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.

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• 2022 • 200	Development of polysulfone ultrafiltration membranes with enhanced antifouling performance for the valorisation of side streams in the pulp and paper industry Burts, K.S. and Plisko, T.V. and Bildyukevich, A.V. and Rodrigues, G. and Sjölin, M. and Lipnizki, F. and Ulbricht, M. Colloids and Surfaces A: Physicochemical and Engineering Aspects 632 (2022) One-stage method of polysulfone (PSf) membrane modification by the addition of polyacrylic acid (PAA, Mn = 250 kg·mol−1) to the coagulation bath during membrane preparation via non-solvent induced phase separation (NIPS) was proposed. The effect of PAA concentration on the membrane structure, hydrophilicity, zeta potential, separation performance and antifouling stability in ultrafiltration of lysozyme, polyvinylpyrrolidone (PVP K-30, Mn = 40 kg mol−1) and humic acid model solutions as well as thermomechanical pulp mill process (ThMP) water was studied. Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), measurements of the tangential flow streaming potential and water contact angle were used for membrane characterization. It was found that addition of PAA into coagulation bath resulted in decreasing pore size and porosity of the selective layer as well as the formation of a thicker and denser selective layer. Water contact angle of the modified membranes was found to decrease significantly and zeta potential of the selective layer was shown to become more negative in the studied pH range 3–10, all compared to the reference membrane. It was revealed that pure water flux (PWF) decreased and lysozyme and PVP K-30 rejection increased with the increase in PAA concentration in the coagulation bath. It was found that membranes modified with PAA demonstrated better antifouling stability in ultrafiltration of humic acid solution and ThMP process water. Modified membranes were found to have higher flux, fouling recovery ratio and hemicelluloses rejection in ThMP process water ultrafiltration compared to the reference PSf membrane that allows application of these membranes for hemicelluloses concentration and purification. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.colsurfa.2021.127742

• 2022 • 199	From MAX Phase Carbides to Nitrides: Synthesis of V2GaC, V2GaN, and the Carbonitride V2GaC1-xN x Kubitza, N. and Reitz, A. and Zieschang, A.-M. and Pazniak, H. and Albert, B. and Kalha, C. and Schlueter, C. and Regoutz, A. and Wiedwald, U. and Birkel, C.S. Inorganic Chemistry 61 10634-10641 (2022) The research in MAX phases is mainly concentrated on the investigation of carbides rather than nitrides (currently >150 carbides and only <15 nitrides) that are predominantly synthesized by conventional solid-state techniques. This is not surprising since the preparation of nitrides and carbonitrides is more demanding due to the high stability and low diffusion rate of nitrogen-containing compounds. This leads to several drawbacks concerning potential variations in the chemical composition of the MAX phases as well as control of morphology, the two aspects that directly affect the resulting materials properties. Here, we report how alternative solid-state hybrid techniques solve these limitations by combining conventional techniques with nonconventional precursor synthesis methods, such as the "urea-glass"sol-gel or liquid ammonia method. We demonstrate the synthesis and morphology control within the V-Ga-C-N system by preparing the MAX phase carbide and nitride-the latter in the form of bulkier and more defined smaller particle structures-as well as a hitherto unknown carbonitride V2GaC1-xNx MAX phase. This shows the versatility of hybrid methods starting, for example, from wet chemically obtained precursors that already contain all of the ingredients needed for carbonitride formation. All products are characterized in detail by X-ray powder diffraction, electron microscopy, and electron and X-ray photoelectron spectroscopies to confirm their structure and morphology and to detect subtle differences between the different chemical compositions. © 2022 American Chemical Society.
  	view abstract	doi: 10.1021/acs.inorgchem.2c00200

• 2021 • 198	Cobalt Metal ALD: Understanding the Mechanism and Role of Zinc Alkyl Precursors as Reductants for Low-Resistivity Co Thin Films Zanders, D. and Liu, J. and Obenlüneschloß, J. and Bock, C. and Rogalla, D. and Mai, L. and Nolan, M. and Barry, S.T. and Devi, A. Chemistry of Materials (2021) In this work, we report a new and promising approach toward the atomic layer deposition (ALD) of metallic Co thin films. Utilizing the simple and known CoCl2(TMEDA) (TMEDA = N,N,N′,N′-tetramethylethylenediamine) precursor in combination with the intramolecularly stabilized Zn aminoalkyl compound Zn(DMP)2 (DMP = dimethylaminopropyl) as an auxiliary reducing agent, a thermal ALD process is developed that enables the deposition of Zn-free Co thin films. ALD studies demonstrate the saturation behavior of both precursors and linearity depending on the applied number of cycles as well as temperature dependency of film growth in a regime of 140-215 °C. While the process optimization is carried out on Si with native oxide, additional growth studies are conducted on Au and Pt substrates. This study is complemented by initial reactivity and suitability tests of several potential Zn alkyl-reducing agents. For the CoCl2(TMEDA)-Zn(DMP)2 combination, these findings allow us to propose a series of elemental reaction steps hypothetically leading to pure Co film formation in the ALD process whose feasibility is probed by a set of density functional theory (DFT) calculations. The DFT results show that for reactions of the precursors in the gas phase and on Co(111) substrate surfaces, a pathway involving C-C coupling and diamine formation through reductive elimination of an intermediate Co(II) alkyl species is preferred. Co thin films with an average thickness of 10-25 nm obtained from the process are subjected to thorough analysis comprising atomic force microscopy, scanning electron microscopy, and Rutherford backscattering spectrometry/nuclear reaction analysis as well as depth profiling X-ray photoemission spectroscopy (XPS). From XPS analysis, it was found that graphitic and carbidic carbon coexist in the Co metal film bulk. Despite carbon concentrations of ∼20 at. % in the Co thin film bulk, resistivity measurements for ∼22 nm thick films grown on a defined SiO2 insulator layer yield highly promising values in a range of 15-20 μω cm without any postgrowth treatment. © 2021 American Chemical Society.
  	view abstract	doi: 10.1021/acs.chemmater.1c00877

• 2021 • 197	Identification of Active Sites in the Catalytic Oxidation of 2-Propanol over Co1+xFe2–xO4 Spinel Oxides at Solid/Liquid and Solid/Gas Interfaces Falk, T. and Budiyanto, E. and Dreyer, M. and Pflieger, C. and Waffel, D. and Büker, J. and Weidenthaler, C. and Ortega, K.F. and Behrens, M. and Tüysüz, H. and Muhler, M. and Peng, B. ChemCatChem 13 2942-2951 (2021) A series of Co1+xFe2–xO4 (0≤x≤2) spinel nanowires was synthesized by nanocasting using SBA-15 silica as hard template, which was characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The Co1+xFe2–xO4 spinels were applied in the aerobic oxidation of aqueous 2-propanol solutions to systematically study the influence of exposed Co and Fe cations on the catalytic properties. The activity of the catalysts was found to depend strongly on the Co content, showing an exponential increase of the reaction rate with increasing Co content. Ensembles of Co3+cus (coordinatively unsaturated) sites were identified as the active sites for selective 2-propanol oxidation, which are assumed to consist of more than six Co ions. In addition, gas-phase oxidation with and without water vapor co-feeding was performed to achieve a comparison with liquid-phase oxidation kinetics. An apparent activation energy of 94 kJ mol−1 was determined for 2-propanol oxidation over Co3O4 in the liquid phase, which is in good agreement with the gas-phase oxidation in the presence of water vapor. In contrast to gas-phase conditions, the catalysts showed high stability and reusability in the aqueous phase with constant conversion in three consecutive runs. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/cctc.202100352

• 2021 • 196	Metal-Ligand Interface and Internal Structure of Ultrasmall Silver Nanoparticles (2 nm) Wetzel, O. and Hosseini, S. and Loza, K. and Heggen, M. and Prymak, O. and Bayer, P. and Beuck, C. and Schaller, T. and Niemeyer, F. and Weidenthaler, C. and Epple, M. Journal of Physical Chemistry B 125 5645-5659 (2021) Ultrasmall silver nanoparticles were prepared by reduction with NaBH4 and surface-terminated with glutathione (GSH). The particles had a solid core diameter of 2 nm as shown by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). NMR-DOSY gave a hydrodynamic diameter of 2 to 2.8 nm. X-ray photoelectron spectroscopy (XPS) showed that silver is bound to the thiol group of the central cysteine in glutathione under partial oxidation to silver(+I). In turn, the thiol group is deprotonated to thiolate. X-ray powder diffraction (XRD) together with Rietveld refinement confirmed a twinned (polycrystalline) fcc structure of ultrasmall silver nanoparticles with a lattice compression of about 0.9% compared to bulk silver metal. By NMR spectroscopy, the interaction between the glutathione ligand and the silver surface was analyzed, also with 13C-labeled glutathione. The adsorbed glutathione is fully intact and binds to the silver surface via cysteine. In situ 1H NMR spectroscopy up to 85 °C in dispersion showed that the glutathione ligand did not detach from the surface of the silver nanoparticle, i.e. the silver-sulfur bond is remarkably strong. The ultrasmall nanoparticles had a higher cytotoxicity than bigger particles in in vitro cell culture with HeLa cells with a cytotoxic concentration of about 1 μg mL-1 after 24 h incubation. The overall stoichiometry of the nanoparticles was about Ag∼250GSH∼155. © 2021 The Authors. Published by American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcb.1c02512

• 2020 • 195	In Situ Generation of Electrolyte inside Pyridine-Based Covalent Triazine Frameworks for Direct Supercapacitor Integration Troschke, E. and Leistenschneider, D. and Rensch, T. and Grätz, S. and Maschita, J. and Ehrling, S. and Klemmed, B. and Lotsch, B.V. and Eychmüller, A. and Borchardt, L. and Kaskel, S. ChemSusChem 13 3192-3198 (2020) The synthesis of porous electrode materials is often linked with the generation of waste that results from extensive purification steps and low mass yield. In contrast to porous carbons, covalent triazine frameworks (CTFs) display modular properties on a molecular basis through appropriate choice of the monomer. Herein, the synthesis of a new pyridine-based CTF material is showcased. The porosity and nitrogen-doping are tuned by a careful choice of the reaction temperature. An in-depth structural characterization by using Ar physisorption, X-ray photoelectron spectroscopy, and Raman spectroscopy was conducted to give a rational explanation of the material properties. Without any purification, the samples were applied as symmetrical supercapacitors and showed a specific capacitance of 141 F g−1. Residual ZnCl2, which acted formerly as the porogen, was used directly as the electrolyte salt. Upon the addition of water, ZnCl2 was dissolved to form the aqueous electrolyte in situ. Thereby, extensive and time-consuming washing steps could be circumvented. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
  	view abstract	doi: 10.1002/cssc.202000518

• 2020 • 194	Insights into the mechanochemical synthesis of Sn-β: Solid-state metal incorporation in beta zeolite Joshi, H. and Ochoa-Hernández, C. and Nürenberg, E. and Kang, L. and Wang, F.R. and Weidenthaler, C. and Schmidt, W. and Schüth, F. Microporous and Mesoporous Materials 309 (2020) Sn-β zeolite is an active material for the isomerization of glucose to fructose, which is one of the critical reactions for the valorization of biomass. The material is synthesized either by a top-down or bottom-up approach. In this work, we use a top-down approach for the synthesis of Sn-β to incorporate the tin atoms into the *BEA framework. As compared to the literature, we replace the process of manual grinding with the use of ball milling to make the process reproducible, flexible, and scalable. The primary focus of this work is to investigate the processes occurring during the synthesis by a variety of characterization tools. These techniques include thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), physisorption, X-ray diffraction (XRD), and chemisorption monitored by Fourier-transform infrared spectroscopy (FTIR). The synthesis is followed by characterizing the material at various stages of synthesis. Finally, the materials are tested for the isomerization of glucose to fructose to assess the chemical nature of Sn-β zeolites. The results of this investigation provide several insights into the mechanochemical process for the incorporation of atoms in a zeolite framework. For instance, the importance of the size of precursors, distribution of Sn atoms during synthesis, and chemical changes occurring during milling are highlighted. These insights could produce a blueprint for the synthesis of a variety of solid catalysts. © 2020
  	view abstract	doi: 10.1016/j.micromeso.2020.110566

• 2020 • 193	Memory of professor charles (Chuck) S. Fadley (1941.9−2019.8) Daimon, H. and Schneider, C.M. and Mun, B.S. e-Journal of Surface Science and Nanotechnology 18 235-238 (2020) Professor Charles S. Fadley (nicknamed Chuck), who was a global leader in photoelectron spectroscopy using synchrotron radiation, passed away on 1st August 2019 at the age of 77. He was a well-known founder of photoelectron diffraction, and as a front runner in photoelectron spectroscopy using synchrotron radiation he initiated and promoted several novel approaches; such as, photoelectron holography, hard X-ray photoelectron spectroscopy, soft-X-ray standing wave spectroscopy, and more. He contributed to many scientific activities and served scientific communities including this ALC conference. He was an honorable member of the JSPS 141st Committee and a laureate of JSPS 141st Committee Award. This paper summarizes his life to honor his great achievements in science and contributions to scientific communities. © 2020 The Japan Society of Vacuum and Surface Science. All rights reserved.
  	view abstract	doi: 10.1380/EJSSNT.2020.235

• 2019 • 192	Electronic Structure of a Graphene-like Artificial Crystal of NdNiO3 Arab, A. and Liu, X. and Köksal, O. and Yang, W. and Chandrasena, R.U. and Middey, S. and Kareev, M. and Kumar, S. and Husanu, M.-A. and Yang, Z. and Gu, L. and Strocov, V.N. and Lee, T.-L. and Minár, J. and Pentcheva, R. and Ch... Nano Letters 19 8311-8317 (2019) Artificial complex-oxide heterostructures containing ultrathin buried layers grown along the pseudocubic [111] direction have been predicted to host a plethora of exotic quantum states arising from the graphene-like lattice geometry and the interplay between strong electronic correlations and band topology. To date, however, electronic-structural investigations of such atomic layers remain an immense challenge due to the shortcomings of conventional surface-sensitive probes with typical information depths of a few angstroms. Here, we use a combination of bulk-sensitive soft X-ray angle-resolved photoelectron spectroscopy (SX-ARPES), hard X-ray photoelectron spectroscopy (HAXPES), and state-of-the-art first-principles calculations to demonstrate a direct and robust method for extracting momentum-resolved and angle-integrated valence-band electronic structure of an ultrathin buckled graphene-like layer of NdNiO3 confined between two 4-unit cell-thick layers of insulating LaAlO3. The momentum-resolved dispersion of the buried Ni d states near the Fermi level obtained via SX-ARPES is in excellent agreement with the first-principles calculations and establishes the realization of an antiferro-orbital order in this artificial lattice. The HAXPES measurements reveal the presence of a valence-band bandgap of 265 meV. Our findings open a promising avenue for designing and investigating quantum states of matter with exotic order and topology in a few buried layers. Copyright © 2019 American Chemical Society.
  	view abstract	doi: 10.1021/acs.nanolett.9b03962

• 2019 • 191	Functionalization of titania nanotubes with electrophoretically deposited silver and calcium phosphate nanoparticles: Structure, composition and antibacterial assay Chernozem, R.V. and Surmeneva, M.A. and Krause, B. and Baumbach, T. and Ignatov, V.P. and Prymak, O. and Loza, K. and Epple, M. and Ennen-Roth, F. and Wittmar, A. and Ulbricht, M. and Chudinova, E.A. and Rijavec, T. and Lapanje, A... Materials Science and Engineering C 97 420-430 (2019) Herein TiO2 nanotubes (NTs) were fabricated via electrochemical anodization and coated with silver and calcium phosphate (CaP) nanoparticles (NPs) by electrophoretic deposition. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) revealed that Ag and CaP NPs were successfully deposited onto the TiO2 NTs. Using X-ray diffraction, only anatase and Ti were observed after deposition of Ag and CaP NPs. However, X-ray photoelectron spectroscopy (XPS) analysis revealed that the binding energy (BE) of the Ag and CaP NP core levels corresponded to metallic Ag, hydroxyapatite and amorphous calcium phosphate, based on the knowledge that CaP NPs synthesized by precipitation have the nanocrystalline structure of hydroxyapatite. The application of Ag NPs allows for decreasing the water contact angle and thus increasing the surface free energy. It was concluded that the CaP NP surfaces are superhydrophilic. A significant antimicrobial effect was observed on the TiO2 NT surface after the application of Ag NPs and/or CaP NPs compared with that of the pure TiO2 NTs. Thus, fabrication of TiO2 NTs, Ag NPs and CaP NPs with PEI is promising for diverse biomedical applications, such as in constructing a biocompatible coating on the surface of Ti that includes an antimicrobial effect. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msec.2018.12.045

• 2019 • 190	Tunable Magnetic Phases at Fe 3 O 4 /SrTiO 3 Oxide Interfaces Hamed, M.H. and Hinz, R.A. and Lömker, P. and Wilhelm, M. and Gloskovskii, A. and Bencok, P. and Schmitz-Antoniak, C. and Elnaggar, H. and Schneider, C.M. and Müller, M. ACS Applied Materials and Interfaces 11 7576-7583 (2019) We demonstrate the emergence and control of magnetic phases between magnetite (Fe 3 O 4 ), a ferrimagnetic halfmetal, and SrTiO 3 , a transparent nonmagnetic insulator considered the bedrock of oxide-based electronics. The Verwey transition (T V ) was detected to persist from bulk-like down to ultrathin Fe 3 O 4 films, decreasing from 117 ± 4 K (38 nm) to 25 ± 4 K (2 nm), respectively. Element-selective electronic and magnetic properties of the ultrathin films and buried interfaces are studied by angle-dependent hard X-ray photoelectron spectroscopy and X-ray magnetic circular dichroism techniques. We observe a reduction of Fe 2+ ions with decreasing film thickness, accompanied by an increase of Fe 3+ ions in both tetrahedral and octahedral sites and conclude on the formation of a magnetically active ferrimagnetic 2 u.c. γ-Fe 2 O 3 intralayer. To manipulate the interfacial magnetic phase, a postannealing process causes the controlled reduction of the Î-Fe 2 O 3 that finally leads to stoichiometric and ferrimagnetic Fe 3 O 4 /SrTiO 3 (001) heterointerfaces. © 2019 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.8b20625

• 2018 • 189	Amphiphilic Alginates for Marine Antifouling Applications Jakobi, V. and Schwarze, J. and Finlay, J.A. and Nolte, K.A. and Spöllmann, S. and Becker, H.-W. and Clare, A.S. and Rosenhahn, A. Biomacromolecules 19 402-408 (2018) Amphiphilic polymers are promising candidates for novel fouling-release coatings for marine applications. We grafted amphiphilic alginates with fluorinated side chains to glass and silicon substrates and characterized the obtained films by contact angle goniometry, spectroscopic ellipsometry, XPS, and ATR-FTIR. The potential to inhibit protein attachment was tested against four different proteins, and intermediate fluorine loadings showed the strongest reduction with respect to hydrophobic, aliphatic controls. A similar trend was observed in dynamic attachment experiments using Navicula perminuta diatoms and settlement experiments with zoospores of the green algae Ulva linza. The results indicate that amphiphilic alginates are promising natural and renewable biomacromolecules that could be included in future protective coating technologies. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acs.biomac.7b01498

• 2018 • 188	Atomic Layer Deposition of Nickel on ZnO Nanowire Arrays for High-Performance Supercapacitors Ren, Q.-H. and Zhang, Y. and Lu, H.-L. and Wang, Y.-P. and Liu, W.-J. and Ji, X.-M. and Devi, A. and Jiang, A.-Q. and Zhang, D.W. ACS Applied Materials and Interfaces 10 468-476 (2018) A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g-1), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g-1). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.7b13392

• 2018 • 187	Low-temperature MOCVD deposition of Bi2Te3 thin films using Et2BiTeEt as single source precursor Bendt, G. and Gassa, S. and Rieger, F. and Jooss, C. and Schulz, S. Journal of Crystal Growth 490 77-83 (2018) Et2BiTeEt was used as single source precursor for the deposition of Bi2Te3 thin films on Si(1 0 0) substrates by metal organic chemical vapor deposition (MOCVD) at very low substrate temperatures. Stoichiometric and crystalline Bi2Te3 films were grown at 230 °C, which is approximately 100 °C lower compared to conventional MOCVD processes using one metal organic precursors for each element. The Bi2Te3 films were characterized using scanning electron microscopy, high-resolution transmission electron microscopy and X-ray diffraction. The elemental composition of the films, which was determined by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy, was found to be strongly dependent of the substrate temperature. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jcrysgro.2018.03.021

• 2018 • 186	Oxidation and stability of multi-walled carbon nanotubes in hydrogen peroxide solution Safo, I.A. and Liu, F. and Xie, K. and Xia, W. Materials Chemistry and Physics 214 472-481 (2018) The oxidation and stability of multi-walled carbon nanotubes (CNTs) have been investigated by exposing CNTs in 30% w/v H2O2 solution at room temperature (RT) for up to 8 weeks and at 80 °C for up to 8 h. H2O2 oxidation not only generated surface oxygen-containing groups, but also created surface defects, as disclosed by results of temperature-programmed desorption and X-ray Photoelectron Spectroscopy. The total surface oxygen content was found to be correlated to the final H2O2 concentration. The higher the total surface oxygen content on CNTs, the lower the final H2O2 concentration. Meanwhile, the carbon oxidation and simultaneous H2O2 decomposition were observed and confirmed by an online analysis of evolved gases during the oxidation stepwise heated from room temperature to 80 °C. Raman study showed that the D/G and D'/G ratios of the CNTs oxidized at RT first decreased with an oxidation time of 4 weeks and then increased when prolonging the oxidation time up to 8 weeks. Similar trend was also observed on the CNTs oxidized at 80 °C. The size of CNTs was gradually reduced with increasing oxidation time as shown by SEM studies. Our work reveals the critical changes in the surface oxygen groups as well as the changes in morphology at two distinct stages of hydrogen peroxide treatment, purification and then functionalization. CNTs can withstand 30% w/v H2O2 oxidation for only a certain time, while they may be damaged or consumed eventually in long-term applications. Our study contributes to filling in the knowledge gap about CNT surface oxidation and structural changes with H2O2 treatment under industrial conditions. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.matchemphys.2018.05.001

