, i.e., chemical reduction of metal salt precursors, electrochemical synthesis, and controlled decomposition of organometallic compounds and metal-surfactant complexes, are used to synthesize metal nanoparticles. Their catalytic activity and selectivity depend on the shape, size and composition of the metal nanoparticles, and the support effect, as shown for many reactions in quasi-homogeneous and heterogeneous catalysis. A specially designed type of thermally stable catalysts - "embedded" metal catalysts, in which metal nanoparticles are isolated by porous support shells so that metal sintering is effectively avoided at high temperatures, are also introduced. The ultilization of pre-prepared colloidal metal nanoparticles with tuned size, shape and composition as components of designed catalysts opens up new field in catalysis. © 2011 the Owner Societies.
    view abstractdoi: 10.1039/c0cp02680h
  • 2011 • 39 F-doped Co3O4 photocatalysts for sustainable H 2 generation from water/ethanol
    Gasparotto, A. and Barreca, D. and Bekermann, D. and Devi, A. and Fischer, R.A. and Fornasiero, P. and Gombac, V. and Lebedev, O.I. and MacCato, C. and Montini, T. and Van Tendeloo, G. and Tondello, E.
    Journal of the American Chemical Society 133 19362-19365 (2011)
    p-Type Co3O4 nanostructured films are synthesized by a plasma-assisted process and tested in the photocatalytic production of H 2 from water/ethanol solutions under both near-UV and solar irradiation. It is demonstrated that the introduction of fluorine into p-type Co3O4 results in a remarkable performance improvement with respect to the corresponding undoped oxide, highlighting F-doped Co 3O4 films as highly promising systems for hydrogen generation. Notably, the obtained yields were among the best ever reported for similar semiconductor-based photocatalytic processes. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja210078d
  • 2011 • 38 High-temperature stable, iron-based core-shell catalysts for ammonia decomposition
    Feyen, M. and Weidenthaler, C. and Güttel, R. and Schlichte, K. and Holle, U. and Lu, A.-H. and Schüth, F.
    Chemistry - A European Journal 17 598-605 (2011)
    High-temperature, stable core-shell catalysts for ammonia decomposition have been synthesized. The highly active catalysts, which were found to be also excellent model systems for fundamental studies, are based on α-Fe 2O 3 nanoparticles coated by porous silica shells. In a bottom-up approach, hematite nanoparticles were firstly obtained from the hydrothermal reaction of ferric chlorides, L-lysine, and water with adjustable average sizes of 35, 47, and 75nm. Secondly, particles of each size could be coated by a porous silica shell by means of the base-catalyzed hydrolysis of tetraethylorthosilicate (TEOS) with cetyltetramethylammonium bromide (CTABr) as porogen. After calcination, TEM, high-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray (EDX), XRD, and nitrogen sorption studies confirmed the successful encapsulation of hematite nanoparticles inside porous silica shells with a thickness of 20nm, thereby leading to composites with surface areas of approximately 380 m 2g -1 and iron contents between 10.5 and 12.2wt%. The obtained catalysts were tested in ammonia decomposition. The influence of temperature, iron oxide core size, possible diffusion limitations, and dilution effects of the reagent gas stream with noble gases were studied. The catalysts are highly stable at 750°C with a space velocity of 120000 cm 3 g cat -1h -1 and maintained conversions of around 80% for the testing period time of 33 h. On the basis of the excellent stability under reaction conditions up to 800°C, the system was investigated by in situ XRD, in which body-centered iron was determined, in addition to FeN x, as the crystalline phase under reaction conditions above 650deg;C. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201001827
  • 2011 • 37 Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst
    Tedsree, K. and Li, T. and Jones, S. and Chan, C.W.A. and Yu, K.M.K. and Bagot, P.A.J. and Marquis, E.A. and Smith, G.D.W. and Tsang, S.C.E.
    Nature Nanotechnology 6 302-307 (2011)
    Formic acid (HCOOH) has great potential as an in situ source of hydrogen for fuel cells, because it offers high energy density, is non-toxic and can be safely handled in aqueous solution. So far, there has been a lack of solid catalysts that are sufficiently active and/or selective for hydrogen production from formic acid at room temperature. Here, we report that Ag nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H 2 from formic acid at ambient temperature. Atom probe tomography confirmed that the nanoparticles have a core-shell configuration, with the shell containing between 1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically promoted by the Ag core, leading to significantly enhanced catalytic properties. Our nanocatalysts could be used in the development of micro polymer electrolyte membrane fuel cells for portable devices and could also be applied in the promotion of other catalytic reactions under mild conditions. © 2011 Macmillan Publishers. All rights reserved.
    view abstractdoi: 10.1038/nnano.2011.42
  • 2011 • 36 Nanostructured Ti-catalyzed MgH2 for hydrogen storage
    Shao, H. and Felderhoff, M. and Schüth, F. and Weidenthaler, C.