• 2017 • 185	Composite targets in HiPIMS plasmas: Correlation of in-vacuum XPS characterization and optical plasma diagnostics Layes, V. and Monje, S. and Corbella, C. and Schulz-Von der Gathen, V. and Von Keudell, A. and De Los Arcos, T. Journal of Applied Physics 121 (2017) In-vacuum characterization of magnetron targets after High Power Impulse Magnetron Sputtering (HiPIMS) has been performed by X-ray photoelectron spectroscopy (XPS). Al-Cr composite targets (circular, 50 mm diameter) mounted in two different geometries were investigated: an Al target with a small Cr disk embedded at the racetrack position and a Cr target with a small Al disk embedded at the racetrack position. The HiPIMS discharge and the target surface composition were characterized in parallel for low, intermediate, and high power conditions, thus covering both the Ar-dominated and the metal-dominated HiPIMS regimes. The HiPIMS plasma was investigated using optical emission spectroscopy and fast imaging using a CCD camera; the spatially resolved XPS surface characterization was performed after in-vacuum transfer of the magnetron target to the XPS chamber. This parallel evaluation showed that (i) target redeposition of sputtered species was markedly more effective for Cr atoms than for Al atoms; (ii) oxidation at the target racetrack was observed even though the discharge ran in pure Ar gas without O2 admixture, the oxidation depended on the discharge power and target composition; and (iii) a bright emission spot fixed on top of the inserted Cr disk appeared for high power conditions. © 2017 Author(s).
  	view abstract	doi: 10.1063/1.4977820

• 2017 • 184	Controlling the conductivity of Ti3C2 MXenes by inductively coupled oxygen and hydrogen plasma treatment and humidity Römer, F.M. and Wiedwald, U. and Strusch, T. and Halim, J. and Mayerberger, E. and Barsoum, M.W. and Farle, M. RSC Advances 7 13097-13103 (2017) We report on the effects of plasma treatment and humidity on the electrical conductivities of Ti3C2 MXene thin films. The latter-spincoated from a colloidal solution produced by LiF/HCl etching of Ti3AlC2 powders-were 13 nm thick with an area of 6.8 mm2. The changes in the films exposed to hydrogen (H) and oxygen (O) plasmas in vacuum were analyzed by X-ray photoelectron spectroscopy. We find that the film resistivities can be switched reproducibly by plasma treatment between 5.6 μΩm (oxidized state) to 4.6 μΩm (reduced state). Both states show metallic like conductivity. In high vacuum, the film resistivity was 243 Ω; when the relative humidity was 80% the film resistance increased to 6340 Ω, a 26 fold increase. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c6ra27505b

• 2017 • 183	Effects of Post Annealing Treatments on the Interfacial Chemical Properties and Band Alignment of AlN/Si Structure Prepared by Atomic Layer Deposition Sun, Long and Lu, Hong-Liang and Chen, Hong-Yan and Wang, Tao and Ji, Xin-Ming and Liu, Wen-Jun and Zhao, Dongxu and Devi, Anjana and Ding, Shi-Jin and Zhang, David Wei Nanoscale Research Letters 12 102 (2017) The influences of annealing temperature in N-2 atmosphere on interfacial chemical properties and band alignment of AlN/Si structure deposited by atomic layer deposition have been investigated based on x-ray photoelectron spectroscopy and spectroscopic ellipsometry. It is found that more oxygen incorporated into AlN film with the increasing annealing temperature, resulting from a little residual H2O in N-2 atmosphere reacting with AlN film during the annealing treatment. Accordingly, the Si-N bonding at the interface gradually transforms to Si-O bonding with the increasing temperature due to the diffusion of oxygen from AlN film to the Si substrate. Specially, the Si-O-AI bonding state can be detected in the 900 degrees C-annealed sample. Furthermore, it is determined that the band gap and valence band offset increase with increasing annealing temperature.
  	view abstract	doi: 10.1186/s11671-016-1822-x

• 2017 • 182	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 abstract	doi: 10.1021/acscatal.6b02963

• 2017 • 181	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 abstract	doi: 10.1016/j.ultramic.2017.05.003

• 2017 • 180	Hollow fiber membrane lumen modified by polyzwitterionic grafting Lieu Le, N. and Quilitzsch, M. and Cheng, H. and Hong, P.-Y. and Ulbricht, M. and Nunes, S.P. and Chung, T.-S. Journal of Membrane Science 522 1-11 (2017) In this study, we demonstrate an effective way to modify the lumen of polyetherimide hollow fibers by grafting zwitterionic poly(sulfobetaine) to increase the membrane resistance to fouling. Surface-selective grafting of the protective hydrogel layers has been achieved in a facile two-step process. The first step is the adsorption of a macromolecular redox co-initiator on the lumen-side surface of the membrane, which in the second step, after flushing the lumen of the membrane with a solution comprising monomers and a complementary redox initiator, triggers the in situ cross-linking copolymerization at room temperature. The success of grafting reaction has been verified by the surface elemental analyses using X-ray photoelectron spectroscopy (XPS) and the surface charge evaluation using zeta potential measurements. The hydrophilicity of the grafted porous substrate is improved as indicated by the change of contact angle value from 44° to 30°, due to the hydration layer on the surface produced by the zwitterionic poly(sulfobetaine). Compared to the pristine polyetherimide (PEI) substrate, the poly(sulfobetaine) grafted substrates exhibit high fouling resistance against bovine serum albumin (BSA) adsorption, E. coli attachment and cell growth on the surface. Fouling minimization in the lumen is important for the use of hollow fibers in different processes. For instance, it is needed to preserve power density of pressure-retarded osmosis (PRO). In high-pressure PRO tests, a control membrane based on PEI with an external polyamide selective layer was seriously fouled by BSA, leading to a high water flux drop of 37%. In comparison, the analogous membrane, whose lumen was modified with poly(sulfobetaine), not only had a less water flux decline but also had better flux recovery, up to 87% after cleaning and hydraulic pressure impulsion. Clearly, grafting PRO hollow fiber membranes with zwitterionic polymeric hydrogels as a protective layer potentially sustains PRO performance for power generation. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.memsci.2016.08.038

• 2017 • 179	Hybrid biocomposites based on titania nanotubes and a hydroxyapatite coating deposited by RF-magnetron sputtering: Surface topography, structure, and mechanical properties Chernozem, R.V. and Surmeneva, M.A. and Krause, B. and Baumbach, T. and Ignatov, V.P. and Tyurin, A.I. and Loza, K. and Epple, M. and Surmenev, R.A. Applied Surface Science 426 229-237 (2017) In this study, biocomposites based on porous titanium oxide structures and a calcium phosphate (CaP) or hydroxyapatite (HA) coating are described and prepared. Nanotubes (NTs) with different pore dimensions were processed using anodic oxidation of Ti substrates in a NH4F-containing electrolyte solution at anodization voltages of 30 and 60 V with a DC power supply. The external diameters of the nanotubes prepared at 30 V and 60 V were 53 ± 10 and 98 ± 16 nm, respectively. RF-magnetron sputtering of the HA target in a single deposition run was performed to prepare a coating on the surface of TiO2 NTs prepared at 30 and 60 V. The thickness of the CaP coating deposited on the mirror-polished Si substrate in the same deposition run with TiO2 NTs was determined by optical ellipsometry (SE) 95 ± 5 nm. Uncoated and CaP-coated NTs were annealed at 500 °C in air. Afterwards, the presence of TiO2 (anatase) was observed. The scanning electron microscopy (SEM), X-ray diffraction (XRD), photoelectron spectroscopy (XPS) and nanoindentation results revealed the influence that the NT dimensions had on the CaP coating deposition process. The tubular surfaces of the NTs were completely coated with the HA coating when prepared at 30 V, and no homogeneous CaP coating was observed when prepared at 60 V. The XRD patterns show peaks assigned to crystalline HA only for the coated TiO2 NTs prepared at 30 V. High-resolution XPS spectra show binding energies (BE) of Ca 2p, P 2p and O 1s core-levels corresponding to HA and amorphous calcium phosphate on TiO2 NTs prepared at 30 V and 60 V, respectively. Fabrication of TiO2 NTs results in a significant decrease to the elastic modulus and nanohardness compared to the Ti substrate. The porous structure of the NTs causes an increase in the elastic strain to failure of the coating (H/E) and the parameter used to describe the resistance of the material to plastic deformation (H3/E2) at the nanoscale level compared to the Ti substrate. Furthermore, only the HA coating on the NTs exhibits a significantly increased H/E ratio and H3/E2 factor compared to the NTs and Ti substrate. Increases in resistance to penetration for the indenter were also observed for HA-coated TiO2 NTs prepared at 30 V compared to uncoated and CaP-coated NTs prepared at 60 V. © 2017 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2017.07.199

• 2017 • 178	Hydrogen effects on microstructural evolution and passive film characteristics of a duplex stainless steel Luo, H. and Li, Z. and Chen, Y.-H. and Ponge, D. and Rohwerder, M. and Raabe, D. Electrochemistry Communications 79 28-32 (2017) We revealed the effects of hydrogen on the microstructural evolution and passive film properties of a 2205 duplex stainless steel by the joint use of electron backscatter diffraction (EBSD), electron channeling contrast imaging (ECCI), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The microstructural analysis results show that effects of hydrogen on the two phases are different: (i) in austenite, stacking faults are induced by hydrogen, and (ii) in ferrite, hydrogen causes an increase of the dislocation density. The XPS analysis revealed that hydrogen reduced the occurrence of Cr2O3 and nitrogen in the passive film, leading to the reduction of their overall thickness. Furthermore, for the first time we demonstrated that the hydrogen release time plays an important role in the electrochemical behavior of the hydrogen charged steel. © 2017 Elsevier B.V.
  	view abstract	doi: 10.1016/j.elecom.2017.04.013

• 2017 • 177	Improving the zT value of thermoelectrics by nanostructuring: tuning the nanoparticle morphology of Sb2Te3 by using ionic liquids Schaumann, J. and Loor, M. and Ünal, D. and Mudring, A. and Heimann, S. and Hagemann, U. and Schulz, S. and Maculewicz, F. and Schierning, G. Dalton Transactions 46 656-668 (2017) A systematic study on the microwave-assisted thermolysis of the single source precursor (Et2Sb)2Te (1) in different asymmetric 1-alkyl-3-methylimidazolium- and symmetric 1,3-dialkylimidazolium-based ionic liquids (ILs) reveals the distinctive role of both the anion and the cation in tuning the morphology and microstructure of the resulting Sb2Te3 nanoparticles as evidenced by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). A comparison of the electrical and thermal conductivities as well as the Seebeck coefficient of the Sb2Te3 nanoparticles obtained from different ILs reveals the strong influence of the specific IL, from which C4mimI was identified as the best solvent, on the thermoelectric properties of as-prepared nanosized Sb2Te3. This work provides design guidelines for ILs, which allow the synthesis of nanostructured thermoelectrics with improved performances. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c6dt04323b

• 2017 • 176	Laser-induced surface activation of biocomposites for electroless metallization Rytlewski, P. and Bahners, T. and Polewski, F. and Gebert, B. and Gutmann, J.S. and Hartmann, N. and Hagemann, U. and Moraczewski, K. Surface and Coatings Technology 311 104-112 (2017) In this work biocomposites containing polylactide (PLA), polycaprolactone (PCL), copper(II) oxide and copper acetylacetonate were manufactured by an extrusion process. The extruded composites differed with respect to the PLA/PCL ratio whereas the content of mixed copper(II) oxide and copper acetylacetonate powders was held constant at 20 wt%. The main aims for the addition of PCL was to increase impact strength resistance, improve surface catalytic properties and reduce the temperature of extrusion, thus limiting degradation effects initiated by copper acetylacetonate. The composite samples were irradiated with an ArF excimer laser varying the number of laser pulses and then metalized by electroless plating. Based on optical microscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) measurements, it was found that (i) PCL was dispersed in the form of droplets in all volume of PLA, (ii) the copper compounds were preferably located in the dispersed PCL phase, and (iii) composites with higher PCL content were more effectively metalized. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2016.12.048

• 2017 • 175	Low-Temperature Atomic Layer Deposition of Cobalt Oxide as an Effective Catalyst for Photoelectrochemical Water-Splitting Devices Kim, J. and Iivonen, T. and Hämäläinen, J. and Kemell, M. and Meinander, K. and Mizohata, K. and Wang, L. and Räisänen, J. and Beranek, R. and Leskelä, M. and Devi, A. Chemistry of Materials 29 5796-5805 (2017) We have developed a low-temperature atomic layer deposition (ALD) process for depositing crystalline and phase pure spinel cobalt oxide (Co3O4) films at 120 °C using [Co(tBu2DAD)2] and ozone as coreagent. X-ray diffraction, UV-vis spectroscopy, atomic force microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis were performed to characterize the structure and properties of the films. The as-deposited Co3O4 films are crystalline with a low amount of impurities (<2% C and <5% H) despite low deposition temperatures. Deposition of Co3O4 onto thin TiO2 photoanodes (100 nm) for water oxidation resulted in 30% improvement of photocurrent (after 10 ALD cycles yielding small Co3O4 particles) as compared to pristine TiO2 films), and exhibited no detrimental effects on photocurrent response up to 300 deposition cycles (approximately 35 nm thick films), demonstrating the applicability of the developed ALD process for deposition of effective catalyst particles and layers in photoelectrochemical water-splitting devices. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acs.chemmater.6b05346

• 2017 • 174	Nano-sized metal organic framework to improve the structural properties and desalination performance of thin film composite forward osmosis membrane Zirehpour, A. and Rahimpour, A. and Ulbricht, M. Journal of Membrane Science 531 59-67 (2017) In the present study, nano-sized metal-organic framework (MOF) particles consisting of silver (I) and 1,3,5-benzene tricarboxylic acid were synthesized and applied to improve the structural properties as well as desalination performance of thin-film composite (TFC) forward osmosis (FO) membranes. The MOF nanocrystals were incorporated into the polyamide layer of membranes through interfacial polymerization. Characterizations by Field emission scanning electron microscopy and X-ray photoelectron spectroscopy enabled the detection of MOF nanocrystals within the selective layer of the resultant membranes. The MOF incorporation led to changes of the membrane active layer in terms of hydrophilicity and transport properties, without detrimental effects on the layer selectivity. These features enhanced pure water permeability of the membranes to 129%, which was provided through 0.04% MOF loading of the organic phase during interfacial polymerization. As a result, the modified membrane exhibited an enhanced FO seawater desalination performance in comparison with the control membrane. The performance stability of TFC membrane was also improved by presence of MOF in active layer (as seen by a water flux decline of about 7% for modified membrane against about 18% for unmodified membrane when tested with real seawater). This study demonstrates the potential of MOF particles to enhance desalination performance of TFC membranes in FO systems. © 2017 Elsevier B.V.
  	view abstract	doi: 10.1016/j.memsci.2017.02.049

• 2017 • 173	New amidinate complexes of indium(III): Promising CVD precursors for transparent and conductive In2O3 thin films Gebhard, M. and Hellwig, M. and Kroll, A. and Rogalla, D. and Winter, M. and Mallick, B. and Ludwig, Ar. and Wiesing, M. and Wieck, A.D. and Grundmeier, G. and Devi, A. Dalton Transactions 46 10220-10231 (2017) For the first time, synthesis of two new amidinate-ligand comprising heteroleptic indium complexes, namely [InCl(amd)2] (1) and [InMe(amd)2] (2), via salt-metathesis and their detailed characterization is reported. For comparison, the earlier reported homoleptic tris-amidinate [In(amd)3] (3) was also synthesized and analyzed in detail especially with respect to the thermal properties and molecular crystal structure analysis which are reported here for the first time. From nuclear magnetic resonance spectroscopy (NMR) and single-crystal X-ray diffraction (XRD), all three compounds were found to be monomeric with C2 (compound 1 and 2) and C3 symmetry (compound 3). Both halide-free compounds 2 and 3 were evaluated regarding their thermal properties using temperature-dependent 1H-NMR, thermogravimetric analysis (TGA) and iso-TGA, revealing suitable volatility and thermal stability for their application as potential precursors for chemical vapor phase thin film deposition methods. Indeed, metalorganic chemical vapor deposition (MOCVD) experiments over a broad temperature range (400 °C-700 °C) revealed the suitability of these two compounds to fabricate In2O3 thin films in the presence of oxygen on Si, thermally grown SiO2 and fused silica substrates. The as-deposited thin films were characterized in terms of their crystallinity via X-ray diffraction (XRD), morphology by scanning electron microscopy (SEM) and composition through complementary techniques such as Rutherford-backscattering spectrometry (RBS) in combination with nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS). From UV/Vis spectroscopy, the deposited In2O3 thin films on fused silica substrates were found to be highly transparent (T > 95% at 560 nm, compound 3). In addition, Hall measurements revealed high charge carrier densities of 1.8 × 1020 cm-3 (2) and 6.5 × 1019 cm-3 (3) with a Hall-mobility of 48 cm2 V-1 s-1 (2) and 74 cm2 V-1 s-1 (3) for the respective thin films, rendering the obtained thin films applicable as a transparent conducting oxide that could be suitable for optoelectronic applications. © 2017 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c7dt01280b

• 2017 • 172	Plasma-Activated Copper Nanocube Catalysts for Efficient Carbon Dioxide Electroreduction to Hydrocarbons and Alcohols Gao, D. and Zegkinoglou, I. and Divins, N.J. and Scholten, F. and Sinev, I. and Grosse, P. and Roldan Cuenya, B. ACS Nano 11 4825-4831 (2017) Carbon dioxide electroreduction to chemicals and fuels powered by renewable energy sources is considered a promising path to address climate change and energy storage needs. We have developed highly active and selective copper (Cu) nanocube catalysts with tunable Cu(100) facet and oxygen/chlorine ion content by low-pressure plasma pretreatments. These catalysts display lower overpotentials and higher ethylene, ethanol, and n-propanol selectivity, resulting in a maximum Faradaic efficiency (FE) of ∼73% for C2 and C3 products. Scanning electron microscopy and energy-dispersive X-ray spectroscopy in combination with quasi-in situ X-ray photoelectron spectroscopy revealed that the catalyst shape, ion content, and ion stability under electrochemical reaction conditions can be systematically tuned through plasma treatments. Our results demonstrate that the presence of oxygen species in surface and subsurface regions of the nanocube catalysts is key for achieving high activity and hydrocarbon/alcohol selectivity, even more important than the presence of Cu(100) facets. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acsnano.7b01257

• 2017 • 171	Redox Activity of Oxo-Bridged Iridium Dimers in an N,O-Donor Environment: Characterization of Remarkably Stable Ir(IV,V) Complexes Sinha, S.B. and Shopov, D.Y. and Sharninghausen, L.S. and Stein, C.J. and Mercado, B.Q. and Balcells, D. and Pedersen, T.B. and Reiher, M. and Brudvig, G.W. and Crabtree, R.H. Journal of the American Chemical Society 139 9672-9683 (2017) Chemical and electrochemical oxidation or reduction of our recently reported Ir(IV,IV) mono-μ-oxo dimers results in the formation of fully characterized Ir(IV,V) and Ir(III,III) complexes. The Ir(IV,V) dimers are unprecedented and exhibit remarkable stability under ambient conditions. This stability and modest reduction potential of 0.99 V vs NHE is in part attributed to complete charge delocalization across both Ir centers. Trends in crystallographic bond lengths and angles shed light on the structural changes accompanying oxidation and reduction. The similarity of these mono-μ-oxo dimers to our Ir "blue solution" water-oxidation catalyst gives insight into potential reactive intermediates of this structurally elusive catalyst. Additionally, a highly reactive material, proposed to be a Ir(V,V) μ-oxo species, is formed on electrochemical oxidation of the Ir(IV,V) complex in organic solvents at 1.9 V vs NHE. Spectroelectrochemistry shows reversible conversion between the Ir(IV,V) and proposed Ir(V,V) species without any degradation, highlighting the exceptional oxidation resistance of the 2-(2-pyridinyl)-2-propanolate (pyalk) ligand and robustness of these dimers. The Ir(III,III), Ir(IV,IV) and Ir(IV,V) redox states have been computationally studied both with DFT and multiconfigurational calculations. The calculations support the stability of these complexes and provide further insight into their electronic structures. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/jacs.7b04874