    Nanotechnology 22 (2011)
    Nanocrystalline Ti-catalyzed MgH2 can be prepared by a homogeneously catalyzed synthesis method. Comprehensive characterization of this sample and measurements of hydrogen storage properties are discussed and compared to a commercial MgH2 sample. The catalyzed MgH2 nanocrystalline sample consists of two MgH2 phases-a tetrahedral β-MgH2 phase and an orthorhombic high-pressure modification γ-MgH2. Transmission electron microscopy was used for the observation of the morphology of the samples and to confirm the nanostructure. N2 adsorption measurement shows a BET surface area of 108m 2g-1 of the nanostructured material. This sample exhibits a hydrogen desorption temperature more than 130 °C lower compared to commercial MgH2. After desorption, the catalyzed nanocrystalline sample absorbs hydrogen 40 times faster than commercial MgH2 at 300 °C. Both the Ti catalyst and the nanocrystalline structure with correspondingly high surface area are thought to play important roles in the improvement of hydrogen storage properties. The desorption enthalpy and entropy values of the catalyzed MgH2 nanocrystalline sample are 77.7kJmol-1H2 and 138.3JK-1mol -1H2, respectively. Thermodynamic properties do not change with the nanostructure. © 2011 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0957-4484/22/23/235401
  • 2011 • 35 Photocurrent generation by photosystem 1 integrated in crosslinked redox hydrogels
    Badura, A. and Guschin, D. and Kothe, T. and Kopczak, M.J. and Schuhmann, W. and Rögner, M.
    Energy and Environmental Science 4 2435-2440 (2011)
    Photosystem 1 (PS1) catalyzes the light driven translocation of electrons in the process of oxygenic photosynthesis. Isolated PS1 was immobilised on a gold electrode surface via an Os complex containing redox polymer hydrogel which simultaneously is used as immobilisation matrix and as electron donor for PS1. On addition of methyl viologen as sacrificial electron acceptor, a catalytic photocurrent with densities of up to 29 μA cm -2 at a light intensity of 1.8 mW cm -2 was observed upon illumination - equivalent to an incident photon to carrier efficiency (IPCE) of 3.1%. The strong dependence of the catalytic reaction on the light intensity and the dissolved oxygen concentration indicates that a significant photocurrent from excited PS1 to the electrode can only be realized in the presence of oxygen. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c1ee01126j
  • 2011 • 34 Polythiophene-assisted vapor phase synthesis of carbon nanotube-supported rhodium sulfide as oxygen reduction catalyst for HCl electrolysis
    Jin, C. and Nagaiah, T.C. and Xia, W. and Bron, M. and Schuhmann, W. and Muhler, M.
    ChemSusChem 4 927-930 (2011)
    Rhodium Drive: Carbon nanotube-supported rhodium sulfide electrocatalysts are prepared by sequential chemical vapor deposition of iron, controlled vapor phase polymerization of thiophene, and finally impregnation of the rhodium precursor and pyrolysis. The electrocatalysts are applied in the oxygen reduction reaction under HCl electrolysis conditions. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201000315
  • 2011 • 33 Shape-selective synthesis of methylamines over the RRO zeolite Al-RUB-41
    Tijsebaert, B. and Yilmaz, B. and Müller, U. and Gies, H. and Zhang, W. and Bao, X. and Xiao, F.-S. and Tatsumi, T. and De Vos, D.
    Journal of Catalysis 278 246-252 (2011)
    Aluminum was incorporated into the layered silicate RUB-39, which is transformed by calcination into RUB-41. This new zeolite with RRO topology contains 8- and 10-ring pores, and the acid sites in the aluminated material catalyze the synthesis of methylamines, in particular mono- and dimethylamine, by amination of methanol. Owing to the shape-selective catalytic properties of (H)Al-RUB-41, low selectivity to the thermodynamically favored trimethylamine product is obtained in comparison with results on RUB-39 or non-shape-selective materials. Both activity and selectivity are highest for RUB-41 catalysts with a high Si to Al ratio. Silylation reduces the number of unselective sites and results in a further suppression of trimethylamine formation. The introduction of acidity in the intact RUB-41 structure is supported by Al-MAS NMR and NH 3-TPD data. Additional characterization by XRD and SEM is provided. © 2010 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2010.12.010
  • 2011 • 32 Structure, chemical composition, and reactivity correlations during the in situ oxidation of 2-propanol
    Paredis, K. and Ono, L.K. and Mostafa, S. and Li, L. and Zhang, Z. and Yang, J.C. and Barrio, L. and Frenkel, A.I. and Cuenya, B.R.
    Journal of the American Chemical Society 133 6728-6735 (2011)
    Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (∼1 nm) supported on nanocrystalline γ-Al2O3 during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (< 140 °C), while the complete oxidation (&gt;140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O2 adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja200178f
  • 2011 • 31 Synthesis of active carbon-based catalysts by chemical vapor infiltration for nitrogen oxide conversion
    Busch, M. and Bergmann, U. and Sager, U. and Schmidt, W. and Schmidt, F. and Notthoff, C. and Atakan, B. and Winterer, M.
    Journal of Nanoscience and Nanotechnology 11 7956-7961 (2011)
    Direct reduction of nitrogen oxides is still a challenge. Strong efforts have been made in developing noble and transition metal catalysts on microporous support materials such as active carbons or zeolites. However, the required activation energy and low conversion rates still limit its break-through. Furthermore, infiltration of such microporous matrix materials is commonly performed by wet chemistry routes. Deep infiltration and homogeneous precursor distribution are often challenging due to precursor viscosity or electrostatic shielding and may be inhibited by pore clogging. Gas phase infiltration, as an alternative, can resolve viscosity issues and may contribute to homogeneous infiltration of precursors. In the present work new catalysts based on active carbon substrates were synthesized via chemical vapor infiltration. Iron oxide nano clusters were deposited in the microporous matrix material. Detailed investigation of produced catalysts included nitrogen oxide adsorption, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Catalytic activity was studied in a recycle flow reactor by time-resolved mass spectrometry at a temperature of 423 K. The infiltrated active carbons showed very homogeneous deposition of iron oxide nano clusters in the range of below 12 to 19 nm, depending on the amount of infiltrated precursor. The specific surface area was not excessively reduced, nor was the pore size distribution changed compared to the original substrate. Catalytic nitrogen oxides conversion was detected at temperatures as low as 423 K. Copyright © 2011 American Scientific Publishers. All rights reserved.
    view abstractdoi: 10.1166/jnn.2011.5074
  • 2011 • 30 Synthesis of bifunctional Au/Pt/Au core/shell nanoraspberries for in situ SERS monitoring of platinum-catalyzed reactions
    Xie, W. and Herrmann, C. and Kömpe, K. and Haase, M. and Schlücker, S.
    Journal of the American Chemical Society 133 19302-19305 (2011)
    The synthesis of bifunctional Au/Pt/Au nanoraspberries for use in quantitative in situ monitoring of platinum-catalyzed reactions by surface-enhanced Raman scattering (SERS) is presented. Highly convolved SERS spectra of reaction mixtures can be decomposed into the contributions of distinct molecular species by multivariate data analysis. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja208298q
  • 2011 • 29 The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: A quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study
    Graf, B. and Muhler, M.
    Physical Chemistry Chemical Physics 13 3701-3710 (2011)
    The adsorption of carbon monoxide on an either unpromoted or potassium-promoted bulk iron catalyst was investigated at 303 K and 613 K by means of pulse chemisorption, adsorption calorimetry, temperature-programmed desorption and temperature-programmed surface reaction in hydrogen. CO was found to adsorb mainly molecularly in the absence of H 2 at 303 K, whereas the presence of H 2 induced CO dissociation at higher temperatures leading to the formation of CH 4 and H 2O. The hydrogenation of atomic oxygen chemisorbed on metallic iron was found to occur faster than the hydrogenation of atomically adsorbed carbon. At 613 K CO adsorption occurred only dissociatively followed by recombinative CO 2 formation according to C ads + 2O ads → CO 2(g). The presence of the potassium promoter on the catalyst surface led to an increasing strength of the Fe-C bond both at 303 K and 613 K: the initial differential heat of molecular CO adsorption on the pure iron catalyst at 303 K amounted to 102 kJ mol -1, whereas it increased to 110 kJ mol -1 on the potassium-promoted sample, and the initial differential heat of dissociative CO adsorption on the unpromoted iron catalyst at 613 K amounted to 165 kJ mol -1, which increased to 225 kJ mol -1 in the presence of potassium. The calorimetric CO adsorption experiments also reveal a change of the energetic distribution of the CO adsorption sites present on the catalyst surface induced by the potassium promoter, which was found to block a fraction of the CO adsorption sites. © the Owner Societies 2011.
    view abstractdoi: 10.1039/c0cp01875a
  • 2011 • 28 The interaction of carbon monoxide with clean and surface-modified zinc oxide nanoparticles: A UHV-FTIRS study
    Noei, H. and Wöll, C. and Muhler, M. and Wang, Y.
    Applied Catalysis A: General 391 31-35 (2011)
    The interaction of CO with differently modified polycrystalline ZnO has been studied by FTIR spectroscopy under ultrahigh vacuum conditions (UHV-FTIRS). After exposing the clean, adsorbate-free ZnO nanoparticles to CO at 110 K we observe an intense vibrational band at 2187 cm-1 which is assigned to a majority of CO species bound to the Zn2+ sites on the mixed-terminated ZnO(101̄0) surface. After the exposure of CO 2-pretreated ZnO nanoparticles to CO at 110 K, a new CO band is observed at 2215 cm-1, which originates from CO species adsorbed on the "free" Zn sites embedded within the (2 × 1) tridentate carbonate structure on the ZnO(101̄0) surface. UHV-FTIRS data recorded at different sample temperatures demonstrate that the binding energy of CO on polycrystalline ZnO is substantially increased in the presence of pre-adsorbed CO2. The presence of hydroxyl species on the ZnO powder particles does not lead to substantial changes of the CO vibrational bands detected at 110 K under UHV conditions. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apcata.2010.05.015
  • 2011 • 27 Wiring photosynthetic enzymes to electrodes
    Badura, A. and Kothe, T. and Schuhmann, W. and Rögner, M.