• 2017 • 170	Solid electrolyte interphase (SEI) at TiO2 electrodes in li-ion batteries: Defining apparent and effective SEI based on evidence from X-ay photoemission spectroscopy and scanning electrochemical microscopy Ventosa, E. and Madej, E. and Zampardi, G. and Mei, B. and Weide, P. and Antoni, H. and La Mantia, F. and Muhler, M. and Schuhmann, W. ACS Applied Materials and Interfaces 9 3123-3130 (2017) The high (de)lithiation potential of TiO2 (ca. 1.7 V vs Li/ Li+ in 1 M Li+) decreases the voltage and, thus, the energy density of a corresponding Li-ion battery. On the other hand, it offers several advantages such as the (de)lithiation potential far from lithium deposition or absence of a solid electrolyte interphase (SEI). The latter is currently under controversial debate as several studies reported the presence of a SEI when operating TiO2 electrodes at potentials above 1.0 V vs Li/Li+. We investigate the formation of a SEI at anatase TiO2 electrodes by means of X-ray photoemission spectroscopy (XPS) and scanning electrochemical microscopy (SECM). The investigations were performed in different potential ranges, namely, during storage (without external polarization), between 3.0-2.0 V and 3.0-1.0 V vs Li/Li+, respectively. No SEI is formed when a completely dried and residues-free TiO2 electrode is cycled between 3.0 and 2.0 V vs Li/Li+. A SEI is detected by XPS in the case of samples stored for 6 weeks or cycled between 3.0 and 1.0 V vs Li/Li+. With use of SECM, it is verified that this SEI does not possess the electrically insulating character as expected for a "classic" SEI. Therefore, we propose the term apparent SEI for TiO2 electrodes to differentiate it from the protecting and ef fective SEI formed at graphite electrodes. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.6b13306

• 2017 • 169	Synthesis and evaluation of new copper ketoiminate precursors for a facile and additive-free solution-based approach to nanoscale copper oxide thin films Karle, Sarah and Rogalla, Detlef and Ludwig, Arne and Becker, Hans-Werner and Wieck, Andreas Dirk and Grafen, Markus and Ostendorf, Andreas and Devi, Anjana Dalton Transactions 46 2670--2679 (2017) Novel copper ketoiminate compounds were synthesized and for the first time applied for additive-free solution-based deposition of nanoscale copper oxide thin films. The two closely related compounds, namely the bis[4-(2-ethoxyethyl-imino)-3-pentanonato] copper, [Cu(EEKI)(2)], and bis[4-(3-methoxypropylimino)- 3-pentanonato] copper, [Cu(MPKI)(2)], were characterized by means of elemental and thermogravimetric analysis (TGA), as well as electron impact mass spectrometry (EI-MS). The advantages of these compounds are that they are liquid and possess excellent solubility in common organic solvents in addition to an optimum reactivity towards ambient moisture that enables a facile solution-based approach to nanoscale copper oxide thin films. Moreover, no additives or aging is needed to stabilize the solution processing of the copper oxide layers. [Cu(MPKI)(2)] was tested in detail for the deposition of copper oxide thin films by spin coating. Upon one-step annealing, high-quality, uniform, crystalline copper oxide thin films were deposited on Si, SiO2, as well as on quartz substrates. Structural, morphological and compositional characteristics of the copper oxide nanostructures were investigated in detail by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and a combined analysis using Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). It was possible to control the copper oxide phases (CuO and Cu2O) by systematic tuning of the post-deposition annealing conditions. The functional properties in terms of optical band gap were investigated using UV/Vis spectroscopy, while the transport properties, such as resistivity, mobility and carrier concentration were analyzed employing Hall measurements, which confirmed the p-type conductivity of the copper oxide layers.
  	view abstract	doi: 10.1039/c6dt04399b

• 2016 • 168	Antifouling and Antibacterial Multifunctional Polyzwitterion/Enzyme Coating on Silicone Catheter Material Prepared by Electrostatic Layer-by-Layer Assembly Vaterrodt, A. and Thallinger, B. and Daumann, K. and Koch, D. and Guebitz, G.M. and Ulbricht, M. Langmuir 32 1347-1359 (2016) The formation of bacterial biofilms on indwelling medical devices generally causes high risks for adverse complications such as catheter-associated urinary tract infections. In this work, a strategy for synthesizing innovative coatings of poly(dimethylsiloxane) (PDMS) catheter material, using layer-by-layer assembly with three novel functional polymeric building blocks, is reported, i.e., an antifouling copolymer with zwitterionic and quaternary ammonium side groups, a contact biocidal derivative of that polymer with octyl groups, and the antibacterial hydrogen peroxide (H2O2) producing enzyme cellobiose dehydrogenase (CDH). CDH oxidizes oligosaccharides by transferring electrons to oxygen, resulting in the production of H2O2. The design and synthesis of random copolymers which combine segments that have antifouling properties by zwitterionic groups and can be used for electrostatically driven layer-by-layer (LbL) assembly at the same time were based on the atom-transfer radical polymerization of dimethylaminoethyl methacrylate and subsequent partial sulfobetainization with 1,3-propane sultone followed by quaternization with methyl iodide only or octyl bromide and thereafter methyl iodide. The alternating multilayer systems were formed by consecutive adsorption of the novel polycations with up to 50% zwitterionic groups and of poly(styrenesulfonate) as the polyanion. Due to its negative charge, enzyme CDH was also firmly embedded as a polyanionic layer in the multilayer system. This LbL coating procedure was first performed on prefunctionalized silicon wafers and studied in detail with ellipsometry as well as contact angle (CA) and zetapotential (ZP) measurements before it was transferred to prefunctionalized PDMS and analyzed by CA and ZP measurements as well as atomic force microscopy. The coatings comprising six layers were stable and yielded a more neutral and hydrophilic surface than did PDMS, the polycation with 50% zwitterionic groups having the largest effect. Enzyme activity was found to be dependent on the depth of embedment in the multilayer coating. Depending on the used polymeric building block, up to a 60% reduction in the amount of adhering bacteria and clear evidence for killed bacteria due to the antimicrobial functionality of the coating could be confirmed. Overall, this work demonstrates the feasibility of an easy to perform and shape-independent method for preparing an antifouling and antimicrobial coating for the significant reduction of biofilm formation and thus reducing the risk of acquiring infections by using urinary catheters. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/acs.langmuir.5b04303

• 2016 • 167	Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study Jendrzej, S. and Gökce, B. and Amendola, V. and Barcikowski, S. Journal of Colloid and Interface Science 463 299-307 (2016) Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50 days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1. day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions. © 2015.
  	view abstract	doi: 10.1016/j.jcis.2015.10.032

• 2016 • 166	Cr2O3 Nanoparticles on Ba5Ta4O15 as a Noble-Metal-Free Oxygen Evolution Co-Catalyst for Photocatalytic Overall Water Splitting Soldat, J. and Busser, G.W. and Muhler, M. and Wark, M. ChemCatChem 8 153-156 (2016) The (1 1 1)-layered perovskite material Ba5Ta4O15 represents a suitable photoabsorber with remarkable photocatalytic activity in overall water splitting. We are the first to demonstrate overall water splitting without the presence of a noble-metal-based co-catalyst over this catalyst. The photocatalytic activity of Ba5Ta4O15 was investigated by overall water splitting after reductive photodeposition of amorphous Cr2O3. The formation of Cr2O3 nanoparticles for water splitting was evidenced by X-ray photoelectron spectroscopy and transmission electron microscopy. The reductive photodeposition of very low amounts of Cr2O3 on Ba5Ta4O15 induces stable rates in overall water splitting up to 465 μmol h-1 H2 and 228 μmol h-1 O2. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cctc.201500977

• 2016 • 165	Effect of pH on the spontaneous synthesis of palladium nanoparticles on reduced graphene oxide Zhang, X. and Ooki, W. and Kosaka, Y.R. and Okonogi, A. and Marzun, G. and Wagener, P. and Barcikowski, S. and Kondo, T. and Nakamura, J. Applied Surface Science 389 911-915 (2016) Palladium (Pd) nanoparticles were spontaneously deposited on reduced graphene oxide (rGO) without any external reducing agents. The prepared Pd/rGO composites were then characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Spontaneous deposition occurred because of a redox reaction between the Pd precursor and rGO, which involved reduction of bivalent Pd to metallic Pd0 and oxidation of the sp2 carbon of rGO to oxygen-containing functional groups. The amount of Pd deposited on rGO varied with pH, and this was attributed to electrostatic interactions between the Pd precursor and rGO based on the results of zeta potential measurements. The importance of the redox reaction in the spontaneous deposition was demonstrated in the experiment with Zn, Ni, Cu, Ag, Pt, Pd, and Au. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2016.08.014

• 2016 • 164	Energy dissipation from a correlated system driven out of equilibrium Rameau, J.D. and Freutel, S. and Kemper, A.F. and Sentef, M.A. and Freericks, J.K. and Avigo, I. and Ligges, M. and Rettig, L. and Yoshida, Y. and Eisaki, H. and Schneeloch, J. and Zhong, R.D. and Xu, Z.J. and Gu, G.D. and Johnson... Nature Communications 7 (2016) In complex materials various interactions have important roles in determining electronic properties. Angle-resolved photoelectron spectroscopy (ARPES) is used to study these processes by resolving the complex single-particle self-energy and quantifying how quantum interactions modify bare electronic states. However, ambiguities in the measurement of the real part of the self-energy and an intrinsic inability to disentangle various contributions to the imaginary part of the self-energy can leave the implications of such measurements open to debate. Here we employ a combined theoretical and experimental treatment of femtosecond time-resolved ARPES (tr-ARPES) show how population dynamics measured using tr-ARPES can be used to separate electron-boson interactions from electron-electron interactions. We demonstrate a quantitative analysis of a well-defined electron-boson interaction in the unoccupied spectrum of the cuprate Bi 2 Sr 2 CaCu 2 O 8+x characterized by an excited population decay time that maps directly to a discrete component of the equilibrium self-energy not readily isolated by static ARPES experiments.
  	view abstract	doi: 10.1038/ncomms13761

• 2016 • 163	Growth, characterization, and transport properties of ternary (Bi1-xSbx)2Te3 topological insulator layers Weyrich, C. and Drögeler, M. and Kampmeier, J. and Eschbach, M. and Mussler, G. and Merzenich, T. and Stoica, T. and Batov, I.E. and Schubert, J. and Plucinski, L. and Beschoten, B. and Schneider, C.M. and Stampfer, C. and Grütz... Journal of Physics Condensed Matter 28 (2016) Ternary (Bi1-xSbx)2Te3 films with an Sb content between 0 and 100% were deposited on a Si(1 1 1) substrate by means of molecular beam epitaxy. X-ray diffraction measurements confirm single crystal growth in all cases. The Sb content is determined by x-ray photoelectron spectroscopy. Consistent values of the Sb content are obtained from Raman spectroscopy. Scanning Raman spectroscopy reveals that the (Bi1-xSbx)2Te3 layers with an intermediate Sb content show spatial composition inhomogeneities. The observed spectra broadening in angular-resolved photoemission spectroscopy (ARPES) is also attributed to this phenomena. Upon increasing the Sb content from x = 0 to 1 the ARPES measurements show a shift of the Fermi level from the conduction band to the valence band. This shift is also confirmed by corresponding magnetotransport measurements where the conductance changes from n- to p-type. In this transition region, an increase of the resistivity is found, indicating a location of the Fermi level within the band gap region. More detailed measurements in the transition region reveals that the transport takes place in two independent channels. By means of a gate electrode the transport can be changed from n- to p-type, thus allowing a tuning of the Fermi level within the topologically protected surface states. © 2016 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0953-8984/28/49/495501

• 2016 • 162	In Situ EPR Study of the Redox Properties of CuO-CeO2 Catalysts for Preferential CO Oxidation (PROX) Wang, F. and Büchel, R. and Savitsky, A. and Zalibera, M. and Widmann, D. and Pratsinis, S.E. and Lubitz, W. and Schüth, F. ACS Catalysis 6 3520-3530 (2016) Understanding the redox properties of metal oxide based catalysts is a major task in catalysis research. In situ electron paramagnetic resonance (EPR) spectroscopy is capable of monitoring the change of metal ion valences and formation of active sites during redox reactions, allowing for the identification of ongoing redox pathways. Here in situ EPR spectroscopy combined with online gas analysis, supported by ex situ X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), temporal analysis of product (TAP), and mass spectrometry (MS) studies, was utilized to study the redox behavior of CuO-CeO2 catalysts under PROX conditions (preferential oxidation of carbon monoxide in hydrogen). Two redox mechanisms are revealed: (i) a synergetic mechanism that involves the redox pair Ce4+/Ce3+ during oxidation of Cu0/Cu+ species to Cu2+ and (ii) a direct mechanism that bypasses the redox pair Ce4+/Ce3+. In addition, EPR experiments with isotopically enriched 17O2 established the synergetic mechanism as the major redox reaction pathway. The results emphasize the importance of the interactions between Cu and Ce atoms for catalyst performance. With the guidance of these results, an optimized CuO-CeO2 catalyst could be designed. A rather wide temperature operation window of 11 K (from 377 to 388 K), with 99% conversion efficiency and 99% selectivity, was achieved for the preferential oxidation of CO in a H2 feed. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.6b00589

• 2016 • 161	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 abstract	doi: 10.1021/acscatal.5b02305

• 2016 • 160	Nanostructured Ternary FeCrAl Oxide Photocathodes for Water Photoelectrolysis Kondofersky, I. and Müller, A. and Dunn, H.K. and Ivanova, A. and Štefanić, G. and Ehrensperger, M. and Scheu, C. and Parkinson, B.A. and Fattakhova-Rohlfing, D. and Bein, T. Journal of the American Chemical Society 138 1860-1867 (2016) A sol-gel method for the synthesis of semiconducting FeCrAl oxide photocathodes for solar-driven hydrogen production was developed and applied for the production of meso- and macroporous layers with the overall stoichiometry Fe0.84Cr1.0Al0.16O3. Using transmission electron microscopy and energy-dispersive X-ray spectroscopy, phase separation into Fe- and Cr-rich phases was observed for both morphologies. Compared to prior work and to the mesoporous layer, the macroporous FeCrAl oxide photocathode had a significantly enhanced photoelectrolysis performance, even at a very early onset potential of 1.1 V vs RHE. By optimizing the macroporous electrodes, the device reached current densities of up to 0.68 mA cm-2 at 0.5 V vs RHE under AM 1.5 with an incident photon-to-current efficiency (IPCE) of 28% at 400 nm without the use of catalysts. Based on transient measurements, this performance increase could be attributed to an improved collection efficiency. At a potential of 0.75 V vs RHE, an electron transfer efficiency of 48.5% was determined. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/jacs.5b08040

• 2016 • 159	On the role of the stability of functional groups in multi-walled carbon nanotubes applied as support in iron-based high-temperature Fischer-Tropsch synthesis Chew, L.M. and Xia, W. and Düdder, H. and Weide, P. and Ruland, H. and Muhler, M. Catalysis Today 270 85-92 (2016) The role of the stability of surface functional groups in oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) applied as support for iron catalysts in high-temperature Fischer-Tropsch synthesis was studied in a fixed-bed U-tube reactor at 340°C and 25 bar with a H2:CO ratio of 1. Iron oxide nanoparticles supported on untreated oxygen-functionalized CNTs (OCNTs) and nitrogen-functionalized CNTs (NCNTs) as well as thermally treated OCNTs were synthesized by the dry impregnation method using ammonium ferric citrate as iron precursor. The properties of all catalysts were examined using X-ray diffraction, temperature-programmed reduction in H2, X-ray photoelectron spectroscopy and temperature-programmed oxidation in O2. The activity loss for iron nanoparticles supported on untreated OCNTs was found to originate from severe sintering and carbon encapsulation of the iron carbide nanoparticles under reaction conditions. Conversely, the sintering of the iron carbide nanoparticles on thermally treated OCNTs and untreated NCNTs during reaction was far less pronounced. The presence of more stable surface functional groups in both thermally treated OCNTs and untreated NCNTs is assumed to be responsible for the less severe sintering of the iron carbide nanoparticles during reaction. As a result, no activity loss for iron nanoparticles supported on thermally treated OCNTs and untreated NCNTs was observed, which even became gradually more active under reaction conditions. © 2015 Published by Elsevier B.V.
  	view abstract	doi: 10.1016/j.cattod.2015.09.023

• 2016 • 158	Organosilane modified Zr-based conversion layer on Zn–Al alloy coated steel sheets Lostak, T. and Timma, C. and Krebs, S. and Flock, J. and Schulz, S. Surface and Coatings Technology 305 223-230 (2016) Conversion layers based on amorphous Zirconium oxide are still in focus to replace state-of-the-art pre-treatment technologies like chromate- and phosphate-based inorganic protection coatings in different industrial sectors. Besides exceeding corrosion protection properties these layers offer sufficient adhesion behaviours. To investigate the influence of organofunctional silanes on the protection properties of these pre-treatment systems, 3-gylcidoxypropyltrimethoxysilane (γ-GPS) was added to the aqueous model conversion solution containing well-defined amounts of hexafluorozirconic acid (H2ZrF6). The surface composition of these modified conversion layers was determined using X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (FT-IRRAS) and confocal Raman microscopy (CRM). Scanning Kelvin Probe (SKP) measurements were obtained on organic coated samples in order to investigate the corrosive cathodic delamination process in more detail. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2016.08.030

• 2016 • 157	Probing the Dynamic Structure and Chemical State of Au Nanocatalysts during the Electrochemical Oxidation of 2-Propanol Choi, Y. and Sinev, I. and Mistry, H. and Zegkinoglou, I. and Roldan Cuenya, B. ACS Catalysis 6 3396-3403 (2016) A size-dependent trend was observed for the electrochemical total oxidation of 2-propanol to CO2 over Au nanoparticles (NPs), with increasing activity (increased current density and lower overpotential) for decreasing NP size. Furthermore, an enhanced stability against poisoning by the unreacted acetone intermediate was also obtained for NPs smaller than ∼2 nm. Operando X-ray absorption fine structure (XAFS) measurements provided insight into the dynamic evolution of the NP structure and chemical state under reaction conditions, shedding light on the nature of the most catalytically active species and catalyst deactivation phenomena via chemically driven sintering. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.6b00057

• 2016 • 156	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 abstract	doi: 10.1016/j.susc.2016.01.006

• 2016 • 155	Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations Álvarez Galván, C. and Schumann, J. and Behrens, M. and Fierro, J.L.G. and Schlögl, R. and Frei, E. Applied Catalysis B: Environmental 195 104-111 (2016) The physicochemical properties of hydroxycarbonate-based precipitates [zincian malachite (ZM) and aurichalcite precursors], calcined CuO/ZnO precatalysts and finally reduced Cu/ZnO catalysts, with several Cu-Zn ratios, have been investigated by different characterization techniques. Results from isothermal physisorption of N2 (BET), X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), N2O Reactive Frontal Chromatography (N2O-RFC), X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) have been correlated with the catalytic activity for the reverse water-gas shift (rWGS) reaction in order to provide insight into the controversial nature of active species in carbon dioxide activation, respectively the role of Cu and ZnO. Average crystalline domain size of CuO and ZnO show a relationship with the amount of each phase in the calcined sample. This is in agreement with the TPR profiles, which indicate a better dispersion of Cu for the ZnO-rich samples and a shift for the first reduction step to higher temperatures (Tonset for CuII to CuI). XPS measurements point out the surface enrichment of ZnO is less pronounced with higher ZnO/(ZnO + Cu) ratios. Activity results show that catalysts derived from high surface area ex-aurichalcite (Zn content, 50-70% atom) catalysts are more active in rWGS with lower apparent activation energies than ex-ZM catalysts (Zn content, 15-30% atom) with comparable apparent Cu surface area/N2O capacity. Thus, the CO formation rate as function of the apparent Cu surface area indicates that the reaction rate is not dependent on the exposed apparent Cu surface, but from an adjusted interface composition predetermined by the precursor structure and its thermal post-treatment. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apcatb.2016.05.007

• 2016 • 154	Strong metal-support interaction and alloying in Pd/ZnO catalysts for CO oxidation Kast, P. and Friedrich, M. and Girgsdies, F. and Kröhnert, J. and Teschner, D. and Lunkenbein, T. and Behrens, M. and Schlögl, R. Catalysis Today 260 21-31 (2016) Pd/ZnO catalysts with different Pd content have been synthesized, thoroughly characterized and investigated with regard to their reduction behavior in hydrogen or carbon monoxide containing atmospheres, by applying CO-chemisorption, photoelectron spectroscopy, X-ray diffraction, electron microscopy, TPR and DRIFTS techniques. As a catalytic test reaction, CO-oxidation has been applied. The interaction of the noble metal with the support has been revealed in a way that can distinguish between alloying and other surface spreading/wetting phenomena, induced by strong metal-support interaction (SMSI). It was found that while alloy formation promoted CO-oxidation activity additional ZnOx formation by SMSI had the opposite effect. Zinc enrichment at the surface was detected during reduction of the catalysts, depending on the reducing agent and the Pd particle size. © 2015 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.cattod.2015.05.021

• 2016 • 153	Surface investigation and tribological mechanism of a sulfate-based lubricant deposited on zinc-coated steel sheets Timma, C. and Lostak, T. and Janssen, S. and Flock, J. and Mayer, C. Applied Surface Science 390 784-794 (2016) Phosphatation is a well-known technique to improve friction and wear behaviour of zinc coated steel, but has a variety of economic and ecologic limitations. In this study an alternative coating based on ammonium sulfate ((NH4)2SO4) is applied on skin-passed hot-dip galvanized steel sheets in order to investigate its surface chemical and tribological behaviour in a Pin-on-Disk Tribometer. Raman- and X-ray photoelectron spectroscopic results revealed a formation of ammonium zinc sulfate ((NH4)2Zn(SO4)2 * xH2O) on the surface, which is primarily located in the skin-passed areas of the steel material. Sulfate coated samples exhibited a superior friction behaviour in Pin-on-Disk Tests using squalane as a model substance for oil-like lubricated conditions and a formation of a thin lubrication film is obtained in the wear track. Squalane acts as a carrier substance for ammonium zinc sulfate, leading to an effective lubrication film in the wear track. © 2016 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2016.09.002

• 2016 • 152	Surface Structure and Photocatalytic Properties of Bi2WO6 Nanoplatelets Modified by Molybdena Islands from Chemical Vapor Deposition Dittmer, A. and Menze, J. and Mei, B. and Strunk, J. and Luftman, H.S. and Gutkowski, R. and Wachs, I.E. and Schuhmann, W. and Muhler, M. Journal of Physical Chemistry C 120 18191-18200 (2016) We report on a novel route of preparing molybdena-modified bismuth tungstates and their successful application in the photocatalytic oxygen evolution reaction and the oxidation of glycerol. Hierarchically assembled monocrystalline Bi2WO6 nanoplatelets with a specific surface area of 10 m2/g were obtained applying a hydrothermal synthesis method using Na2WO4 and Bi(NO3)3 as precursors, followed by a solvent-free chemical vapor deposition method using Mo(CO)6, resulting in highly dispersed molybdena species. Extensive characterization using X-ray photoelectron spectroscopy, low-energy ion scattering, and Raman spectroscopy showed that microcrystalline MoO3 islands were formed on the bismuth tungstate surface that grew in height and lateral dimension with increasing loading. Correspondingly, the molybdena-modified materials were found to have favorable photocatalytic and photoelectrochemical properties in the oxygen evolution reaction and the selective oxidation of glycerol. © 2016 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcc.6b07007

• 2016 • 151	The effect of sodium on the structure-activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols Anton, J. and Nebel, J. and Song, H. and Froese, C. and Weide, P. and Ruland, H. and Muhler, M. and Kaluza, S. Journal of Catalysis 335 175-186 (2016) A series of Co-modified Cu/ZnO/Al2O3 methanol synthesis catalysts with different Na loadings was prepared and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H2/CO = 1. The bulk and surface properties of the catalysts were characterized after reduction and after 40 h time on stream (TOS) without exposing the catalysts to air during the transfer and the measurements. Increased presence of metallic Co0 after reduction at 350 °C was confirmed by X-ray photoelectron spectroscopy indicating metallic Cu0 to act as a reduction promoter. Catalysts with low Na loadings (≤0.6 wt%) showed strong initial deactivation presumably due to coking of isolated Co0 surface sites favoring hydrocarbon formation. The selectivity to higher alcohols gradually increased during the first 10 h TOS indicating enhanced Cu-Co surface alloy formation considered as active sites for HAS. In contrast, with high Na loadings (≥0.8 wt%) deactivation did not occur and stable performance with constant CO conversion and product distribution was observed indicating significantly altered structural properties. High Na loadings caused the stabilizing amorphous oxide matrix to collapse resulting in strong sintering of the metallic Cu particles, and an increased carbidization of metallic Co0 forming bulk Co2C was observed by X-ray diffraction. Close contact between metallic Co0 and Co2C, which is known to facilitate molecular CO adsorption, is assumed to generate additional active sites for HAS. © 2016 Elsevier Inc. All rights reserved.
  	view abstract	doi: 10.1016/j.jcat.2015.12.016

• 2016 • 150	Thermodynamic stability and control of oxygen reactivity at functional oxide interfaces: EuO on ITO Gerber, T. and Lömker, P. and Zijlstra, B. and Besson, C. and Mueller, D.N. and Zander, W. and Schubert, J. and Gorgoi, M. and Müller, M. Journal of Materials Chemistry C 4 1813-1820 (2016) As a prototypical all-oxide heterostructure, the ferromagnetic insulator europium monoxide (EuO) is synthesized on transparent and conductive indium tin oxide (ITO) virtual substrates. Non-destructive hard X-ray photoelectron spectroscopy is employed to depth profile the chemical composition of the magnetic layer and the buried oxide-oxide interface. We find that thermally activated oxygen diffusion from ITO affects the EuO growth process. We present how to control the oxygen reactivity at the interface and discuss its origin in a thermodynamic analysis. Our complementary methodical strategy allows for a significant improvement of the EuO chemical quality with sizeable magnetic properties. Generally, our approach derives guidelines for the proper choice of oxide substrates and buffer layer materials for functional all-oxide heterostructures. © The Royal Society of Chemistry 2016.
  	view abstract	doi: 10.1039/c6tc00170j

• 2015 • 149	Adsorption phenomena of cubane-type tetranuclear Ni(II) complexes with neutral, thioether-functionalized ligands on Au(111) Heß, V. and Matthes, F. and Bürgler, D.E. and Monakhov, K.Y. and Besson, C. and Kögerler, P. and Ghisolfi, A. and Braunstein, P. and Schneider, C.M. Surface Science 641 210-215 (2015) Abstract The controlled and intact deposition of molecules with specific properties onto surfaces is an emergent field impacting a wide range of applications including catalysis, molecular electronics, and quantum information processing. One strategy is to introduce grafting groups functionalized to anchor to a specific surface. While thiols and disulfides have proven to be quite effective in combination with gold surfaces, other S-containing groups have received much less attention. Here, we investigate the surface anchoring and organizing capabilities of novel charge-neutral heterocyclic thioether groups as ligands of polynuclear nickel(II) complexes. We report on the deposition of a cubane-type {Ni<inf>4</inf>} (= [Ni(μ<inf>3</inf>-Cl)Cl(HL·S)]<inf>4</inf>) single-molecule magnet from dichloromethane solution on a Au(111) surface, investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction, both immediately after deposition and after subsequent post-annealing. The results provide strong evidence for partial decomposition of the coordination complex upon deposition on the Au(111) surface that, however, leaves the magnetic {Ni<inf>4</inf>Cl<inf>4n</inf>} (n = 1 or 2) core intact. Only post-annealing above 480 K induces further decomposition and fragmentation of the {Ni<inf>4</inf>Cl<inf>4n</inf>} core. The detailed insight into the chemisorption-induced decomposition pathway not only provides guidelines for the deposition of thioether-functionalized Ni(II) complexes on metallic surfaces but also reveals opportunities to use multidentate organic ligands decorated with thioether groups as transporters for highly unstable inorganic structures onto conducting surfaces, where they are stabilized retaining appealing electronic and magnetic properties. © 2015 Elsevier B.V.
  	view abstract	doi: 10.1016/j.susc.2015.06.026

• 2015 • 148	Carbon Monoxide-Induced Stability and Atomic Segregation Phenomena in Shape-Selected Octahedral PtNi Nanoparticles Ahmadi, M. and Cui, C. and Mistry, H. and Strasser, P. and Roldan Cuenya, B. ACS Nano 9 10686-10694 (2015) The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed. © 2015 American Chemical Society.
  	view abstract	doi: 10.1021/acsnano.5b01807

• 2015 • 147	CO oxidation as a test reaction for strong metal-support interaction in nanostructured Pd/FeOx powder catalysts Kast, P. and Friedrich, M. and Teschner, D. and Girgsdies, F. and Lunkenbein, T. and D'Alnoncourt, R.N. and Behrens, M. and Schlögl, R. Applied Catalysis A: General 502 8-17 (2015) A series of differently loaded palladium-iron catalysts was prepared by a controlled co-precipitation method of the nitrate precursors, in order to ensure homogeneous Pd particle size-distribution. After characterization of the pre-catalysts by various techniques, different controlled reduction conditions were applied to investigate the interactions within the Pd-iron system, containing reversible and irreversible processes like phase transformations, SMSI, sintering and alloying. Strong indications for the reversible surface decoration of the Pd nanoparticles with iron oxide species via strong metal-support interaction were found by the combined results of DRIFTS, CO-chemisorption, TEM and XPS measurements. This SMSI state was found to be unstable. It was observed independent of bulk phase or palladium particle size. Catalytic CO-oxidation was found to be a suitable test reaction for the study of the phenomenon: higher activity as well as oxidative deactivation of the SMSI state was observed by investigating the light-off behavior in repeated, temperature-programmed cycles as well as by isothermal measurements. The instability was found to be higher in case of higher Pd dispersion. In addition, bulk properties of the Pd-Fe system, like alloying, were investigated by detailed XRD measurements. © 2015 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.apcata.2015.04.010

• 2015 • 146	Formation and Movement of Cationic Defects during Forming and Resistive Switching in SrTiO3 Thin Film Devices Lenser, C. and Koehl, A. and Slipukhina, I. and Du, H. and Patt, M. and Feyer, V. and Schneider, C.M. and Lezaic, M. and Waser, R. and Dittmann, R. Advanced Functional Materials 25 6360-6368 (2015) The resistance switching phenomenon in many transition metal oxides is described by ion motion leading to the formation of oxygen-deficient, highly electron-doped filaments. In this paper, the interface and subinterface region of electroformed and switched metal-insulator-metal structures fabricated from a thin Fe-doped SrTiO3 (STO) film on n-conducting Nb-doped SrTiO3 crystals are investigated by photoemission electron microscopy, transmission electron microscopy, and hard X-ray photoelectron spectroscopy in order to gain a deeper understanding of cation movement in this specific system. During electroforming, the segregation of Sr to the top interface and the generation of defect-rich cones in the film are observed, apparently growing from the anode toward the cathode during electroforming. An unusual binding energy component of the Sr 3d emission line is observed which can be assigned to Sr Ti-VO∗ defect complexes by performing ab initio calculations. Since this Sr component can be reversibly affected by an external electrical bias, the movement of both oxygen and Sr point defects and the formation of defect complexes Sr Ti-VO∗ during resistive switching are suggested. These findings are discussed with regard to the point defect structure of the film and the local oxidation of the donor-doped substrate. In particular, the apparent dichotomy between the observation of acceptor-type defects and increased electronic conductivity in STO is addressed. A low binding energy component of the Sr 3d photoemission line is observed in Fe-doped SrTiO3 memristive devices and assigned to Sr′Ti-V∗O defect complexes by ab initio calculations. Since this Sr component can be reversibly affected by an electrical bias, the movement of both oxygen and Sr vacancies and the formation of Sr′Ti-V∗O defect complexes during resistive switching are suggested. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/adfm.201500851

• 2015 • 145	High-quality functionalized few-layer graphene: Facile fabrication and doping with nitrogen as a metal-free catalyst for the oxygen reduction reaction Sun, Z. and Masa, J. and Weide, P. and Fairclough, S.M. and Robertson, A.W. and Ebbinghaus, P. and Warner, J.H. and Tsang, S.C.E. and Muhler, M. and Schuhmann, W. Journal of Materials Chemistry A 3 15444-15450 (2015) Functionalization of graphene is fundamental to facilitating its processing and offers a wide scope for advanced applications. Here we demonstrate a facile, highly efficient and mild covalent functionalization of graphene using HNO<inf>3</inf> vapour. This results in functionalized few-layer graphene (FLG) that is high in both quantity and quality. We fully characterized the structure and defect level of functionalized FLG by X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The results from this analysis show the tunability of the surface oxygen functionalities of FLG achieved through controlling the oxidation temperature without affecting the major intrinsic properties of graphene. This allows for further doping for applications, for example with nitrogen as a metal-free catalyst in the oxygen reduction reaction. © 2015 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c5ta02248g

• 2015 • 144	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 abstract	doi: 10.1021/acs.jpcc.5b02932

• 2015 • 143	Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces Galbiati, M. and Tatay, S. and Delprat, S. and Barraud, C. and Cros, V. and Jacquet, E. and Coloma, F. and Choueikani, F. and Otero, E. and Ohresser, P. and Haag, N. and Cinchetti, M. and Aeschlimann, M. and Seneor, P. and Mattana... 353 24-28 (2015) Self-Assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La<inf>2/3</inf>Sr<inf>1/3</inf>MnO<inf>3</inf> (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes. © 2015 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.apsusc.2015.06.051

• 2015 • 142	Interface engineering and characterization at the atomic-scale of pure and mixed ion layer gas reaction buffer layers in chalcopyrite thin-film solar cells Cojocaru-Mirédin, O. and Fu, Y. and Kostka, A. and Sáez-Araoz, R. and Beyer, A. and Knaub, N. and Volz, K. and Fischer, C.-H. and Raabe, D. Progress in Photovoltaics: Research and Applications 23 705-716 (2015) In this work, we investigate the p-n junction region for two different buffer/Cu(In,Ga)(Se,S)<inf>2</inf> (CIGSSe) samples having different conversion efficiencies (the cell with pure In<inf>2</inf>S<inf>3</inf> buffer shows a lower efficiency than the nano-ZnS/In<inf>2</inf>S<inf>3</inf> buffered one). To explain the better efficiency of the sample with nano-ZnS/In<inf>2</inf>S<inf>3</inf> buffer layer, combined transmission electron microscopy, atom probe tomography, and X-ray photoelectron spectroscopy studies were performed. In the pure In<inf>2</inf>S<inf>3</inf> buffered sample, a CuIn<inf>3</inf>Se<inf>5</inf> ordered-defect compound is observed at the CIGSSe surface, whereas in the nano-ZnS/In<inf>2</inf>S<inf>3</inf> buffered sample no such compound is detected. The absence of an ordered-defect compound in the latter sample is explained either by the presence of the ZnS nanodots, which may act as a barrier layer against Cu diffusion in CIGSSe hindering the formation of CuIn<inf>3</inf>Se<inf>5</inf>, or by the presence of Zn at the CIGSSe surface, which may disturb the formation of this ordered-defect compound. In the nano-ZnS/In<inf>2</inf>S<inf>3</inf> sample, Zn was found in the first monolayers of the absorber layer, which may lead to a downward band bending at the surface. This configuration is very stable (Fermi level pinning at the conduction band, as observed for Cd in Cu(In,Ga)Se<inf>2</inf>) and reduces the recombination rate at the interface. This effect may explain why the sample with ZnS nanodots possesses a higher efficiency. This work demonstrates the capability of correlative transmission electron microscopy, atom probe tomography, and X-ray photoelectron spectroscopy studies in investigating buried interfaces. The study provides essential information for understanding and modeling the p-n junction at the nanoscale in CIGSSe solar cells. Copyright © 2014 John Wiley & Sons, Ltd.
  	view abstract	doi: 10.1002/pip.2484

• 2015 • 141	Interface engineering and nanoscale characterization of Zn(S,O) alternative buffer layer for CIGS thin film solar cells Soni, P. and Cojocaru-Miredin, O. and Raabe, D. 2015 IEEE 42nd Photovoltaic Specialist Conference, PVSC 2015 (2015) The buffer layers in Cu(In,Ga)Se2 solar cells play a crucial role in device performance, although their thickness is only a few tens of nanometers. Moreover, often Zn(S,O) alternative buffer layers have been studied in view of their structure, band alignment, and optical properties, but not much work exists on their nanoscale chemical properties. This work focuses on the chemical characterization of Zn(S,O) using x-ray photoelectron spectroscopy for determination of the Zn(S,O) and Cu(In,Ga)Se2 depth composition, and atom probe tomography for probing the nano-scale chemical fluctuations at the Zn(S,O)/Cu(In,Ga)Se2 interface. The Zn(O,S) buffer layer was deposited by RF magnetron sputtering. The aim is to study the nanoscale concentration changes and atomic interdiffusion between CIGS and Zn(S,O) after sputter deposition at room temperature and after post-deposition heat treatment at 200°C. © 2015 IEEE.
  	view abstract	doi: 10.1109/PVSC.2015.7355889

• 2015 • 140	Iron-doped nickel oxide nanocrystals as highly efficient electrocatalysts for alkaline water splitting Fominykh, K. and Chernev, P. and Zaharieva, I. and Sicklinger, J. and Stefanic, G. and Döblinger, M. and Müller, A. and Pokharel, A. and Böcklein, S. and Scheu, C. and Bein, T. and Fattakhova-Rohlfing, D. ACS Nano 9 5180-5188 (2015) Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible Fe<inf>x</inf>Ni<inf>1-x</inf>O nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe<inf>0.1</inf>Ni<inf>0.9</inf>O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s-1 at the overpotential of 300 mV. The current density of 10 mA cm-2 is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec-1. The extremely high catalytic activity, facile preparation, and low cost of the single crystalline Fe<inf>x</inf>Ni<inf>1-x</inf>O nanoparticles make them very promising catalysts for the oxygen evolution reaction. © 2015 American Chemical Society.
  	view abstract	doi: 10.1021/acsnano.5b00520

• 2015 • 139	MOCVD of TiO2 thin films from a modified titanium alkoxide precursor Kim, S.J. and Dang, V.-S. and Xu, K. and Barreca, D. and Maccato, C. and Carraro, G. and Bhakta, R.K. and Winter, M. and Becker, H.-W. and Rogalla, D. and Sada, C. and Fischer, R.A. and Devi, A. Physica Status Solidi (A) Applications and Materials Science 212 1563-1570 (2015) A new titanium precursor, [Ti(OPri)<inf>2</inf>(deacam)<inf>2</inf>] (deacam = N,N-diethylacetoacetamide), was developed by the reaction of the parent Ti alkoxide with the β-ketoamide. The compound, obtained as a monomeric six-coordinated complex, was used in metal organic chemical vapor deposition (MOCVD) of TiO<inf>2</inf> both as a single source precursor (SSP) and in the presence of oxygen. The high thermal stability of [Ti(OPri)<inf>2</inf>(deacam)<inf>2</inf>] enabled the fabrication of TiO<inf>2</inf> films over a wide temperature range, with steady growth rates between 500 and 800 °C. The microstructure of the obtained systems was analyzed by X-ray diffraction (XRD) and Raman spectroscopy, whereas atomic force microscopy (AFM) and field emission-scanning electron microscopy (FE-SEM) measurements were performed to investigate the surface morphology and nanoorganization. Film composition was investigated by complementary techniques like Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA), X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectrometry (SIMS). The electrical properties of the layers were investigated by performing capacitance voltage (C-V) and leakage current measurements. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
  	view abstract	doi: 10.1002/pssa.201532271

• 2015 • 138	Nitrogen uptake of nickel free austenitic stainless steel powder during heat treatment-an XPS study Weddeling, A. and Lefor, K. and Hryha, E. and Huth, S. and Nyborg, L. and Weber, S. and Theisen, W. Surface and Interface Analysis 47 413-422 (2015) In austenitic stainless steel nitrogen stabilizes the austenitic phase improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn-prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X-ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide-free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.
  	view abstract	doi: 10.1002/sia.5730

• 2015 • 137	Photothermally induced bromination of carbon/polymer bipolar plate materials for fuel cell applications Schade, M. and Franzka, S. and Cappuccio, F. and Peinecke, V. and Heinzel, A. and Hartmann, N. Applied Surface Science 336 85-88 (2015) A facile photothermal procedure for direct functionalization of carbon/polymer bipolar plate materials is demonstrated. Through irradiation with a microfocused beam of an Ar+-laser at λ = 514 nm in gaseous bromine and distinct laser powers and pulse lengths local bromination of the carbon/polymer material takes place. At a 1/e spot diameter of 2.1 μm, functionalized surface areas with diameters down to 5 μm are fabricated. In complementary experiments large-area bromination is investigated using an ordinary tungsten lamp. For characterization contact angle goniometry, X-ray photoelectron spectroscopy and electron microscopy in conjunction with labeling techniques are employed. After irradiation bromine groups can easily be substituted by other chemical functionalities, e.g. azide and amine groups. This provides a facile approach in order to fabricate surface patterns and gradient structures with varying wetting characteristics. Mechanistic aspects and prospects of photothermal routines in micropatterning of carbon/polymer materials are discussed. © 2014 Published by Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2014.09.161

• 2015 • 136	Propanoate grafting on (H,OH)-Si(0 0 1)-2×1 Bournel, F. and Gallet, J.-J. and Köhler, U. and Ellakhmissi, B.B. and Kubsky, S. and Carniato, S. and Rochet, F. Journal of Physics Condensed Matter 27 (2015) We have examined the reactivity of water-covered Si(0 0 1)-2?×1, (H,OH)-Si(0 0 1)-2?×1, with propanoic (C2H5COOH) acid at room temperature. Using a combination of spectroscopic techniques probing the electronic structure (XPS, NEXAFS) and the vibrational spectrum (HREELS), we have proved that the acid is chemisorbed on the surface as a propanoate. Once the molecule is chemisorbed, the strong perturbation of the electronic structure of the hydroxyls, and of their vibrational spectrum, suggests that the molecule makes hydrogen bonds with the surrounding hydroxyls. As we find evidence that surface hydroxyls are involved in the adsorption reaction, we discuss how a concerted or a radical-mediated reaction (involving the surface silicon dangling bonds) could lead to water elimination and formation of the ester. © 2015 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0953-8984/27/5/054005

• 2015 • 135	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 abstract	doi: 10.1016/j.apsusc.2015.01.108