    Energy and Environmental Science 4 3263-3274 (2011)
    The efficient electron transfer between redox enzymes and electrode surfaces can be obtained by wiring redox enzymes using, for instance, polymer-bound redox relays as has been demonstrated as a basis for the design of amperometric biosensors, logic gates or sensor arrays and more general as a central aspect of "bioelectrochemistry". Related devices allow exploiting the unique catalytic properties of enzymes, among which photosynthetic enzymes are especially attractive due to the possibility to trigger the redox reactions upon irradiation with light. Photocatalytic properties such as the light-driven water splitting by photosystem 2 make them unique candidates for the development of semiartificial devices which convert light energy into stable chemical products, like hydrogen. This review summarizes recent concepts for the integration of photosystem 1 and photosystem 2 into bioelectrochemical devices with special focus on strategies for the design of electron transfer pathways between redox enzymes and conductive supports. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c1ee01285a
  • 2011 • 26 Yolk-shell gold nanoparticles as model materials for support-effect studies in heterogeneous catalysis: Au, @C and Au, @ZrO2 for CO oxidation as an example
    Galeano, C. and Güttel, R. and Paul, M. and Arnal, P. and Lu, A.-H. and Schüth, F.
    Chemistry - A European Journal 17 8434-8439 (2011)
    The use of nanostructured yolk-shell materials offers a way to discriminate support and particle-size effects for mechanistic studies in heterogeneous catalysis. Herein, gold yolk-shell materials have been synthesized and used as model catalysts for the investigation of support effects in CO oxidation. Carbon has been selected as catalytically inert support to study the intrinsic activity of the gold nanoparticles, and for comparison, zirconia has been used as oxidic support. Au, @C materials have been synthesized through nanocasting using two different nonporous-core@mesoporous-shell exotemplates: Au@SiO 2@ZrO2 and Au@SiO2@m-SiO2. The catalytic activity of Au, @C with a gold core of about 14nm has been evaluated and compared with Au, @ZrO2 of the same gold core size. The strong positive effect of metal oxide as support material on the activity of gold has been proved. Additionally, size effects were investigated using carbon as support to determine only the contribution of the nanoparticle size on the catalytic activity of gold. Therefore, Au, @C with a gold core of about 7nm was studied showing a less pronounced positive effect on the activity than the metal oxide support effect. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201100318
  • 2010 • 25 A novel continuous approach for the synthesis and characterization of pure and mixed metal oxide systems applied in heterogeneous catalysis
    Kaluza, S. and Muhler, M.
    Studies in Surface Science and Catalysis 175 217-220 (2010)
    An extensive set of characterization methods is required to study the processes occurring during the evolution of the initially amorphous precursor towards the complex Cu/ZnO/Al 2O 3 system. A novel preparation method was therefore developed that provides the possibility of a systematic study of all components in the different stages of the precipitation of the ternary catalyst. As a result, a continuously operating synthesis route was established as an alternative to the industrially applied process. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/S0167-2991(10)75027-8
  • 2010 • 24 An efficient nickel catalyst for the reduction of carbon dioxide with a borane
    Chakraborty, S. and Zhang, J. and Krause, J.A. and Guan, H.
    Journal of the American Chemical Society 132 8872-8873 (2010)
    Nickel hydride with a diphosphinite-based ligand catalyzes the highly efficient reduction of CO2 with catecholborane, and the hydrolysis of the resulting methoxyboryl species produces CH3OH in good yield. The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for CO2. The reaction may also be catalyzed by an air-stable nickel formate. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja103982t
  • 2010 • 23 An integrated catalytic approach to fermentable sugars from cellulose
    Rinaldi, R. and Engel, P. and Büchs, J. and Spiess, A.C. and Schüth, F.
    ChemSusChem 3 1151-1153 (2010)
    The production of fermentable sugars from cellulose in almost quantitative yield is accelerated. Starting from cello-oligomers obtained by acid hydrolysis of cellulose in an ionic liquid, the catalytic approach described herein, integrating acid and enzymatic catalysis, quantitatively converts cellulose to fermentable sugars (glucose and cellobiose) within only a few hours. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.201000153
  • 2010 • 22 Characterization of irreversible kinase inhibitors by directly detecting covalent bond formation: A tool for dissecting kinase drug resistance
    Klüter, S. and Simard, J.R. and Rode, H.B. and Grütter, C. and Pawar, V. and Raaijmakers, H.C.A. and Barf, T.A. and Rabiller, M. and Van Otterlo, W.A.L. and Rauh, D.
    ChemBioChem 11 2557-2566 (2010)
    Targeting protein kinases in cancer therapy with irreversible small-molecule inhibitors is moving to the forefront of kinase-inhibitor research and is thought to be an effective means of overcoming mutation-associated drug resistance in epidermal growth factor receptor kinase (EGFR). We generated a detection technique that allows direct measurements of covalent bond formation without relying on kinase activity, thereby allowing the straightforward investigation of the influence of steric clashes on covalent inhibitors in different resistant kinase mutants. The obtained results are discussed together with structural biology and biochemical studies of catalytic activity in both wild-type and gatekeeper mutated kinase variants to draw conclusions about the impact of steric hindrance and increased catalytic activity in drug-resistant kinase variants. Dissecting the mechanisms of kinase drug resistance: We describe a straightforward assay system, which allowed real-time detection of irreversible kinase inhibition without requiring ATP or time-dependent IC50 measurements. This assay system provided an effective tool for dissecting drug-resistance mechanisms resulting from point mutations at the gatekeeper position. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cbic.201000352
  • 2010 • 21 Development of molecular and solid catalysts for the direct low-temperature oxidation of methane to methanol
    Palkovits, R. and von Malotki, C. and Baumgarten, M. and Müllen, K. and Baltes, C. and Antonietti, M. and Kuhn, P. and Weber, J. and Thomas, A. and Schüth, F.