• 2015 • 134	Spin-resolved low-energy and hard x-ray photoelectron spectroscopy of off-stoichiometric Co2MnSi Heusler thin films exhibiting a record TMR Fetzer, R. and Ouardi, S. and Honda, Y. and Liu, H.-X. and Chadov, S. and Balke, B. and Ueda, S. and Suzuki, M. and Uemura, T. and Yamamoto, M. and Aeschlimann, M. and Cinchetti, M. and Fecher, G.H. and Felser, C. 48 (2015) Half-metallic Co<inf>2</inf>MnSi-based Heusler compounds have attracted attention because they yield very high tunnelling magnetoresistance (TMR) ratios. Record TMR ratios of 1995% (at 4.2 K) are obtained from off-stoichiometric Co<inf>2</inf>MnSi-based magnetic tunnel junctions. This work reports on a combination of band structure calculations and spin-resolved and photon-polarisation-dependent photoelectron spectroscopy for off-stoichiometric Heusler thin films with the composition Co<inf>2</inf>Mn<inf>1.30</inf>Si<inf>0.84</inf>. Co and Mn are probed by magnetic dichroism in angle-resolved photoelectron spectroscopy at the 2p core level. In contrast to the delocalised Co 3d states, a pronounced localisation of the Mn 3d states is deduced from the corresponding 2p core level spectra. The valence states are investigated by linear dichroism using both hard x-ray and very-low-photon-energy excitation. When a very low photon energy is used for excitation, the valence bands exhibit a spin polarisation of about 30% at the Fermi energy. First principles calculations reveal that the low spin polarisation might be caused by a spin-flip process in the photoelectron final states. © 2015 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0022-3727/48/16/164002

• 2015 • 133	Van der Waals epitaxial MOCVD-growth of (BixSb1-x)2Te3 (0 < x < 1) films Bendt, G. and Sonntag, J. and Lorke, A. and Assenmacher, W. and Hagemann, U. and Schulz, S. Semiconductor Science and Technology 30 (2015) Epitaxial (Bi<inf>x</inf>Sb<inf>1-x</inf>)<inf>2</inf>Te<inf>3</inf> films with (0 < x < 1) were grown by the metal-organic chemical vapour deposition (MOCVD) process at 400 °C using the tailor-made precursors Et<inf>2</inf>Te<inf>2</inf>, i-Pr<inf>3</inf>Sb and Et<inf>3</inf>Bi. The films grown on Al<inf>2</inf>O<inf>3</inf>(0001) substrates show a very smooth surface morphology as shown by a scanning electron microscope (SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM), while those grown on Si(100) are rather polycrystalline. The chemical composition of the crystalline films (x-ray powder diffraction (XRD)) was investigated by energy-dispersive x-ray (EDX) and x-ray photoelectron spectroscopy (XPS), and the in-plane transport properties were measured, and a strong dependency from the bismuth content was found, which allows the tuning of the carrier concentration and mobility in a wide range. © 2015 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0268-1242/30/8/085021

• 2015 • 132	X-ray photoelectron spectroscopy investigations of the surface reaction layer and its effects on the transformation properties of nanoscale Ti51Ni38Cu11 shape memory thin films König, D. and Naujoks, D. and De Los Arcos, T. and Grosse-Kreul, S. and Ludwig, Al. Advanced Engineering Materials 17 669-673 (2015) The depth-dependent chemical constitution of Ti<inf>51</inf>Ni<inf>38</inf>Cu<inf>11</inf> thin films of different total film thickness from 400 to 50-nm was characterized using X-ray photoelectron spectroscopy (XPS). It was analyzed how reaction layers, which form on the surface of the film significantly change the chemical composition of the transforming phase, which leads in turn to altered phase transformation properties. For thinner films, the deviation from the nominal chemical composition increases. For a film thickness of 50-nm, a Ti loss of ≈9-at% is observed. The Ni content is increased by ≈5-at%, whereas the Cu content stays relatively constant for films of different thickness. The results are summarized in a layer model, which supports designing nanoscale shape memory thin films. Ti<inf>51</inf>Ni<inf>38</inf>Cu<inf>11</inf> thin films of different film thickness are investigated regarding the influence of the reaction layers on the chemical composition of the transforming phase and the corresponding functional properties. A model is proposed describing the different reaction layers on the surface of the thin film and at the substrate/thin film interface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/adem.201400317

• 2015 • 131	[001] Preferentially-oriented 2D tungsten disulfide nanosheets as anode materials for superior lithium storage Yang, W. and Wang, J. and Si, C. and Peng, Z. and Frenzel, J. and Eggeler, G. and Zhang, Z. Journal of Materials Chemistry A 3 17811-17819 (2015) Rechargeable lithium ion batteries (LIBs) have transformed portable electronics and will play a crucial role in transportation, such as electric vehicles. For higher energy storage in LIBs, two issues should be addressed, that is, the fundamental understanding of the chemistry taking place in LIBs and the discovery of new materials. Here we design and fabricate two-dimensional (2D) WS<inf>2</inf> nanosheets with preferential [001] orientation and perfect single crystalline structures. Being used as an anode for LIBs, the WS<inf>2</inf>-nanosheet electrode exhibits a high specific capacity, good cycling performance and excellent rate capability. Considering the controversy in the lithium storage mechanism of WS<inf>2</inf>, ex-situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) analyses clearly verify that the recharge product (3.0 V vs. Li+/Li) of the WS<inf>2</inf> electrode after fully discharging to 0.01 V (vs. Li+/Li) tends to reverse to WS<inf>2</inf>. More remarkably, the [001] preferentially-oriented 2D WS<inf>2</inf> nanosheets are also promising candidates for applications in photocatalysis, water splitting, and so forth. © The Royal Society of Chemistry 2015.
  	view abstract	doi: 10.1039/c5ta04176g

• 2014 • 130	A carbon-coated TiO2(B) nanosheet composite for lithium ion batteries Sun, Z. and Huang, X. and Muhler, M. and Schuhmann, W. and Ventosa, E. Chemical Communications 50 5506-5509 (2014) The carbon-coated TiO2(B) nanosheet composite synthesized by one-step hydrolysis of TiCl3 followed by vacuum annealing and air annealing delivers outstanding electrochemical performance as a negative electrode for Li-ion batteries, i.e. reversible capacity above 150 mA h g -1 at 30 C (10 A g-1). This journal is © the Partner Organisations 2014.
  	view abstract	doi: 10.1039/c4cc01888e

• 2014 • 129	Adsorption and reactivity of nitrogen atoms on silica surface under plasma exposure Marinov, D. and Guaitella, O. and de los Arcos, T. and von Keudell, A. and Rousseau, A. Journal of Physics D-applied Physics 47 475204 (2014) The kinetics of adsorption, desorption and recombination of nitrogen atoms on a silica surface is investigated. Stable nitrogen atoms are grafted to the inner surface of a fused silica discharge tube by a discharge in N-2 at 0.53 mbar. After the pre-treatment, the surface is analysed using x-ray photoelectron spectroscopy and an isotopic exchange technique. The latter consists of the exposure of the pre-treated surface with a discharge in the heavy nitrogen isotope N-30(2). Nitrogen isotopologues N-29(2) and N-28(2) produced on the surface are detected using a mass spectrometer and provide information about the coverage and reactivity of adsorbed N-14 atoms. It is found that during the pre-treatment, a silicon oxynitride (SiOxNy) layer is formed on the initially clean SiO2 surface. The coverage of N on the surface increases from 5 x 10(13) to 5 x 10(15) cm(-2) for a pre-treatment duration in the range of 10(-2) - 10(4) s. Atoms on the surface demonstrate a distribution of reactivity, which is attributed to a distribution of their binding energies and configurations on the surface. We demonstrate that stable chemisorbed N-ads are not the main recombination sites for N atoms on the surface contrary to previous studies. We conclude that recombination takes place mainly on weakly bonding active sites with the binding energy smaller than 1 eV.
  	view abstract	doi: 10.1088/0022-3727/47/47/475204

• 2014 • 128	Amine-based solvents for exfoliating graphite to graphene outperform the dispersing capacity of N-methyl-pyrrolidone and surfactants Sun, Z. and Huang, X. and Liu, F. and Yang, X. and Rösler, C. and Fischer, R.A. and Muhler, M. and Schuhmann, W. Chemical Communications 50 10382-10385 (2014) Four organic amine-based solvents were discovered which enable direct exfoliation of graphite to produce high-quality and oxygen-free graphene nanosheets. These solvents outperform previously used solvents and additives such as N-methyl-pyrrolidone and surfactants in terms of their dispersing capacity. The resulting dispersions allow the facile fabrication of zeolitic imidazolate framework (ZIF)-graphene nanocomposites with remarkable CO 2 storage capability. This journal is © the Partner Organisations 2014.
  	view abstract	doi: 10.1039/c4cc03923h

• 2014 • 127	Atomic layer deposition of TiO2 and ZrO2 thin films using heteroleptic guanidinate precursors Kaipio, M. and Blanquart, T. and Banerjee, M. and Xu, K. and Niinistö, J. and Longo, V. and Mizohata, K. and Devi, A. and Ritala, M. and Leskelä, M. Chemical Vapor Deposition 20 209-216 (2014) In this study the atomic layer deposition (ALD) of TiO2 and ZrO2 using two heteroleptic amido-guanidinate precursors, [Ti(NEtMe)3(guan-NEtMe)] and [Zr(NEtMe)3(guan-NEtMe)], together with water or ozone as oxygen sources, are investigated. All processes exhibit self-limiting growth at a deposition temperature of 275°C. The zirconium precursor especially gives high growth rates (0.8/1.0Å per cycle with H2O/O3). The films are also relatively smooth, as determined by atomic force microscopy (AFM). The composition of the films is examined using X-ray photoelectron spectroscopy (XPS) and time of flight elastic recoil detection analysis (TOF-ERDA). When using ozone as the oxygen source the films present very high purity. The results are compared and discussed with respect to earlier studies on guanidinate, as well as homoleptic amido precursors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201407115

• 2014 • 126	Bulk sensitive hard x-ray photoemission electron microscopy Patt, M. and Wiemann, C. and Weber, N. and Escher, M. and Gloskovskii, A. and Drube, W. and Merkel, M. and Schneider, C.M. Review of Scientific Instruments 85 (2014) Hard x-ray photoelectron spectroscopy (HAXPES) has now matured into a well-established technique as a bulk sensitive probe of the electronic structure due to the larger escape depth of the highly energetic electrons. In order to enable HAXPES studies with high lateral resolution, we have set up a dedicated energy-filtered hard x-ray photoemission electron microscope (HAXPEEM) working with electron kinetic energies up to 10 keV. It is based on the NanoESCA design and also preserves the performance of the instrument in the low and medium energy range. In this way, spectromicroscopy can be performed from threshold to hard x-ray photoemission. The high potential of the HAXPEEM approach for the investigation of buried layers and structures has been shown already on a layered and structured SrTiO3 sample. Here, we present results of experiments with test structures to elaborate the imaging and spectroscopic performance of the instrument and show the capabilities of the method to image bulk properties. Additionally, we introduce a method to determine the effective attenuation length of photoelectrons in a direct photoemission experiment. © 2014 AIP Publishing LLC.
  	view abstract	doi: 10.1063/1.4902141

• 2014 • 125	Combined In Situ XPS and UHV- Chemical Force Microscopy ( CFM) Studies of the Plasma Induced Surface Oxidation of Polypropylene Ozkaya, B. and Grosse-Kreul, S. and Corbella, C. and von Keudell, A. and Grundmeier, G. Plasma Processes and Polymers 11 256--262 (2014) Modification of the surface chemistry and correlated adhesive properties of polypropylene (PP) by means of an electron cyclotron resonance (ECR) oxygen plasma source is studied based on an in situ ultra-high-vacuum (UHV)-analytical approach. To determine the plasma induced chemical changes without exposure to atmosphere, X-ray excited valence band (VB) spectroscopy and core level X-ray photoelectron spectroscopy (XPS) are performed. Adhesive properties are characterized by means of UHV chemical force microscopy (UHV-CFM). Correlation of XPS and UHV-CFM data indicate that interactions between a SiO2-tip and the modified PP surface is dominated by hydrogen bonds between surface silanol groups on the tip and induced oxidized species on PP surface. Such interactions are maximized in the initial phase of surface oxidation.
  	view abstract	doi: 10.1002/ppap.201300105

• 2014 • 124	Effect of ternary element addition on the corrosion behaviour of NiTi shape memory alloys Kassab, E. and Neelakantan, L. and Frotscher, M. and Swaminathan, S. and Maaß, B. and Rohwerder, M. and Gomes, J. and Eggeler, G. Materials and Corrosion 65 18-22 (2014) The goal of this study is to compare the corrosion behaviour of selected ternary nickel titanium (NiTi)-based alloys (Ni45Ti 50Cu5, Ni47Ti50Fe3 and Ni39Ti50Pd11) with a binary, pseudoelastic Ni50.7Ti49.3 alloy. We examine the influence of the ternary elements on the corrosion behaviour using standard electrochemical techniques. All measurements were done in a physiological solution (0.9% NaCl) simulating a body temperature of 37 ± 1 °C. The influence of Cu and Pd addition on the surface oxide film was characterised by X-ray photoelectron spectroscopy (XPS). The results revealed that, the localised corrosion resistance of these ternary alloys is lower than the binary NiTi alloy. By comparing the different NiTi-based alloys, the following relation has been proposed for their localised corrosion resistances: NiTiCu < NiTiFe < NiTiPd < NiTi. Depth profiling by XPS showed that the surface oxide film on all the investigated NiTi-based alloys is mainly of TiO2, however, the NiTiPd and NiTiCu alloys showed metallic ternary element distributed within TiO2 layer. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/maco.201206587

• 2014 • 123	High-concentration graphene dispersions with minimal stabilizer: a scaffold for enzyme immobilization for glucose oxidation Sun, Z. and Vivekananthan, J. and Guschin, D.A. and Huang, X. and Kuznetsov, V. and Ebbinghaus, P. and Sarfraz, A. and Muhler, M. and Schuhmann, W. Chemistry (Weinheim an der Bergstrasse, Germany) 20 5752-5761 (2014) Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre-exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL(-1) by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene-to-stabilizer ratio. Characterization by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/chem.201400098

• 2014 • 122	Immobilization of proteins in their physiological active state at functionalized thiol monolayers on ATR-germanium crystals Schartner, J. and Gavriljuk, K. and Nabers, A. and Weide, P. and Muhler, M. and Gerwert, K. and Kötting, C. ChemBioChem 15 2529-2534 (2014) Protein immobilization on solid surfaces has become a powerful tool for the investigation of protein function. Physiologically relevant molecular reaction mechanisms and interactions of proteins can be revealed with excellent signal-to-noise ratio by vibrational spectroscopy (ATR-FTIR) on germanium crystals. Protein immobilization by thiol chemistry is well-established on gold surfaces, for example, for surface plasmon resonance. Here, we combine features of both approaches: a germanium surface functionalized with different thiols to allow specific immobilization of various histidine-tagged proteins with over 99% specific binding. In addition to FTIR, the surfaces were characterized by XPS and fluorescence microscopy. Secondary-structure analysis and stimulus-induced difference spectroscopy confirmed protein activity at the atomic level, for example, physiological cation channel formation of Channelrhodopsin 2. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cbic.201402478

• 2014 • 121	Influence of the PM-Processing Route and Nitrogen Content on the Properties of Ni-Free Austenitic Stainless Steel Lefor, K. and Walter, M. and Weddeling, A. and Hryha, E. and Huth, S. and Weber, S. and Nyborg, L. and Theisen, W. Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 46 1154-1167 (2014) Ni-free austenitic steels alloyed with Cr and Mn are an alternative to conventional Ni-containing steels. Nitrogen alloying of these steel grades is beneficial for several reasons such as increased strength and corrosion resistance. Low solubility in liquid and δ-ferrite restricts the maximal N-content that can be achieved via conventional metallurgy. Higher contents can be alloyed by powder-metallurgical (PM) production via gas–solid interaction. The performance of sintered parts is determined by appropriate sintering parameters. Three major PM-processing routes, hot isostatic pressing, supersolidus liquid phase sintering (SLPS), and solid-state sintering, were performed to study the influence of PM-processing route and N-content on densification, fracture, and mechanical properties. Sintering routes are designed with the assistance of thermodynamic calculations, differential thermal analysis, and residual gas analysis. Fracture surfaces were studied by X-ray photoelectron spectroscopy, secondary electron microscopy, and energy dispersive X-ray spectroscopy. Tensile tests and X-ray diffraction were performed to study mechanical properties and austenite stability. This study demonstrates that SLPS process reaches high densification of the high-Mn-containing powder material while the desired N-contents were successfully alloyed via gas–solid interaction. Produced specimens show tensile strengths >1000 MPa combined with strain to fracture of 60 pct and thus overcome the other tested production routes as well as conventional stainless austenitic or martensitic grades. © 2014, The Author(s).
  	view abstract	doi: 10.1007/s11661-014-2701-7

• 2014 • 120	Interface reactions of Ag@TiO2 nanocomposite films Zuo, J. and Rao, J. and Eggeler, G. Materials Chemistry and Physics 145 90-98 (2014) TiO2 films were sputtered on 100-nm-thick Ag layers at various O2 partial pressures to study forming processes at the interface. The interfacial reactions during the deposition process were investigated by means of transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and UV-vis reflection spectra. The sputtering process led to formation of Ag nanoparticles surrounded by Ag 2O and TiO2 in the TiO2 film matrix as well as on the surface. The presence of oxygen in the plasma resulted in enrichment of silver oxides on the surface and an intermixing of Ag in the TiO2 matrix. The film structures could be explained based on the interplay among the formation of silver oxide, the nucleation and growth of TiO2, as well as the mobility of silver and silver oxides within the growing TiO2 films. © 2014 Elsevier B.V.
  	view abstract	doi: 10.1016/j.matchemphys.2014.01.041

• 2014 • 119	Large-scale synthesis and catalytic activity of nanoporous Cu-O system towards CO oxidation Kou, T. and Si, C. and Gao, Y. and Frenzel, J. and Wang, H. and Yan, X. and Bai, Q. and Eggeler, G. and Zhang, Z. RSC Advances 4 65004-65011 (2014) Nanoporous Cu-O system catalysts with different oxidation states of Cu have been fabricated through a combination of dealloying as-milled Al66.7Cu33.3 alloy powders and subsequent thermal annealing. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the microstructure and surface chemical states of Cu-O catalysts. The peculiar nanoporous structure can be retained in Cu-O catalysts after thermal treatment. Catalytic experiments reveal that all the Cu-O samples exhibit complete CO conversion below 170 °C. The optimal catalytic performance could be achieved through the combination of annealing in air with hydrogen treatment for the Cu-O catalyst, which shows a near complete conversion temperature (T90%) of 132 °C and an activation energy of 91.3 KJ mol-1. In addition, the present strategy (ball milling, dealloying and subsequent thermal treatment) could be scaled up to fabricate high-performance Cu-O catalysts towards CO oxidation. This journal is © The Royal Society of Chemistry 2014.
  	view abstract	doi: 10.1039/c4ra12227e

• 2014 • 118	Nanostructured Er2O3 thin films grown by metalorganic chemical vapour deposition Xu, K. and Dang, V.-S. and Ney, A. and De Los Arcos, T. and Devi, A. Journal of Nanoscience and Nanotechnology 14 5095-5102 (2014) Metalorganic chemical vapor deposition (MOCVD) of nanostructured Er 2O3 thin films was performed using the Er-tris-guanidinate precursor [Er(DPDMG)3] (DPDMG = diisopropyl-2- dimethylamidoguanidinato) as the Er source and oxygen. Film deposition was carried out on Si(100) and quartz glass substrates and the process parameters namely temperature, pressure and oxygen flow rate were varied. The resulting thin films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) for investigating the crystallinity and morphology, respectively. The chemical composition of the film was investigated by X-ray photoelectron spectroscopy (XPS) measurements. Transmittance and absorption spectra of the 600 °C film grown on glass substrates were performed by UV-vis measurements revealing more than 80% transmittance. The potential of Er2O3 thin films as gate dielectrics was verified by carrying out capacitance-voltage (C-V ) and current-voltage (I-V ) measurements. Dielectric constants estimated from the accumulation capacitance were found to be in the range of 10-12 in AC frequencies of 1 MHz down to 10 kHz and the leakage current of the order of 2×10-8 A/cm2 at the applied field of 1 MV cm-1 was measured for films deposited under optimised process conditions. The low leakage current and high dielectric constant implies good quality of the Er2O3 layers relevant for high-k applications. These layers were found to be paramagnetic with a slightly reduced magnetic moment of the Er3+ ions. Copyright © 2014 American Scientific Publishers All rights reserved.
  	view abstract	doi: 10.1166/jnn.2014.8848

• 2014 • 117	New insights into SEI formation in lithium ion batteries: Inhomogeneous distribution of irreversible charge losses across graphite electrodes Klink, S. and Weide, P. and Ventosa, E. and Muhler, M. and Schuhmann, W. and La Mantia, F. ECS Transactions 62 265-271 (2014) A vertical split electrode (VSE) with three layers was developed to investigate the formation of the solid electrolyte interphase (SEI) during first charge of graphite electrodes in lithium ion batteries. Ex-situ X-ray photoelectron spectroscopy (XPS) on each layer revealed that the first layer showed distinctively different signal patterns in the O 1s and C 1s regions. It was concluded that the SEI formed in the first layer closest to the counter electrode is thicker as well as different in chemical nature as compared to the SEI in the electrode bulk. © The Electrochemical Society.
  	view abstract	doi: 10.1149/06201.0265ecst

• 2014 • 116	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 (>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 abstract	doi: 10.1039/c4cc07527g

• 2014 • 115	Oxygen-deficient titania as alternative support for Pt catalysts for the oxygen reduction reaction Zhao, A. and Masa, J. and Xia, W. Journal of Energy Chemistry 23 701-707 (2014) Insufficient electrochemical stability is a major challenge for carbon materials in oxygen reduction reaction (ORR) due to carbon corrosion and insufficient metal-support interactions. In this work, titania is explored as an alternative support for Pt catalysts. Oxygen deficient titania samples including TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> were obtained by thermal treatment of anatase TiO<inf>2</inf> under flowing H<inf>2</inf> and NH<inf>3</inf>, respectively. Pt nanoparticles were deposited on the titania by a modified ethylene glycol method. The samples were characterized by N<inf>2</inf>-physisorption, X-ray diffraction and X-ray photoelectron spectroscopy. The ORR activity and long-term stability of supported Pt catalysts were evaluated using linear sweep voltammetry and chronoamperometry in 0.1 mol/L HClO<inf>4</inf>. Pt/TiO<inf>2-x</inf> and Pt/TiO<inf>2-x</inf>N<inf>y</inf> showed higher ORR activities than Pt/TiO<inf>2</inf> as indicated by higher onset potentials. Oxygen deficiency in TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> contributed to the high ORR activity due to enhanced charge transfer, as disclosed by electrochemical impedance spectroscopy studies. Electrochemical stability studies revealed that Pt/TiO<inf>2-x</inf> exhibited a higher stability with a lower current decay rate than commercial Pt/C, which can be attributed to the stable oxide support and strong interaction between Pt nanoparticles and the oxygen-deficient TiO<inf>2-x</inf> support. © 2014 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/S2095-4956(14)60202-3

• 2014 • 114	Photoemission electron microscopy and scanning electron microscopy of magnetospirillum magnetotacticum 's magnetosome chains Keutner, C. and Von Bohlen, A. and Berges, U. and Espeter, P. and Schneider, C.M. and Westphal, C. Analytical Chemistry 86 9590-9594 (2014) Magnetotactic bacteria are of great interdisciplinary interest, since a vast field of applications from magnetic recording media to medical nanorobots is conceivable. A key feature for a further understanding is the detailed knowledge about the magnetosome chain within the bacteria. We report on two preparation procedures suitable for UHV experiments in reflective geometry. Further, we present the results of scanning electron microscopy, as well as the first photoemission electron microscopy experiments, both accessing the magnetosomes within intact magnetotactic bacteria and compare these to scanning electron microscopy data from the literature. From the images, we can clearly identify individual magnetosomes within their chains. © 2014 American Chemical Society.
  	view abstract	doi: 10.1021/ac502050j

• 2014 • 113	Properties of anodic oxides grown on a hafnium-tantalum-titanium thin film library Mardare, A.I. and Ludwig, Al. and Savan, A. and Hassel, A.W. Science and Technology of Advanced Materials 15 (2014) A ternary thin film combinatorial materials library of the valve metal system Hf-Ta-Ti obtained by co-sputtering was studied. The microstructural and crystallographic analysis of the obtained compositions revealed a crystalline and textured surface, with the exception of compositions with Ta concentration above 48 at.% which are amorphous and show a flat surface. Electrochemical anodization of the composition spread thin films was used for analysing the growth of the mixed surface oxides. Oxide formation factors, obtained from the potentiodynamic anodization curves, as well as the dielectric constants and electrical resistances, obtained from electrochemical impedance spectroscopy, were mapped along two dimensions of the library using a scanning droplet cell microscope. The semiconducting properties of the anodic oxides were mapped using Mott-Schottky analysis. The degree of oxide mixing was analysed qualitatively using x-ray photoelectron spectroscopy depth profiling. A quantitative analysis of the surface oxides was performed and correlated to the as-deposited metal thin film compositions. In the concurrent transport of the three metal cations during oxide growth a clear speed order of Ti > Hf > Ta was proven. © 2014 National Institute for Materials Science.
  	view abstract	doi: 10.1088/1468-6996/15/1/015006

• 2014 • 112	Reactivity of mesoporous carbon against water - An in-situ XPS study Reiche, S. and Blume, R. and Zhao, X.C. and Su, D. and Kunkes, E. and Behrens, M. and Schlögl, R. Carbon 77 175-183 (2014) Functionalized mesoporous carbon catalysts can be used in the acid catalyzed dehydration of fructose to 5-hydroxymethyl furfural (HMF). However, strong deactivation can be observed after preconditioning of the material in the reaction solvent 2-butanol. Surface changes caused by the pretreatment have been studied by XPS. The comparison of the pristine sample and the pretreated carbon sample showed similar distribution of oxygen functional groups by ex-situ XPS, as well as similar behavior during heating in vacuum. However, the addition of water (0.1 mbar vapor pressure) and subsequent heating to 130 °C exhibited prominent differences in the evolution of the O1s, as well as for the C1s spectra of the two samples. Changes in the surface termination and hydrophobicity of the materials are discussed under the aspect of possible reactions of surface functional groups with the alcoholic solvent and water. © 2014 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.carbon.2014.05.019

• 2014 • 111	Reliable benchmark material for anatase TiO2 in Li-ion batteries: On the role of dehydration of commercial TiO2 Madej, E. and La Mantia, F. and Mei, B. and Klink, S. and Muhler, M. and Schuhmann, W. and Ventosa, E. Journal of Power Sources 266 155-161 (2014) Commercially available anatase TiO2 nanoparticles (ca. 15-20 nm particle size) were investigated as negative electrode material for Li-ion batteries. Despite the high initial specific charge of 200 mAh g-1 at 0.5C, the pristine commercial TiO2 failed to retain the reversible capacity upon cycling, keeping only 23% of the initial value after 80 cycles. X-ray photoelectron spectroscopy (XPS) results together with electrochemical data suggest that the failure in cyclability is of kinetic nature as the loss in specific charge is not completely irreversible. Thermogravimetry analysis revealed that the pristine TiO2 contained a significant amount of TiO(OH)2 (ca. 8%) which can be easily removed by dehydration when annealing in air above 250 °C. Air-annealing of TiO2 at 300 °C resulted in a remarkable improvement in cyclability retaining 83% of initial specific charge after 80 cycles at 0.5C. No further improvement in cyclability was observed for TiO2 annealed at 450 °C suggesting that the dehydration of TiO(OH)2 was the primary source of the improvement. Knowing the role of dehydration of TiO2 allows obtaining a reliable benchmark material via simple air-annealing and becomes a key factor when developing advanced materials from commercial TiO2. © 2014 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.jpowsour.2014.05.018

• 2014 • 110	Spinel Mn-Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting Zhao, A. and Masa, J. and Xia, W. and Maljusch, A. and Willinger, M.-G. and Clavel, G. and Xie, K. and Schlögl, R. and Schuhmann, W. and Muhler, M. Journal of the American Chemical Society 136 7551-7554 (2014) The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future. © 2014 American Chemical Society.
  	view abstract	doi: 10.1021/ja502532y

• 2014 • 109	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 abstract	doi: 10.1016/j.jcat.2014.06.019

• 2014 • 108	Structural and functional characterization of enamel pigmentation in shrews Dumont, M. and Tütken, T. and Kostka, A. and Duarte, M.J. and Borodin, S. Journal of Structural Biology 186 38-48 (2014) Pigmented tooth enamel occurs in several vertebrate clades, ranging from mammals to fish. Although an iron compound is associated with this orange to red colored pigmentation, its chemical and structural organization within the enamel is unknown. To determine the nature of the iron compound, we investigated heavily pigmented teeth of the northern short-tailed shrew Blarina brevicauda using combined characterization techniques such as scanning and transmission electron microscopy and synchrotron X-ray diffraction. We found that the pigmentation of the enamel with an iron content of around 8. wt% results from a close to amorphous magnetite phase deposited around the nm-sized enamel crystals. Furthermore, the influence of the pigmentation on the enamel hardness was determined by nanoindentation measurements. Finally, the biomechanical function and biological context are discussed in light of the obtained results. © 2014 Elsevier Inc.
  	view abstract	doi: 10.1016/j.jsb.2014.02.006

• 2014 • 107	Surface dynamics of the intermetallic catalyst Pd2Ga, Part i - Structural stability in UHV and different gas atmospheres Wowsnick, G. and Teschner, D. and Kasatkin, I. and Girgsdies, F. and Armbrüster, M. and Zhang, A. and Grin, Y. and Schlögl, R. and Behrens, M. Journal of Catalysis 309 209-220 (2014) The structural and electronic properties of unsupported Pd2Ga were investigated after different pre-treatments. Pd2Ga provides with respect to elemental Pd a significantly modified electronic structure with its d-band center being shifted away from the Fermi level. It was found that the electronic structure of the surface depends strongly on its pre-treatment and on the chemical environment. We report a detailed bulk and surface characterization of the intermetallic compound by means of XRD, DTA/TG/MS, SEM, XPS, and HR-TEM. At moderate temperatures, the bulk of Pd2Ga is chemically resistant against H2 or O2 atmosphere and against mechanical load. Contrariwise its surface is highly sensitive against even traces of oxidizing agents, leading quickly to a disparity between bulk and surface structure and composition. The reversibility of this dynamic effect depends on the degree of decomposition and on the sample history. An almost pure intermetallic surface can only be achieved in highly reducing atmospheres. © 2013 Elsevier Inc. All rights reserved.
  	view abstract	doi: 10.1016/j.jcat.2013.09.019

• 2014 • 106	The effect of surface reactions of O, O-3 and N on film properties during the growth of silica-like films Rugner, K. and Reuter, R. and von Keudell, A. and Benedikt, J. Journal of Physics D-applied Physics 47 224005 (2014) The effect of surface reactions of O, O-3 and N radicals during the growth of silica-like (SiOxCyHz) films on film properties is investigated. A SiOxCyHz film is deposited from a He/Hexamethyldisiloxan (HMDSO) cold atmospheric plasma on a rotating substrate. The surface of this film is, during the growth, treated on the opposite site of the substrate by a second cold atmospheric plasma with helium and an addition of O-2 or N-2. A reactor with four separated cells and gas curtains between them is used to avoid cross-contamination of the ambient atmosphere in each cell. The changes in film composition after the deposition with and without a treatment by O, O-3 and N are investigated by Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy. Additionally, the effect of each species on the deposition rate is also presented and discussed.
  	view abstract	doi: 10.1088/0022-3727/47/22/224005

• 2013 • 105	"grafting-from" Polymerization of PMMA from stainless steel surfaces by a raft-mediated polymerization process Zammarelli, N. and Luksin, M. and Raschke, H. and Hergenröder, R. and Weberskirch, R. Langmuir 29 12834-12843 (2013) The synthesis of grafted PMMA homopolymer films is reported using a surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization from a RAFT-agent immobilized on a silanized stainless steel surface. Therefore, stainless steel surfaces were hydroxylated with piranha solution followed by silanization with 3-aminopropylsilane (APS). The pendant primary amino groups of the cross-linked polysiloxane layer were reacted with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid N-hydroxysuccinimide ester to produce a surface with covalently immobilized RAFT agents. PMMA homopolymers of different molecular weights between 13 060 and 45 000 g/mol were then prepared by a surface-initiated RAFT polymerization. Molecular weight (MW) and polydispersity index (PDI) were determined from sacrificial polymerization in solution. The different steps of stainless steel surface modification and the ultrathin films were investigated using atomic force microscopy (AFM), static, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR-IR), and ellipsometry. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/la402870p

• 2013 • 104	Activation and stabilization of nitrogen-doped carbon nanotubes as electrocatalysts in the oxygen reduction reaction at strongly alkaline conditions Zhao, A. and Masa, J. and Schuhmann, W. and Xia, W. Journal of Physical Chemistry C 117 24283-24291 (2013) Nitrogen-doped carbon nanotubes (NCNTs) are highly active electrocatalysts in the oxygen reduction reaction (ORR) at alkaline conditions. However, the initial activation and stabilization of NCNTs have rarely been investigated at industrially relevant conditions. Three types of NCNTs were synthesized by catalytic growth (NCNT-growth) or posttreatment of oxygen-functionalized CNTs with NH3 (NCNT-NH3) or aniline (NCNT-aniline). The obtained NCNTs were treated in 10 M KOH at 80 C for 5 h, and the formation of oxygen groups by alkaline treatment and their interaction with existing nitrogen groups was analyzed. X-ray photoelectron spectroscopy showed that the concentrations of pyridinic and quaternary nitrogen increased in NCNT-growth due to the KOH treatment accompanied by the decrease of pyrrolic nitrogen, whereas the nitrogen groups changed differently in NCNT-NH3 and NCNT-aniline. NCNT-NH3 showed the highest ORR activity before alkaline treatment. After the treatment, the activity of NCNT-growth was higher, whereas those of NCNT-NH3 and NCNT-aniline were lower. These results were found to be correlated with changes in the nitrogen groups caused by alkaline treatment. Furthermore, NCNTs showed different C=O/C-O ratios after alkaline treatment as compared to a strong increase of C-O in CNTs, indicating that the presence of nitrogen in NCNTs influences the formation of oxygen groups on carbon and surface oxidation. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/jp4059438

• 2013 • 103	Band offsets in complex-oxide thin films and heterostructures of SrTiO 3/LaNiO3 and SrTiO3/GdTiO3 by soft and hard X-ray photoelectron spectroscopy Conti, G. and Kaiser, A.M. and Gray, A.X. and Nemšák, S. and Pálsson, G.K. and Son, J. and Moetakef, P. and Janotti, A. and Bjaalie, L. and Conlon, C.S. and Eiteneer, D. and Greer, A.A. and Keqi, A. and Rattanachata, A. and Saw... Journal of Applied Physics 113 (2013) The experimental determination of valence band offsets (VBOs) at interfaces in complex-oxide heterostructures using conventional soft x-ray photoelectron spectroscopy (SXPS, hν 1500 eV) and reference core-level binding energies can present challenges because of surface charging when photoelectrons are emitted and insufficient probing depth to clearly resolve the interfaces. In this paper, we compare VBOs measured with SXPS and its multi-keV hard x-ray analogue (HXPS, hν > 2000 eV). We demonstrate that the use of HXPS allows one to minimize charging effects and to probe more deeply buried interfaces in heterostructures such as SrTiO3/LaNiO3 and SrTiO3/GdTiO 3. The VBO values obtained by HXPS for these interfaces are furthermore found to be close to those determined by first-principles calculations. © 2013 American Institute of Physics.
  	view abstract	doi: 10.1063/1.4795612

• 2013 • 102	Designing magnetic field responsive nanofiltration membranes Yang, Q. and Himstedt, H.H. and Ulbricht, M. and Qian, X. and Ranil Wickramasinghe, S. Journal of Membrane Science 430 70-78 (2013) Base, thin film composite polyamide, nanofiltration membranes have been modified using surface initiated atom transfer radical polymerization to graft poly(2-hydroxyethyl methacrylate) (polyHEMA) chains from the surface of the membrane. A modified Gabriel synthesis procedure was used to attach superparamagnetic (Fe3O4) nanoparticles to the chain ends. Chain density and chain length were independently varied by adjusting the initiator density and polymerization time. Membranes were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy and contact angle measurements. The performance of modified membranes was investigated by determining deionized water fluxes as well as permeate fluxes and salt rejection for aqueous feed streams containing 500ppm CaCl2 and 2000ppm MgSO4. All experiments were conducted in dead end mode. Modified membranes display a reduced permeate flux and increased salt rejection compared to unmodified membranes in the absence of a magnetic field. Since both grafted chain density and chain length are expected to affect membrane performance differently, the decrease in permeate flux and increase in salt rejection is not directly proportional to the increase in grafted polymer weight. Modified membranes display both increased permeate fluxes and increased salt rejection in the presence of an oscillating magnetic field compared to their performance in the absence of an oscillating magnetic field. Magnetically responsive membranes could represent a new class of fouling resistant membranes. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.memsci.2012.11.068

• 2013 • 101	Effect of Sn surface states on the photocatalytic activity of anatase TiO2 Oropeza, F.E. and Mei, B. and Sinev, I. and Becerikli, A.E. and Muhler, M. and Strunk, J. Applied Catalysis B: Environmental 140-141 51-59 (2013) The influence of surface Sn-doping on the photocatalytic properties of anatase TiO2 has been investigated in samples prepared by a grafting route using Sn(IV) tert-butoxide as Sn precursor. The grafting procedure leads to the formation of isolated Sn(IV) sites on the surface of anatase TiO2 powders as gauged by structural characterisation based on XRD, Raman spectroscopy and XAS. Studies of the surface reduction based on TPR experiments and XPS provide the conditions for a selective reduction of surface Sn(IV) to the divalent oxidation state. Electronic structure characterisation based on valence band XPS and DRS shows that there is a slight widening of the band gap upon Sn(IV)-grafting, but Sn(II) related states emerge at the top of the main valence band upon reduction at temperatures up to 350°C, and this induces visible light absorption. Grafting of TiO2 with Sn(IV) increases the formation rate of OH radicals on the surface of the material. Reduction of the Sn(IV)-grafted TiO2 to form surface Sn(II) brings about substantial increase of the photocatalytic efficiency for the methylene blue degradation under irradiation with λ≥320nm compared with Sn(IV)-grafted and pure anatase TiO2. This observation is explained based on a surface hole trapping by the Sn(II)-related surface states which lie above the top of the main valence band and can therefore act as trapping sites for holes produced under photoexcitation. © 2013 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apcatb.2013.03.043

• 2013 • 100	Enhancing the activity of Pd on carbon nanofibers for deoxygenation of amphiphilic fatty acid molecules through support polarity Gosselink, R.W. and Xia, W. and Muhler, M. and De Jong, K.P. and Bitter, J.H. ACS Catalysis 3 2397-2402 (2013) The influence of support polarity on Pd/CNF for the deoxygenation of fatty acids was studied. Catalysts with a low (O/C = 3.5 × 10-2 at/at from X-ray photoelectron spectroscopy (XPS)) and a high (O/C = 5.9 × 10-2 at/at from XPS) amount of oxygen containing groups on the support were prepared. The latter were introduced via a HNO3 gas phase oxidation treatment on Pd loaded supports. The presence of oxygen containing groups was beneficial for the activity of Pd for the deoxygenation of the amphiphilic stearic acid. This is attributed to a favorable mode of adsorption of the reactant via the carboxylic acid group on the more polar support in the vicinity of the catalytically active Pd nanoparticles. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/cs400478q

• 2013 • 99	Eu-doped ZnO nanowire arrays grown by electrodeposition Lupan, O. and Pauporté, T. and Viana, B. and Aschehoug, P. and Ahmadi, M. and Cuenya, B.R. and Rudzevich, Y. and Lin, Y. and Chow, L. Applied Surface Science 282 782-788 (2013) The preparation of efficient light emitting diodes requires active optical layers working at low voltage for light emission. Trivalent lanthanide doped wide-bandgap semiconducting oxide nanostructures are promising active materials in opto-electronic devices. In this work we report on the electrochemical deposition (ECD) of Eu-doped ZnO (ZnO:Eu) nanowire arrays on glass substrates coated with F-doped polycrystalline SnO2. The structural, chemical and optical properties of ZnO:Eu nanowires have been systematically characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and photoluminescence. XRD results suggest the substitution of Zn2+ by Eu ions in the crystalline lattice. High-resolution TEM and associated electron diffraction studies indicate an interplanar spacing of 0.52 nm which corresponds to the (0 0 0 1) crystal plane of the hexagonal ZnO, and a growth along the c-direction. The ZnO:Eu nanowires have a single crystal structure, without noticeable defects. According to EDX, SIMS and XPS studies, cationic Eu species are detected in these samples showing the incorporation of Eu into the ZnO matrix. The oxidation states of europium ions in the nanowires are determined as +3 (74%) and +2 (26%). Photoluminescence studies demonstrated red emission from the Eu-doped ZnO nanowire arrays. When Eu was incorporated during the nanowire growth, the sharp 5D0-7F 2 transition of the Eu3+ ion at around 612 nm was observed. These results suggest that Eu doped ZnO nanowires could pave the way for efficient, multispectral LEDs and optical devices. © 2013 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.apsusc.2013.06.053

• 2013 • 98	Experimental and numerical atomistic investigation of the third body formation process in dry tungsten/tungsten-carbide tribo couples Stoyanov, P. and Romero, P.A. and Järvi, T.T. and Pastewka, L. and Scherge, M. and Stemmer, P. and Fischer, A. and Dienwiebel, M. and Moseler, M. Tribology Letters 50 67-80 (2013) The third body in tungsten/tungsten-carbide sliding systems is studied using a combination of experiments and atomistic simulations. Ex situ X-ray photoelectron spectroscopy and focused ion beam analysis of the structural and chemical changes near the surfaces reveals that sliding of tungsten against tungsten-carbide results in plastic deformation of the W surface, leading to grain refinement, and the formation of a mechanically mixed amorphous layer on the WC counter body. Molecular dynamics simulations of W/WC sliding couples exhibit the formation of a nanoscale amorphous W/WC interface. The infrequent occurrence of atomic jamming events in the interface resulted in the emission of dislocations into the W bulk and the generation of amorphous shear bands in the WC counter body in agreement with the different third bodies observed in W and WC after the experiments. © 2012 Springer Science+Business Media New York.
  	view abstract	doi: 10.1007/s11249-012-0085-7

• 2013 • 97	Friction and wear mechanisms of tungsten-carbon systems: A comparison of dry and lubricated conditions Stoyanov, P. and Stemmer, P. and Järvi, T.T. and Merz, R. and Romero, P.A. and Scherge, M. and Kopnarski, M. and Moseler, M. and Fischer, A. and Dienwiebel, M. ACS Applied Materials and Interfaces 5 6123-6135 (2013) The unfolding of a sheared mechanically mixed third-body (TB) in tungsten/tungsten carbide sliding systems is studied using a combination of experiments and simulations. Experimentally, the topographical evolution and the friction response, for both dry and lubricated sliding, are investigated using an online tribometer. Ex situ X-ray photoelectron spectroscopy, transmission electron microscopy, and cross-sectional focused ion beam analysis of the structural and chemical changes near the surfaces show that dry sliding of tungsten against tungsten carbide results in plastic deformation of the tungsten surface, leading to grain refinement, and the formation of a mechanically mixed layer on the WC counterface. Sliding with hexadecane as a lubricant results in a less pronounced third-body formation due to much lower dissipated frictional power. Molecular dynamics simulations of the sliding couples predict chemical changes near the surface in agreement with the interfacial processes observed experimentally. Finally, online topography measurements demonstrate an excellent correlation between the evolution of the roughness and the frictional resistance during sliding. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/am4010094