    ChemSusChem 3 277-282 (2010)
    The direct low-temperature oxidation of methane to methanol is demonstrated on a highly active homogeneous molecular catalyst system and on heterogeneous molecular catalysts based on polymeric materials possessing ligand motifs within the material structure. The N-(2-methylpropyl)-4,5-diazacarbazolyl-dichloro-platinum(II) complex reaches significantly higher activity compared to the well-known Periana system and allows first conclusions on electronic and structural requirements for high catalytic activity in this reaction. Interestingly, comparable activities could be achieved utilizing a platinum modified poly(benzimidazole) material, which demonstrates for the first time a solid catalyst with superior activity compared to the Periana system. Although the material shows platinum leaching, improved activity and altered electronic properties, compared to the conventional Periana system, support the proposed conclusions on structure-activity relationships. In comparison, platinum modified triazine-based catalysts show lower catalytic activity, but rather stable platinum coordination even after several catalytic cycles. Based on these systems, further development of improved solid catalysts for the direct low-temperature oxidation of methane to methanol is feasible. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.200900123
  • 2010 • 20 Efficient phase separation and product recovery in organic-aqueous bioprocessing using supercritical carbon dioxide
    Brandenbusch, C. and Bühler, B. and Hoffmann, P. and Sadowski, G. and Schmid, A.
    Biotechnology and Bioengineering 107 642-651 (2010)
    Biphasic hydrocarbon functionalizations catalyzed by recombinant microorganisms have been shown to be one of the most promising approaches for replacing common chemical synthesis routes on an industrial scale. However, the formation of stable emulsions complicates downstream processing, especially phase separation. This fact has turned out to be a major hurdle for industrial implementation. To overcome this limitation, we used supercritical carbon dioxide (scCO2) for both phase separation and product purification. The stable emulsion, originating from a stereospecific epoxidation of styrene to (S)-styrene oxide, a reaction catalyzed by recombinant Escherichia coli, could be destabilized efficiently and irreversibly, enabling complete phase separation within minutes. By further use of scCO2 as extraction agent, the product (S)-styrene oxide could be obtained with a purity of 81% (w/w) in one single extraction step. By combining phase separation and product purification using scCO2, the number of necessary workup steps can be reduced to one. This efficient and easy to use technique is generally applicable for the workup of biphasic biocatalytic hydrocarbon functionalizations and enables a cost effective downstream processing even on a large scale. Biotechnol. Bioeng. 2010;107:642-651. © 2010 Wiley Periodicals, Inc.
    view abstractdoi: 10.1002/bit.22846
  • 2010 • 19 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 • 18 First-row transition metal catalyzed reduction of carbonyl functionalities: A mechanistic perspective
    Chakraborty, S. and Guan, H.
    Dalton Transactions 39 7427-7436 (2010)
    The use of first-row transition metals for the catalytic reduction of carbonyl functionalities has become increasingly important in homogeneous catalysis. This Perspective examines the mechanistic aspects of these reduction reactions, with a focus on various interactions between metal complexes and substrates. Four different types of catalytic pathways, namely catalysis with dihydride (or dihydrogen) complexes, catalysis with monohydride complexes, metal-ligand bifunctional catalysis, and catalysis involving ionic mechanisms, are discussed with recent examples highlighted. © 2010 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c002942d
  • 2010 • 17 Formation, binding, and stability of O-Ag-CO2-Ag-O compounds on Ag(100) investigated by low temperature scanning tunneling microscopy and manipulation
    Hsieh, M.-F. and Li, H.-D. and Lin, D.-S. and Morgenstern, K.
    Journal of Physical Chemistry C 114 14173-14179 (2010)
    The understanding of reaction intermediates in heterogeneous catalysis has important implications for the design of novel catalysts. We investigate the adsorption of CO2 on oxygen precovered Ag(100) at low temperature (17 K) by scanning tunneling microscopy and inelastic electron tunneling manipulation at 5 K. On the terraces, the adsorption leads to O-Ag-CO 2-Ag-O compounds with reduced binding of the oxygen to the surface as compared to the separately adsorbed molecules. The compound can be either dissociated into a bistable O-Ag-CO2 compound at 1.6 V, dissociated into its constituents at 2.2 V, or reacted at 6.5 V into a species, which we tentatively attribute to CO3. The thus obtained carbon trioxide or carbonate is an intriguing reaction intermediate, because it is not stable in the gas phase. Our detailed study of coadsorbed species outlines a possibility to investigate precursors of reactions that involve the substrate atoms. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/jp104170b
  • 2010 • 16 From glycerol to allyl alcohol: Iron oxide catalyzed dehydration and consecutive hydrogen transfer
    Liu, Y. and Tüysüz, H. and Jia, C.-J. and Schwickardi, M. and Rinaldi, R. and Lu, A.-H. and Schmidt, W. and Schüth, F.
    Chemical Communications 46 1238-1240 (2010)
    Using iron oxide as catalyst, glycerol can be converted to allyl alcohol through a dehydration and consecutive hydrogen transfer. © 2010 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/b921648k
  • 2010 • 15 Fullerene-Mediated Activation of Dihydrogen: A New Method of Metal-Free Catalytic Hydrogenation
    Niemeyer, J. and Erker, G.
    ChemCatChem 2 499-500 (2010)
    doi: 10.1002/cctc.201000038
  • 2010 • 14 Highly active iron oxide supported gold catalysts for CO oxidation: How small must the gold nanoparticles be?
    Liu, Y. and Jia, C.-N. and Yamasaki, J. and Terasaki, O. and Schüth, F.
    Angewandte Chemie - International Edition 49 5771-5775 (2010)
    (Figure Presented) The shape of gold: The title catalyst has been prepared through a colloidal deposition method. Scanning transmission electron microscopy studies confirmed that for the catalyst, gold clusters with a bilayer structure and a diameter of about 0.5 nm are not mandatory to achieve the high activity (see image). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201000452
  • 2010 • 13 Hydrogen Loading of Oxide Powder Particles: A Transmission IR Study for the Case of Zinc Oxide
    Noei, H. and Qiu, H. and Wang, Y. and Muhler, M. and Wöll, C.
    ChemPhysChem 11 3604-3607 (2010)
    Exposing ZnO nanoparticles to atomic and molecular hydrogen at room temperature decreases the transmission coefficient, which demonstrates that diffusion of hydrogen atoms to subsurface and bulk ZnO sites already occurs at these fairly low temperatures (see figure). The interstitial hydrogen atoms act as n-type shallow donors, which increase the density of electrons in the conduction band. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cphc.201000312
  • 2010 • 12 MOF-5 based mixed-linker metal-organic frameworks: Synthesis, thermal stability and catalytic application
    Kleist, W. and Maciejewski, M. and Baiker, A.
    Thermochimica Acta 499 71-78 (2010)
    Based on the well-known metal-organic framework material MOF-5 we developed a new route for the synthesis of highly porous mixed-linker metal-organic frameworks (MIXMOFs) where 5% and 10% of the benzene-1,4-dicarboxylate linkers have been substituted by a functionalized linker, namely 2-aminobenzene-1,4-dicarboxylate. The thermal stability of the materials decreased with increasing degree of substitution. However, all materials showed thermal stability up to at least 350 °C in oxidizing atmosphere which renders the MIXMOFs promising for catalytic applications. Choosing the optimum ratio of the two linker molecules both the number of active sites and thermal stability of the resulting catalysts could be tuned. The amino group at the functionalized linker proved to be beneficial for the immobilization of Pd species. The Pd loading achieved by equilibrium adsorption could be controlled by the number of NH 2 groups in the material. Although the thermal stability of the organic framework was affected to some extent in the presence of Pd, the Pd/MIXMOF materials could successfully be applied as catalysts in the oxidation of CO at elevated temperatures which was chosen as a test reaction. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tca.2009.11.004
  • 2010 • 11 Nitrogen-doped carbon nanotubes as a cathode catalyst for the oxygen reduction reaction in alkaline medium
    Nagaiah, T.C. and Kundu, S. and Bron, M. and Muhler, M. and Schuhmann, W.
    Electrochemistry Communications 12 338-341 (2010)
    A new approach to synthesize nitrogen-doped carbon nanotubes (NCNTs) as catalysts for oxygen reduction by treating oxidized CNTs with ammonia is presented. The surface properties and oxygen reduction activities were characterized by cyclic voltammetry, rotating disk electrode and X-ray photoelectron spectroscopy. NCNTs treated at 800 °C show improved electrocatalytic activity for oxygen reduction as compared with commercially available Pt/C catalysts. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.elecom.2009.12.021
  • 2010 • 10 Pd-Ga intermetallic compounds as highly selective semihydrogenation catalysts
    Armbrüster, M. and Kovnir, K. and Behrens, M. and Teschner, D. and Grin, Y. and Schlögl, R.
    Journal of the American Chemical Society 132 14745-14747 (2010)
    The intermetallic compounds Pd3Ga7, PdGa, and Pd 2Ga are found to be highly selective semihydrogenation catalysts for acetylene outperforming established systems. The stability of the crystal and electronic structure under reaction conditions allows the direct relation of structural and catalytic properties and a knowledge-based development of new intermetallic catalyst systems. In the crystal structure of PdGa palladium is exclusively surrounded by gallium atoms. The alteration of the Pd coordination in PdGa leads to a strong modification of the electronic structure around the Fermi level in comparison to elemental Pd. Electronic modification and isolation of active sites causes the excellent catalytic semihydrogenation properties. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja106568t
  • 2010 • 9 Phase-pure Cu,Zn,Al hydrotalcite-like materials as precursors for copper rich Cu/ZnO/Al2O3 catalysts
    Behrens, M. and Kasatkin, I. and Kühl, S. and Weinberg, G.