• 2013 • 96	In situ visualization of Li-ion intercalation and formation of the solid electrolyte interphase on TiO2 based paste electrodes using scanning electrochemical microscopy Zampardi, G. and Ventosa, E. and La Mantia, F. and Schuhmann, W. Chemical Communications 49 9347-9349 (2013) Scanning electrochemical microscopy (SECM) inside a glove box was used for the in situ visualization of solid electrolyte interphase (SEI) formation as well as Li-ion intercalation and de-intercalation on anatase TiO2 based paste electrodes. © 2013 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c3cc44576c

• 2013 • 95	Investigation of a conjugated polyelectrolyte interlayer for inverted polymer:fullerene solar cells Xia, R. and Leem, D.-S. and Kirchartz, T. and Spencer, S. and Murphy, C. and He, Z. and Wu, H. and Su, S. and Cao, Y. and Kim, J.S. and Demello, J.C. and Bradley, D.D.C. and Nelson, J. Advanced Energy Materials 3 718-723 (2013) Inverted bulk heterojunction solar cells are fabricated using a conjugated polyelectrolyte (PFN) as a cathode interlayer. Enhanced photovoltaic performance is achieved by adjusting the PFN thickness. Measurements of the optical transmittance, cathode work function (via UPS) and surface atomic composition (via XPS) provide insights into this optimization. Drift-diffusion simulations point to a reduction in recombination of holes at the cathode as the main cause for improving Voc. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/aenm.201200967

• 2013 • 94	Long-range segregation phenomena in shape-selected bimetallic nanoparticles: Chemical state effects Ahmadi, M. and Behafarid, F. and Cui, C. and Strasser, P. and Cuenya, B.R. ACS Nano 7 9195-9204 (2013) A study of the morphological and chemical stability of shape-selected octahedral Pt0.5Ni0.5 nanoparticles (NPs) supported on highly oriented pyrolytic graphite (HOPG) is presented. Ex situ atomic force microscopy (AFM) and in situ X-ray photoelectron spectroscopy (XPS) measurements were used to monitor the mobility of Pt0.5Ni0.5 NPs and to study long-range atomic segregation and alloy formation phenomena under vacuum, H2, and O2 environments. The chemical state of the NPs was found to play a pivotal role in their surface composition after different thermal treatments. In particular, for these ex situ synthesized NPs, Ni segregation to the NP surface was observed in all environments as long as PtOx species were present. In the presence of oxygen, an enhanced Ni surface segregation was observed at all temperatures. In contrast, in hydrogen and vacuum, the Ni outward segregation occurs only at low temperature (< 200-270 C), while PtOx species are still present. At higher temperatures, the reduction of the Pt oxide species results in Pt diffusion toward the NP surface and the formation of a Ni-Pt alloy. A consistent correlation between the NP surface composition and its electrocatalytic CO oxidation activity was established. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/nn403793a

• 2013 • 93	Low-temperature oxidation of alkali overlayers: Ionic species and reaction kinetics Krix, D. and Nienhaus, H. Applied Surface Science 270 231-237 (2013) Clean and oxidized alkali metal films have been studied using X-ray photoelectron spectroscopy (XPS). Thin films, typically 10 nm thick, of lithium, sodium, potassium, rubidium and cesium have been deposited on silicon substrates and oxidized at 120 K. Plasmon losses were found to dress the primary photo emission structures of the metals' core lines which confirms the metallic, bulk like nature of the films. The emission from the O 1s core levels was used to determine the chemical composition and the reaction kinetics during the exposure to molecular oxygen at low pressures. Molecular oxide ions O2- and O22- as well as atomic oxygen ions O2- were detected in varying amounts depending on the alkali metal used. Diffusive transport of material in the film is shown to greatly determine the composition of the oxides. Especially, the growth of potassium superoxide is explained by the diffusion of potassium atoms to the surface and growth at the surface in a Deal-Grove like model.
  	view abstract	doi: 10.1016/j.apsusc.2013.01.008

• 2013 • 92	Morphology, thermoelectric properties and wet-chemical doping of laser-sintered germanium nanoparticles Stoib, B. and Langmann, T. and Petermann, N. and Matich, S. and Sachsenhauser, M. and Wiggers, H. and Stutzmann, M. and Brandt, M.S. Physica Status Solidi (A) Applications and Materials Science 210 153-160 (2013) Porous, highly doped semiconductors are potential candidates for thermoelectric energy conversion elements. We report on the fabrication of thin films of Ge via short-pulse laser-sintering of Ge nanoparticles (NPs) in vacuum and study the macroporous morphology of the samples by secondary electron microscopy (SEM) imaging. The temperature dependence of the electrical conductivity and the Seebeck coefficient of undoped Ge is discussed in conjunction with the formation of a defect band near the valence band. We further introduce a versatile method of doping the resulting films with a variety of common dopant elements in group-IV semiconductors by using a liquid containing the dopant atoms. This method is fully compatible with laser-direct writing and suited to fabricate small scale thermoelectric generators. The incorporation of the dopants is verified by X-ray photoelectron spectroscopy (XPS) and their electrical activation is studied by conductivity and thermopower measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/pssa.201228392

• 2013 • 91	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 abstract	doi: 10.1016/j.electacta.2013.03.043

• 2013 • 90	Nano-gold diggers: Au-Assisted SiO2-decomposition and desorption in supported nanocatalysts Ono, L.K. and Behafarid, F. and Cuenya, B.R. ACS Nano 7 10327-10334 (2013) An investigation of the thermal stability of size-selected Au nanoparticles (NPs) synthesized via inverse micelle encapsulation and deposited on SiO 2(4 nm)/Si(100) is presented. The size and mobility of individual Au NPs after annealing at elevated temperatures in ultrahigh vacuum (UHV) was monitored via atomic force microscopy (AFM). An enhanced thermal stability against coarsening and lack of NP mobility was observed up to 1343 K. In addition, a drastic decrease in the average NP height was detected with increasing annealing temperature, which was not accompanied by the sublimation of Au atoms/clusters in UHV. The apparent decrease in the Au NP height observed is assigned to their ability to dig vertical channels in the underlying SiO 2 support. More specifically, a progressive reduction in the thickness of the SiO2 support underneath and in the immediate vicinity of the NPs was evidenced, leading to NPs partially sinking into the SiO2 substrate. The complete removal of silicon oxide in small patches was observed to take place around the Au NPs after annealing at 1343 K in UHV. These results reveal a Au-assisted oxygen desorption from the support via reverse oxygen spillover to the NPs. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/nn404744b

• 2013 • 89	Preparation of amorphous and nanocrystalline sodium tantalum oxide photocatalysts with porous matrix structure for overall water splitting Tüysüz, H. and Chan, C.K. Nano Energy 2 116-123 (2013) Herein, we report the preparation of a series of surfactant-free nanostructured sodium tantalum oxide using NaTa(OC3H7)6 as a single precursor. The reaction conditions for the novel synthetic method were optimized and the morphology and crystal structure of the prepared materials were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Condensation and polymerization of NaTa(OC3H7)6 under atmospheric pressure gave a porous amorphous structure that could be converted to crystalline NaTaO3 while crystalline Na2Ta2O6 nanocrystals with a 25nm average particle size could be obtained from a hydrothermal method using NH3 as a base catalyst. In addition, the photocatalytic behaviors of the prepared materials were investigated for overall water splitting into hydrogen and oxygen. Unexpectedly, porous amorphous sodium tantalum oxide showed much better catalytic activity over the crystalline one. The synthesized Na2Ta2O6 nanocrystals also indicated promising activity for overall water splitting without any co-catalyst in comparison to bulk NaTaO3. © 2012 Elsevier Ltd.
  	view abstract	doi: 10.1016/j.nanoen.2012.08.003

• 2013 • 88	Purified oxygen- and nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation Chen, P. and Chew, L.M. and Kostka, A. and Xie, K. and Muhler, M. and Xia, W. Journal of Energy Chemistry 22 312-320 (2013) Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis. Copyright © 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
  	view abstract	doi: 10.1016/S2095-4956(13)60038-8

• 2013 • 87	Separation of semiconducting and ferromagnetic FeSi2- nanoparticles by magnetic filtering Aigner, W. and Niesar, S. and Mehmedovic, E. and Opel, M. and Wagner, F.E. and Wiggers, H. and Stutzmann, M. Journal of Applied Physics 114 (2013) We have investigated the potential of solution-processed β-phase iron disilicide (FeSi2) nanoparticles as a novel semiconducting material for photovoltaic applications. Combined ultraviolet-visible absorption and photothermal deflection spectroscopy measurements have revealed a direct band gap of 0.85 eV and, therefore, a particularly high absorption in the near infrared. With the help of Fourier-transform infrared and X-ray photoelectron spectroscopy, we have observed that exposure to air primarily leads to the formation of a silicon oxide rather than iron oxide. Mössbauer measurements have confirmed that the nanoparticles possess a phase purity of more than 99%. To diminish the small fraction of metallic iron impurities, which were detected by superconducting quantum interference device magnetometry and which would act as unwanted Auger recombination centers, we present a novel concept to magnetically separate the FeSi2 nanoparticles (NPs). This process leads to a reduction of more than 95% of the iron impurities. © 2013 AIP Publishing LLC.
  	view abstract	doi: 10.1063/1.4824293

• 2013 • 86	Silicon oxide barrier films deposited on PET foils in pulsed plasmas: Influence of substrate bias on deposition process and film properties Steves, S. and Ozkaya, B. and Liu, C.-N. and Ozcan, O. and Bibinov, N. and Grundmeier, G. and Awakowicz, P. Journal of Physics D: Applied Physics 46 (2013) A widely used plastic for packaging, polyethylene terephtalate (PET) offers limited barrier properties against gas permeation. For many applications of PET (from food packaging to micro electronics) improved barrier properties are essential. A silicon oxide barrier coating of PET foils is applied by means of a pulsed microwave driven low-pressure plasma. While the adjustment of the microwave power allows for a control of the ion production during the plasma pulse, a substrate bias controls the energy of ions impinging on the substrate. Detailed analysis of deposited films applying oxygen permeation measurements, x-ray photoelectron spectroscopy and atomic force microscopy are correlated with results from plasma diagnostics describing the deposition process. The influence of a change in process parameters such as gas mixture and substrate bias on the gas temperature, electron density, mean electron energy, ion energy and the atomic oxygen density is studied. An additional substrate bias results in an increase in atomic oxygen density up to a factor of 6, although plasma parameter such as electron density of ne = 3.8 ± 0.8 x 1017 m-3 and electron temperature of kBT e = 1.7 ± 0.1 eV are unmodified. It is shown that atomic oxygen densities measured during deposition process higher than nO = 1.8 x 1021 m-3 yield in barrier films with a barrier improvement factor up to 150. Good barrier films are highly cross-linked and show a smooth morphology. © 2013 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0022-3727/46/8/084013

• 2013 • 85	Simple synthesis of superparamagnetic magnetite nanoparticles as highly efficient contrast agent Jha, D.K. and Shameem, M. and Patel, A.B. and Kostka, A. and Schneider, P. and Erbe, A. and Deb, P. Materials Letters 95 186-189 (2013) Magnetite nanoparticles have been prepared by one-pot thermal decomposition process using iron (III) acetylacetonate in stearic acid in ambient environment. In this process, stearic acid acts as solvent as well as capping agent for the particles. These as-prepared hydrophobic magnetite nanoparticles have been converted into a hydrophilic form using tetramethylammonium hydroxide. This controlled surface functionalization approach limits microstructural and phase alteration due to the ligand exchange. A detailed investigation was carried out on the microstructural characteristics of these nanoparticles with the aid of X-ray diffraction, infrared spectroscopy, XPS and transmission electron microscopy. The hydrophilic superparamagnetic magnetite particles posses extraordinary transverse relaxivity and contrast property, making them potential T2 contrast agent in clinical magnetic resonance imaging. © 2013 Elsevier B.V.
  	view abstract	doi: 10.1016/j.matlet.2012.12.096

• 2013 • 84	Synthesis and characterization of Cu-doped ZnO one-dimensional structures for miniaturized sensor applications with faster response Chow, L. and Lupan, O. and Chai, G. and Khallaf, H. and Ono, L.K. and Roldan Cuenya, B. and Tiginyanu, I.M. and Ursaki, V.V. and Sontea, V. and Schulte, A. Sensors and Actuators, A: Physical 189 399-408 (2013) Detection of chemicals and biological species is an important issue to human health and safety. In this paper, we report the hydrothermal synthesis at 95 °C of Cu-doped ZnO low-dimensional rods for room-temperature (RT) sensing applications and enhanced sensor performances. X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman and photoluminescence are used to characterize the material properties. To demonstrate the suitability of the Cu-doped ZnO rods for gas sensor applications and for comparison with pure ZnO, we fabricated a double rod device using Focused Ion Beam. The responses of pure-ZnO and Cu-doped ZnO rods studied in exactly the same condition are reported. We found that Cu-ZnO sensors have enhanced RT sensitivity, faster response time, and good selectivity. Miniaturized Cu-ZnO rod-based sensors can serve as a good candidate for effective H2 detectors with low power consumption. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.sna.2012.09.006

• 2013 • 83	Target implantation and redeposition processes during high-power impulse magnetron sputtering of aluminum Will, A. and de los Arcos, T. and Corbella, C. and Hecimovic, A. and Machura, P. D. and Winter, J. and von Keudell, A. Journal of Physics D-applied Physics 46 084009 (2013) The processes of argon retention by the target and redeposition of target material were investigated by x-ray photoelectron spectroscopy as a function of radial position for different plasma conditions in high-power impulse magnetron sputtering of aluminum targets. Significant differences in Ar radial concentration profiles were observed for different discharge conditions. Inside the racetrack area, Ar ion flux-dominated implantation is compensated by radiation-enhanced diffusion loss terms. Outside the racetrack, the role of ion implantation is diminished, and Ar retention by the target may stem from a balance between gettering by redeposited Al and ion-induced Ar desorption.
  	view abstract	doi: 10.1088/0022-3727/46/8/084009

• 2013 • 82	The structural and electronic promoting effect of nitrogen-doped carbon nanotubes on supported Pd nanoparticles for selective olefin hydrogenation Chen, P. and Chew, L.M. and Kostka, A. and Muhler, M. and Xia, W. Catalysis Science and Technology 3 1964-1971 (2013) A high-performance Pd catalyst for selective olefin hydrogenation was synthesized by supporting Pd nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). X-ray diffraction, hydrogen chemisorption, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize Pd supported on NCNTs and nitrogen-free oxygen-functionalized CNTs (OCNTs). The Pd nanoparticles were stabilized on NCNTs with narrower size distribution compared with OCNTs. The XPS analysis revealed that the nitrogen functional groups favor the reduction of Pd on CNTs suggesting an electronic promoter effect. The Pd/NCNT catalyst showed extraordinary catalytic performance in terms of activity, selectivity and stability in the selective hydrogenation of cyclooctadiene, which is related to the structural and electronic promoting effect of the NCNT support. © 2013 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c3cy00097d

• 2013 • 81	Time-resolved measurement of film growth during reactive high power pulsed magnetron sputtering (HIPIMS) of titanium nitride Mitschker, F. and Prenzel, M. and Benedikt, J. and Maszl, C. and von Keudell, A. Journal of Physics D-applied Physics 46 495201 (2013) The growth rate during reactive high power pulsed magnetron sputtering (HIPIMS) of titanium nitride is an inherent time-dependent process. By using a rotating shutter setup it is possible to gain an insight into its variation with a temporal resolution of up to 25 mu s. In this apparatus a 200 mu m slit is rotated in front of the substrate synchronous with the HIPIMS pulses. This ensures that the incoming growth flux is laterally distributed over the substrate. By measuring the resulting deposition profile with profilometry and x-ray photoelectron spectroscopy, the temporal variation of the titanium and nitrogen growth flux per pulse is deduced. The analysis reveals that film growth occurs mainly during an HIPIMS pulse, with the growth rate following the HIPIMS phases ignition, current rise, gas rarefaction, plateau and afterglow. The growth fluxes of titanium and nitrogen follow slightly different behaviours with titanium dominating at the beginning of the HIPIMS pulse and nitrogen at the end of the pulse. This is explained by the gas rarefaction effect resulting in a dense initial metal plasma and metal films which are subsequently nitrified.
  	view abstract	doi: 10.1088/0022-3727/46/49/495201

• 2013 • 80	Transition metal nitride thin films grown by MOCVD using amidinato based complexes [M(NtBu)2{(iPrN)2CMe}2] (M=Mo, W) as precursors Srinivasan, N.B. and Thiede, T.B. and de los Arcos, T. and Gwildies, V. and Krasnopolski, M. and Becker, H.-W. and Rogalla, D. and Devi, A. and Fischer, R.A. Surface and Coatings Technology 230 130-136 (2013) Thin films of molybdenum nitride and tungsten nitride were deposited by metal organic chemical vapour deposition (MOCVD) employing the mixed amidinato-imido compounds [M(NtBu)2{(iPrN)2CMe}2] (M=Mo (1), W (2)) as potential precursors under single source precursor (SSP) condition and in the presence of ammonia at substrate temperatures of 500°C-800°C. Under SSP conditions, the films consisted of the nitride and carbide phases for both the material systems, while the addition of ammonia during the MOCVD process led to the formation of the respective metal nitrides. The films were smooth and amorphous at 500°C, and comprised of very fine grains at higher temperatures. Elemental composition investigated by complementary techniques such as Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS) revealed that the films grown in the presence of ammonia had increased levels of nitrogen and decreased carbon content relative to films grown under SSP condition. © 2013 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2013.06.024

• 2013 • 79	Universal method for protein immobilization on chemically functionalized germanium investigated by ATR-FTIR difference spectroscopy Schartner, J. and Güldenhaupt, J. and Mei, B. and Rögner, M. and Muhler, M. and Gerwert, K. and Kötting, C. Journal of the American Chemical Society 135 4079-4087 (2013) Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy allows a detailed analysis of surface attached molecules, including their secondary structure, orientation, and interaction with small molecules in the case of proteins. Here, we present a universal immobilization technique on germanium for all oligo-histidine-tagged proteins. For this purpose, new triethoxysilane derivates were developed: we synthesized a linker-silane with a succinimidyl ester as amine-reactive headgroup and a matrix-silane with an unreactive ethylene glycol group. A new methodology for the attachment of triethoxysilanes on germanium was established, and the surface was characterized by ATR-FTIR and X-ray photoelectron spectroscopy. In the next step, the succinimidyl ester was reacted with aminonitrilotriacetic acid. Subsequently, Ni2+ was coordinated to form Ni-nitrilotriacetic acid for His-tag binding. The capability of the functionalized surface was demonstrated by experiments using the small GTPase Ras and photosystem I (PS I). The native binding of the proteins was proven by difference spectroscopy, which probes protein function. The function of Ras as molecular switch was demonstrated by a beryllium trifluoride anion titration assay, which allows observation of the "on" and "off" switching of Ras at atomic resolution. Furthermore, the activity of immobilized PS I was proven by light-induced difference spectroscopy. Subsequent treatment with imidazole removes attached proteins, enabling repeated binding. This universal technique allows specific attachment of His-tagged proteins and a detailed study of their function at the atomic level using FTIR difference spectroscopy. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/ja400253p

• 2013 • 78	X-ray photoemission and density functional theory study of the interaction of water vapor with the Fe3O4(001) surface at near-ambient conditions Kendelewicz, T. and Kaya, S. and Newberg, J.T. and Bluhm, H. and Mulakaluri, N. and Moritz, W. and Scheffler, M. and Nilsson, A. and Pentcheva, R. and Brown Jr., G.E. Journal of Physical Chemistry C 117 2719-2733 (2013) The interaction of water with the Fe3O4(001) surface was investigated in a combined ambient pressure X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) study. The uptake of molecular water and hydroxyl species on the (001) surface of a natural magnetite sample at near-ambient conditions was quantified using O 1s spectra taken in the p(H 2O) range from 10-9 to 2 Torr. At low p(H2O) (≤10-4-10-5 Torr) and room temperature, we found that water does not adsorb dissociatively on the surface, except on defect sites. In contrast, progressive dissociation into surface hydroxyl species was observed between 10-4 and 10-2 Torr p(H2O). The onset of hydroxylation coincides with the increasing presence of molecular water species on the surface, which demonstrates the key role played by cooperative interactions between adsorbed water molecules, leading to dissociation and surface hydroxylation. The measured O 1s chemical shifts of hydroxyl and molecular water species from both isotherm and isobar data are on average ∼1.2 eV and ∼3.3 eV, respectively, relative to lattice oxygen. The chemical shift of the hydroxyl species on magnetite(001) agrees with previously reported values for hydroxyl species on iron oxyhydroxides such as goethite (α-FeOOH). DFT calculations including an on-site Coulomb repulsion parameter (generalized gradient approximation (GGA) + U approach) predict O 1s surface core-level shifts (SCLS) at the clean (21/2×2 1/2)R45 reconstructed Fe3O4(001) surface of up to ∼-1 eV depending on the specific bonding configuration of the surface O atoms. Hydroxyl groups formed by the dissociation of isolated water molecules at O vacancies have an SCLS value of ∼1.2 eV. With increasing coverage there is a transition toward partial dissociation on the (001) surface. The calculated SCLS for hydroxyl and adsorbed water are 1.2-1.9 and 2.6-3.0 eV, respectively, and compare very well with our experimental results. Final-state effects obtained within the Slater-Janak approach thus have the dominant contribution. In addition, the modest reduction of the work function (∼0.5 eV) predicted by DFT calculations for the mixed adsorption of dissociated and intact water molecules agrees well with work function changes measured experimentally. Finally, the similarity between isotherm and isobar data and the DFT calculations for the C-free Fe3O4(001) surface indicate that surface hydroxylation is indeed substrate induced and not catalyzed by the presence of adventitious carbonaceous species. Both theory and experiment show the importance of cooperative effects between adjacent water molecules in the dissociation reaction. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/jp3078024