    Chemistry of Materials 22 386-397 (2010)
    A series of hydrotalcite-like (htl) compounds of the general composition (Cu,Zn)1-xAlx(OH)2-(CO3) x/2 · m H2O was prepared with a fixed Cu:Zn ratio of 70:30. Phase pure samples could be obtained for 0.3 ≤ x ≥ 0.4. The htl precursors thermally decompose in multiple steps. After dehydration and dehydroxylation amorphous materials were obtained at 330 °C. Phase segregation during this mild calcination was only observed for samples with a Zn: Al ratio deviating strongly from 1:2. A mechanism for this low-temperature segregation process basing on the preformation of the ZnAl2O 4 phase within the amorphous material is proposed. Samples with Zn: Al ratios near 1:2 form an amorphous carbonate-modified mixed oxide "(CuO)x(ZnAl2O4)y" of homogeneous microstructure. Crystallization occurs upon carbonate decomposition at temperatures higher than 500 °C. Despite the small size of the Cu nanoparticles (around 7 nm) formed upon reduction, the accessible Cu surface area is below 5 m2g-1. This can be explained by the unfavorable microstructure of the resulting Cu/ZnAl2O4 catalyst: The Cu particles are to a large extent embedded in a compact oxide matrix. The applicability as Cu/ZnO/Al2O3 catalysts and the role of htl precursor phases in course of industrial catalyst preparation are discussed. © 2009 American Chemical Society.
    view abstractdoi: 10.1021/cm9029165
  • 2010 • 8 Platinum nanoparticles: The crucial role of crystal face and colloid stabilizer in the diastereoselective hydrogenation of cinchonidine
    Schmidt, E. and Kleist, W. and Krumeich, F. and Mallat, T. and Baiker, A.
    Chemistry - A European Journal 16 2181-2192 (2010)
    The preparation of stable metal nanoparticles requires a strong interaction between the (organic) stabilizer and the metal surface that might alter the catalytic properties. This behavior has been described as "poisoning" since the stabilizer normally decreases the catalytic activity due to site blocking. Here we show a striking influence of the stabilizer on the selectivity in the hydrogenation of cinchonidine (CD) over poly(acrylic acid) (PAA)-stabilized Pt nanoparticles with well-defined shape distributions. In the hydrogenation of the heteroaromatic ring of cinchonidine in toluene, the diastereomeric excess of the (S)-hexahydrocinchonidine increased upon increasing Pt{111}/Pt{100} ratio, but this distinct shape selectivity was observed only after the oxidative removal of PAA at 473 K. The use of the as-prepared nanoparticles inverted the major diastereomer to R, and this isomer was formed also in acetic acid. This striking change in the diastereoselectivity indicates that poly(acrylic acid), which remains on the Pt surface after preparation, interacts with CD during hydrogenation almost as strongly as the solvent acetic acid. The PAA stabilizer plays a dual role: it allows one to control the size and shape of the nanoparticles during their synthesis, and it affects the rate and diastereoselectivity of the hydrogenation of CD probably through a "surface-localized acidification". © 2010 Wiley-VCH Verlag GmbH & Co. KGaA,.
    view abstractdoi: 10.1002/chem.200902517
  • 2010 • 7 Real-space investigation of non-adiabatic CO2 synthesis
    Gawronski, H. and Mehlhorn, M. and Morgenstern, K.
    Angewandte Chemie - International Edition 49 5913-5916 (2010)
    (Figure Presented) Cannonball run: Preparation of CO2 has been achieved with CO and O2 coadsorbed onto a Cu(III) surface by illumination with 40 fs pulses of laser light at 400 nm. The hot adatom mechanism that follows O2 dissociation leads to a can-nonball trajectory of the product molecules and thus escape of CO2 from the reactant site to the bare terrace (see figure). It was thus demonstrated that non-adiabatic heterogeneous catalysis may be followed in real space. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201001262
  • 2010 • 6 Salen-ligands based on a planar-chiral hydroxyferrocene moiety: Synthesis, coordination chemistry and use in asymmetric silylcyanation
    Niemeyer, J. and Cloppenburg, J. and Fröhlich, R. and Kehr, G. and Erker, G.
    Journal of Organometallic Chemistry 695 1801-1812 (2010)
    Condensation of the O-protected hydroxyferrocene carbaldehyde (Sp)-1 with suitable diamines, followed by liberation of the hydroxyferrocene moiety leads to a new type of ferrocene-based salen ligands (3). While the use of ethylenediamine in the condensation reaction yields the planar-chiral ethylene-bridged ligand [(Sp,Sp)-3a], reaction with the enantiomers of trans-1,2-cyclohexylendiamine gives rise to the corresponding diastereomeric cyclohexylene-bridged systems [(S,S,Sp,Sp)-3b and (R,R,Sp,Sp)-3c], which feature a combination of a planar-chiral ferrocene unit with a centrochiral diamine backbone. Starting with the ferrocene-aldehyde derivative (Rp)-1, the enantiomeric ligand series (3d/e/f) is accessible via the same synthetic route. The (Sp)-series of these newly developed N2O2-type ligands was used for the construction of the corresponding mononuclear bis(isopropoxy)titanium (4a/b/c), methylaluminum (5a/b/c) and chloroaluminum-complexes (6a/b/c), which were isolated in good yields and identified by X-ray diffraction in several cases. The aluminum complexes (5/6) were successfully used in the Lewis-acid catalyzed addition of trimethylsilylcyanide to benzaldehyde, yielding the corresponding cyanohydrins in 45-62% enantiomeric excess. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jorganchem.2010.04.008
  • 2010 • 5 Scaleup of lipase-catalyzed polyester synthesis
    Korupp, C. and Weberskirch, R. and Müller, J.J. and Liese, A. and Hilterhaus, L.
    Organic Process Research and Development 14 1118-1124 (2010)
    One of the critical steps for the commercialization of new enzyme-based products is the successful scaleup of the catalyzed reaction. In the study presented here, we achieved a scaleup for the enzymatic production of glycerol adipate on a 500 g scale in a heated, solvent-free system. The influence of various reaction conditions (i.e., temperature, pressure, enzyme concentration, reactants ratio, stirrer type, stirring rate, and reaction time) on the substrate conversion and molecular weight of the product was investigated. Conversions were higher than 0.9, and molecular weights were in the desired range of 2000-3000 Da. Space time yields of 370 g d-1 L-1 could be achieved. Maximal polymer yield was achieved at 60 °C, < 20 mbar, 3 wt % Novozym 435, glycerol:adipic acid ratio 1.1:1, < 48 h while stirring at 100 rpm. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/op1000868
  • 2010 • 4 Shape-dependent catalytic properties of Pt nanoparticles
    Mostafa, S. and Behafarid, F. and Croy, J.R. and Ono, L.K. and Li, L. and Yang, J.C. and Frenkel, A.I. and Cuenya, B.R.
    Journal of the American Chemical Society 132 15714-15719 (2010)
    Tailoring the chemical reactivity of nanomaterials at the atomic level is one of the most important challenges in catalysis research. In order to achieve this elusive goal, fundamental understanding of the geometric and electronic structure of these complex systems at the atomic level must be obtained. This article reports the influence of the nanoparticle shape on the reactivity of Pt nanocatalysts supported on γ-Al2O3. Nanoparticles with analogous average size distributions (∼0.8-1 nm), but with different shapes, synthesized by inverse micelle encapsulation, were found to display distinct reactivities for the oxidation of 2-propanol. A correlation between the number of undercoordinated atoms at the nanoparticle surface and the onset temperature for 2-propanol oxidation was observed, demonstrating that catalytic properties can be controlled through shape-selective synthesis. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja106679z
  • 2010 • 3 Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects
    Cuenya, B.R.
    Thin Solid Films 518 3127-3150 (2010)
    Exciting new opportunities are emerging in the field of catalysis based on nanotechnology approaches. A new understanding and mastery of catalysis could have broad societal impacts, since about 80% of the processes in the chemical industry depend on catalysts to work efficiently. Efforts in surface science have led to the discovery of new heterogeneous catalysts, however, until recently the only way to develop new or improved catalysts was by empirical testing in trial-and-error experiments. This time-consuming and costly procedure is now rapidly being replaced by rational design methods that utilize fundamental knowledge of catalysts at the nanoscale. The advent of nanoscience and nanotechnology is providing the ability to create controlled structures and geometries to investigate and optimize a broad range of catalytic processes. As a result, researchers are obtaining fundamental insight into key features that influence the activity, selectivity, and lifetime of nanocatalysts. This review article examines several new findings as well as current challenges in the field of nanoparticle based catalysis, including the role played by the particle structure and morphology (size and shape), its chemical composition and oxidation state, and the effect of the cluster support. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2010.01.018
  • 2010 • 2 Which controls the depolymerization of cellulose in ionic liquids: The solid acid catalyst or cellulose?
    Rinaldi, R. and Meine, N. and vom Stein, J. and Palkovits, R. and Schüth, F.
    ChemSusChem 3 266-276 (2010)
    Cellulose is a renewable and widely available feedstock. It is a biopolymer that is typically found in wood, straw, grass, municipal solid waste, and crop residues. Its use as raw material for biofuel production opens up the possibility of sustainable biorefinery schemes that do not compete with food supply. Tapping into this feedstock for the production of biofuels and chemicals requires-as the first-step-its depolymerization or its hydrolysis into intermediates that are more susceptible to chemical and/or biological transformations. We have shown earlier that solid acids selectively catalyze the depolymerization of cellulose solubilized in 1-butyl-3-methylimidazolium chloride (BMIMCl) at 100°C. Here, we address the factors responsible for the control of this reaction. Both cellulose and solid acid catalysts have distinct and important roles in the process. Describing the depolymerization of cellulose by the equivalent number of scissions occurring in the cellulosic chains allows a direct correlation between the product yields and the extent of the polymer breakdown. The effect of the acid strength on the depolymerization of cellulose is discussed in detail. Practical aspects of the reaction, concerning the homogeneous nature of the catalysis in spite of the use of a solid acid catalyst, are thoroughly addressed. The effect of impurities present in the imidazolium-based ionic liquids on the reaction performance, the suitability of different ionic liquids as solvents, and the recyclability of Amberlyst 15DRY and BMIMCl are also presented. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cssc.200900281
  • 2009 • 1 Ordered mesoporous carbide derived carbons: Novel materials for catalysis and adsorption
    Krawiec, P. and Kockrick, E. and Borchardt, L. and Geiger, D. and Corma, A. and Kaskel, S.
    Journal of Physical Chemistry C 113 7755-7761 (2009)
    New ordered mesoporous carbide derived carbon materials with extraordinary high specific surface areas up to ∼2800 m2 g-1 were synthesized by selective extraction of silicon from ordered mesoporous silicon carbide. Although the degree of mesostructure ordering is lower than that of the CMK-type materials they exhibit higher specific surface areas and high protein adsorption capacities. We show that they can be effectively functionalized with sulfonic groups and become excellent solid acid catalysts for processing large organic molecules. © 2009 American Chemical Society.
    view abstractdoi: 10.1021/jp808470s