• 2013 • 77	Zr(NEtMe)2(guan-NEtMe2)2] as a novel atomic layer deposition precursor: ZrO2 film growth and mechanistic studies Blanquart, T. and Niinistö, J. and Aslam, N. and Banerjee, M. and Tomczak, Y. and Gavagnin, M. and Longo, V. and Puukilainen, E. and Wanzenboeck, H.D. and Kessels, W.M.M. and Devi, A. and Hoffmann-Eifert, S. and Ritala, M. and Leskelä, M. Chemistry of Materials 25 3088-3095 (2013) [Zr(NEtMe)2(guan-NEtMe2)2], a recently developed compound, was investigated as a novel precursor for the atomic layer deposition (ALD) of ZrO2. With water as the oxygen source, the growth rate remained constant over a wide temperature range, whereas with ozone the growth rate increased steadily with deposition temperature. Both ALD processes were successfully developed: the characteristic self-limiting ALD growth mode was confirmed at 300 C. The growth rates were exceptionally high, 0.9 and 1.15 Å/cycle with water and ozone, respectively. X-ray diffraction (XRD) indicated that the films were deposited in the high-permittivity cubic phase, even when grown at temperatures as low as 250 C. Compositional analysis performed by means of X-ray photoelectron spectroscopy (XPS) demonstrated low carbon and nitrogen contamination (< 2 at. % when deposited with ozone). The films presented low root-mean-square (rms) roughness, below 5% of the film thickness, as well as excellent step coverage and conformality on 30:1 aspect ratio trench structures. Dielectric characterization was performed on ZrO 2 metal-insulator-metal (MIM) capacitors and demonstrated high permittivity and low leakage current, as well as good stability of the capacitance. The ALD reaction mechanism was studied in situ: adsorption of the precursor through reaction of the two guan-NEtMe2 ligands with the surface-OD groups was confirmed by the quartz crystal microbalance (QCM) and quadrupole mass spectrometric (QMS) results. © 2013 American Chemical Society.
  	view abstract	doi: 10.1021/cm401279v

• 2012 • 76	Atomic layer deposition of HfO 2 thin films employing a heteroleptic hafnium precursor Xu, K. and Milanov, A.P. and Parala, H. and Wenger, C. and Baristiran-Kaynak, C. and Lakribssi, K. and Toader, T. and Bock, C. and Rogalla, D. and Becker, H.-W. and Kunze, U. and Devi, A. Chemical Vapor Deposition 18 27-35 (2012) The application of a heteroleptic hafnium amide-guanidinate precursor for the deposition of HfO 2 thin films via a water-assisted atomic layer deposition (ALD) process is demonstrated for the first time. HfO 2 films are grown in the temperature range 100-300 °C using the compound [Hf(NMe 2) 2(NMe 2-Guan) 2] (1). This compound shows self-limiting ALD-type growth characteristics with growth rates of the order of 1.0-1.2 Å per cycle in the temperature range 100-225 °C. The saturation behavior and a linear dependence on film thickness as a function of number of cycles are verified at various temperatures within the ALD window. The as-deposited HfO 2 films are characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), Rutherford backscattering spectroscopy (RBS), X-ray photoelectron spectroscopy (XPS), and electrical measurements. For a direct comparison of the precursor performance with that of the parent alkyl amide [Hf(NMe 2) 4] (2), ALD experiments are also performed employing compound 2 under similar process conditions, and in this case no typical ALD characteristics are observed. The application of a heteroleptic hafnium amide-guanidinate precursor [Hf(NMe 2) 2(NMe 2-Guan) 2] for the deposition of HfO 2 thin films via a water assisted ALD process has been demonstrated for the first time. This compound showed self-limiting ALD type growth characteristics with the growth rates as high as 1.0-1.2 Å per cycle in the temperature range 100-225 °C. Typical ALD characteristics such as saturation behavior and linear dependence on the film thickness as a function of number of cycles were verified at different temperatures within the ALD window. The as-deposited HfO 2 films were characterized by AFM, SEM, RBS, XPS and electrical measurements. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201106934

• 2012 • 75	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 abstract	doi: 10.1016/j.jcat.2012.04.002

• 2012 • 74	Characterization of the surface of Fe-19Mn-18Cr-C-N during heat treatment in a high vacuum - An XPS study Zumsande, K. and Weddeling, A. and Hryha, E. and Huth, S. and Nyborg, L. and Weber, S. and Krasokha, N. and Theisen, W. Materials Characterization 71 66-76 (2012) Nitrogen-containing CrMn austenitic stainless steels offer evident benefits compared to CrNi-based grades. The production of high-quality parts by means of powder metallurgy could be an appropriate alternative to the standard molding process leading to improved properties. The powder metallurgical production of CrMn austenitic steel is challenging on account of the high oxygen affinity of Mn and Cr. Oxides hinder the densification processes and may lower the performance of the sintered part if they remain in the steel after sintering. Thus, in evaluating the sinterability of the steel Fe-19Mn-18Cr-C-N, characterization of the surface is of great interest. In this study, comprehensive investigations by means of X-ray photoelectron spectroscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy were performed to characterize the surface during heat treatment in a high vacuum. The results show a shift of oxidation up to 600 °C, meaning transfer of oxygen from the iron oxide layer to Mn-based particulate oxides, followed by progressive reduction and transformation of the Mn oxides into stable Si-containing oxides at elevated temperatures. Mass loss caused by Mn evaporation was observed accompanied by Mn oxide decomposition starting at 700 °C. © 2012 Elsevier Inc. All rights reserved.
  	view abstract	doi: 10.1016/j.matchar.2012.06.002

• 2012 • 73	Correlation between tribological properties, sp 2/sp 3-ratio and H-content of low-wear diamond-like carbon (DLC) layers Vogli, E. and Hoffmann, F. and Bartis, E. and Oehrlein, G.S. and Tillmann, W. Materials Science Forum 706-709 2596-2601 (2012) It has been established that hardness and density of diamond-like carbon (DLC) layers can be raised by increasing ion energy during deposition, decreasing H-content and by increasing sp 3-fraction. To confirm differences in hydrogen content of hydrogen containing and hydrogen free DLC films deposited at different bias voltages, layers were etched in oxygen atmosphere in a capacitively coupled plasma device. By employing real-time ellipsometry measurements, the Hcontent of the hydrogen containing a-C:H layers were estimated by determining the optical constants n and k (n-real part and k-imaginary part of the refractive index). In addition, DLC layers were analyzed by X-ray photoelectron spectroscopy to estimate the ratio of sp 2- and sp 3- hybridization. The mechanical and tribological properties of the coatings were evaluated by means of nanoindentation and ball-on-disc-tests. Finally correlations between these properties, H-content and sp 3/sp 2-ratio were obtained in an effort to explain different tribological behaviors of DLC-layers. © 2012 Trans Tech Publications, Switzerland.
  	view abstract	doi: 10.4028/www.scientific.net/MSF.706-709.2596

• 2012 • 72	Direct monophasic replacement of fatty acid by DMSA on SPION surface Gogoi, M. and Deb, P. and Vasan, G. and Keil, P. and Kostka, A. and Erbe, A. Applied Surface Science 258 9685-9691 (2012) Tailoring the surface and understanding the surface characteristics is necessary for biomedical applications of superparamagnetic nanoparticles. In this paper, superparamagnetic iron oxide nanoparticles (SPIONs) were prepared by thermal decomposition of iron nitrate in presence of stearic acid as surfactant. Due to the multilayer organization of surfactant molecules over the nanoparticle surface, the surface potential can be tuned by pH changes and hence the nanoparticles can be made dispersible in nonpolar as well as in polar solvents. We have presented a simple, facile procedure for controlled replacement of stearic acid from maghemite surface and subsequent derivatization by biocompatible dimercaptosuccinic acid (DMSA) to obtain ultrastable hydrophilic nanoparticles with unaltered morphology, phase and properties. The surface chemistry of the functionalized SPIONs was analyzed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) revealing the presence of bound and unbound thiol groups and disulfides, leading to its prolonged stability in aqueous medium. The consequence of spatially selective functionalization on the stability and solubility of surface hydrophilic SPION has also been realized. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2012.06.011

• 2012 • 71	Electronic structure changes across the metamagnetic transition in FeRh via hard X-ray photoemission Gray, A.X. and Cooke, D.W. and Krüger, P. and Bordel, C. and Kaiser, A.M. and Moyerman, S. and Fullerton, E.E. and Ueda, S. and Yamashita, Y. and Gloskovskii, A. and Schneider, C. M. and Drube, W. and Kobayashi, K. and Hellman, F... Physical Review Letters 108 (2012) Stoichiometric FeRh undergoes a temperature-induced antiferromagnetic (AFM) to ferromagnetic (FM) transition at ∼350K. In this Letter, changes in the electronic structure accompanying this transition are investigated in epitaxial FeRh thin films via bulk-sensitive valence-band and core-level hard x-ray photoelectron spectroscopy with a photon energy of 5.95keV. Clear differences between the AFM and FM states are observed across the entire valence-band spectrum and these are well reproduced using density-functional theory. Changes in the 2p core levels of Fe are also observed and interpreted using Anderson impurity model calculations. These results indicate that significant electronic structure changes over the entire valence-band region are involved in this AFM-FM transition. © 2012 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevLett.108.257208

• 2012 • 70	Embedded argon as a tool for sampling local structure in thin plasma deposited aluminum oxide films Prenzel, M. and de los Arcos, T. and Kortmann, A. and Winter, J. and von Keudell, A. Journal of Applied Physics 112 103306 (2012) Al2O3 thin films, either amorphous or of varying degrees of crystallinity, were deposited by two-frequency radio-frequency magnetron sputtering. Film crystallinity was investigated by Fourier transform infrared spectroscopy and X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) was employed to determine the amount of Ar naturally trapped within the films during the deposition process. A clear correlation was found between the existence of crystalline phases, as determined by XRD, and a shift towards lower binding energy positions of the Ar2p core levels of embedded gas. The shift is due to differences in the local Al2O3 matrix (amorphous or crystalline) of the embedded gas, thus, providing an XPS fingerprint that can be used to qualitatively determine the presence or absence of crystalline phases in very thin films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767383]
  	view abstract	doi: 10.1063/1.4767383

• 2012 • 69	Expanding the view into complex material systems: From micro-ARPES to nanoscale HAXPES Schneider, C.M. and Wiemann, C. and Patt, M. and Feyer, V. and Plucinski, L. and Krug, I.P. and Escher, M. and Weber, N. and Merkel, M. and Renault, O. and Barrett, N. Journal of Electron Spectroscopy and Related Phenomena 185 330-339 (2012) The analysis of chemical and electronic states in complex and nanostructured material systems requires electron spectroscopy to be carried out with nanometer lateral resolution, i.e. nanospectroscopy. This goal can be achieved by combining a parallel imaging photoelectron emission microscope with a bandpass energy filter. In this contribution we describe selected experiments employing a dedicated spectromicroscope - the NanoESCA. This instrument has a particular emphasis on the spectroscopic aspects and enables laterally resolved photoelectron spectroscopy from the VUV up into the hard X-ray regime. © 2012 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.elspec.2012.08.003

• 2012 • 68	Experimental and numerical study of surface alloying by femtosecond laser radiation Gurevich, E.L. and Kittel, S. and Hergenröder, R. Applied Surface Science 258 2576-2579 (2012) Here we report on experimental studies of femtosecond laser induced surface metal alloying. We demonstrate that layers of different metals can be mixed in a certain range of laser pulse energies. Numeric simulations demonstrate that the sub-surface melting and mixing is advantaged through the difference in the electron-phonon coupling constants of the metals in the multi-layer system. Dependence of the depth of the mixed layer on the number of laser pulses per unit area is studied. Numeric simulations illustrate physical picture of the laser alloying process. © 2011 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.apsusc.2011.10.094

• 2012 • 67	Gas phase oxidation as a tool to introduce oxygen containing groups on metal-loaded carbon nanofibers Gosselink, R.W. and Van Den Berg, R. and Xia, W. and Muhler, M. and De Jong, K.P. and Bitter, J.H. Carbon 50 4424-4431 (2012) Oxygen containing groups were introduced, onto carbon nanofibers (CNFs) that were previously loaded with palladium, using HNO 3 vapor. Using traditional liquid-phase oxidations this is not possible due to severe metal leaching. For the samples oxidized using HNO 3 vapor temperature programmed desorption and X-ray photoelectron spectroscopy revealed the presence of two major classes of oxygen containing groups, i.e. carboxylic acid groups which are thermally stable up to 300 °C and less acidic (e.g. phenol) and basic groups which were stable up to 700 °C. The amount of acidic oxygen containing groups introduced by this gas-phase treatment ranged from 0.1 to 0.3 mmol/g, as determined by titration. The latter amount is comparable to that introduced by traditional liquid-phase treatment in 65% HNO 3 on bare CNFs. Transmission electron microscopy and H 2-chemisorption measurements show a gradual increase of the average metal particle size from 2.1 nm for the starting Pd/CNF to 4.5 nm for Pd/CNF treated for 75 h in HNO 3 vapor indicating that the extent of sintering with gas-phase treatment is limited. Elemental analysis showed that no leaching occurred upon gas-phase oxidation, whereas 90% of the metal was lost with a liquid-phase reflux HNO 3 treatment. © 2012 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.carbon.2012.05.020

• 2012 • 66	Influence of process parameters on the crystallinity, morphology and composition of tungsten oxide-based thin films grown by metalorganic chemical vapor deposition De Los Arcos, T. and Cwik, S. and Milanov, A.P. and Gwildies, V. and Parala, H. and Wagner, T. and Birkner, A. and Rogalla, D. and Becker, H.-W. and Winter, J. and Ludwig, Al. and Fischer, R.A. and Devi, A. Thin Solid Films 522 11-16 (2012) The growth of tungsten oxide (WO 3) based thin films was achieved via metalorganic chemical vapor deposition using an all-nitrogen coordinated tungsten precursor in combination with oxygen. Film growth was performed on Si(100) substrates in the temperature range of 400-800 °C. Employing multi-technique approaches like X-ray diffraction, scanning electron microscopy, atomic force microscopy, Rutherford back scattering, nuclear reaction analysis and X-ray photoelectron spectroscopy, the variation of the growth characteristics and film properties with deposition temperature were studied in terms of crystallinity, structure, surface roughness and composition. Special attention was devoted to the investigation of variations in the film composition for the as-deposited and annealed films. © 2011 Elsevier B.V.
  	view abstract	doi: 10.1016/j.tsf.2011.12.007

• 2012 • 65	Influence of surface functional groups on lithium ion intercalation of carbon cloth Ventosa, E. and Xia, W. and Klink, S. and La Mantia, F. and Muhler, M. and Schuhmann, W. Electrochimica Acta 65 22-29 (2012) Commercial carbon cloth made of PAN-based carbon fibres was used as free-standing anode for lithium intercalation. The role of surface functional groups on the specific irreversible charge loss and reversible charge during the intercalation and de-intercalation of lithium ions into carbon cloth has been investigated. Oxygen groups have been introduced by nitric acid vapour treatment and subsequently gradually removed by thermal treatment at different temperatures in He or H 2 atmosphere as confirmed by X-ray photoelectron spectroscopy. A clear correlation between the amount of surface-bound oxygen groups and the irreversible specific charge was observed. Three irreversible processes were distinguished during the first cathodic scan: (i) reduction of oxygen groups, (ii) formation of the solid electrolyte interphase (SEI) and (iii) presumably exfoliation. The latter one was only observed for samples with low surface oxygen concentration, and its contribution to the irreversible capacity was small due to the low graphitization degree of the samples. An increased specific reversible charge upon increasing the amount of oxygen-containing groups was observed with the main improvement above 1.5 V. © 2012 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.electacta.2011.12.128

• 2012 • 64	Interface of nanoparticle-coated electropolished stents Neumeister, A. and Bartke, D. and Bärsch, N. and Weingärtner, T. and Guetaz, L. and Montani, A. and Compagnini, G. and Barcikowski, S. Langmuir 28 12060-12066 (2012) Nanostructures entail a high potential for improving implant surfaces, for instance, in stent applications. The electrophoretic deposition of laser-generated colloidal nanoparticles is an appropriate tool for creating large-area nanostructures on surfaces. Until now, the bonding and characteristics of the interface between deposited nanoparticles and the substrate surface has not been known. It is investigated using X-ray photoelectron spectroscopy, Auger electron spectroscopy, and transmission electron microscopy to characterize an electropolished NiTi stent surface coated by laser-generated Au and Ti nanoparticles. The deposition of elemental Au and Ti nanoparticles is observed on the total 3D surface. Ti-coated samples are composed of Ti oxide and Ti carbide because of nanoparticle fabrication and the coating process carried out in 2-propanol. The interface between nanoparticles and the electropolished surface consists of a smooth, monotone elemental depth profile. The interface depth is higher for the Ti nanoparticle coating than for the Au nanoparticle coating. This smooth depth gradient of Ti across the coating-substrate intersection and the thicker interface layer indicate the hard bonding of Ti-based nanoparticles on the surface. Accordingly, electron microscopy reveals nanoparticles adsorbed on the surface without any sorption-blocking intermediate layer. The physicomechanical stability of the bond may benefit from such smooth depth gradients and direct, ligand-free contact. This would potentially increase the coating stability during stent application. © 2012 American Chemical Society.
  	view abstract	doi: 10.1021/la300308w

• 2012 • 63	Interfacial interaction driven CO oxidation: Nanostructured Ce 1-xLa xO 2-δ/TiO 2 solid solutions Katta, L. and Reddy, B.M. and Muhler, M. and Grünert, W. Catalysis Science and Technology 2 745-753 (2012) Titania supported ceria-lanthana solid solutions (Ce xLa 1-xO 2-δ/TiO 2; CLT) have been synthesized by a facile and economical route. Existence of synergism between ceria-lanthana (CL) solid solutions and titania-anatase phase, which leads to decrease in the crystallite size, retarded titania phase transformation, and improved redox properties, has been thoroughly investigated by various techniques, namely, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), Raman spectroscopy (UV-RS and Vis-RS), BET surface area analysis, and temperature programmed reduction (TPR). Two key observations made from the whole exercise were (i) mutual interaction of Ce and Ti ions could impose typical Ce-O-Ti modes at the interfacial region and (ii) the La 3+ ion as a dopant provokes a large number of oxygen vacancies via a charge compensation mechanism. The promising role of these factors in the CO oxidation (one of the most formidable challenges) has been comprehensively described. The observed enhanced activity for the CLT sample is primarily attributed to an apparent specific orientation of the active component over the support, which is endorsed by the interfacial interaction. This specific mode could facilitate the CO adsorption with simultaneous bulk oxygen diffusion for more consumption and in turn better activity. © 2012 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c2cy00449f

• 2012 • 62	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 abstract	doi: 10.1002/cssc.201100284

• 2012 • 61	On the role of the residual iron growth catalyst in the gasification of multi-walled carbon nanotubes with carbon dioxide Jin, C. and Xia, W. and Chen, P. and Muhler, M. Catalysis Today 186 128-133 (2012) The gasification of carbon with CO 2 was applied to examine the role of the residual iron growth catalyst in multi-walled carbon nanotubes (CNTs), which were pre-treated either by refluxing in nitric acid at 120 °C or by nitric acid vapor at 200 °C. Temperature-programmed desorption (TPD) and surface reaction (TPSR) experiments were performed in He and CO 2, respectively. The Fe nanoparticles were retained after the treatment in HNO 3 vapor, whereas the liquid HNO 3 treatment was able to remove the accessible residual Fe catalyst. The exposed Fe nanoparticles were found to catalyze the gasification of CNTs with CO 2 according to the reverse Boudouard reaction C + CO 2 = 2CO. In case of the CNTs pretreated in HNO 3 vapor, evolving CO 2 formed due to the decomposition of oxygen-containing functional groups during the TPD experiments was fully converted above 750 °C into desorbing CO, and the addition of 2000 ppm CO 2 in the feed gas during the TPSR experiments resulted in full conversion at 1000 °C. X-ray photoelectron spectroscopy studies show that the treatment in HNO 3 vapor at 200 °C favors the formation of oxygen species doubly bound to carbon (CO groups). During the TPSR experiments, CO 2 as a weak oxidant partially oxidized the CNTs leading to the formation of CO groups, and a much higher amount of these groups was detected on HNO 3 vapor-treated CNTs with residual Fe catalyst. Their presence suggests that CO groups are reaction intermediates of the CNT gasification with CO 2, which is considered an effective test reaction for the presence of residual catalytically active nanoparticles. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.cattod.2012.02.052

• 2012 • 60	Quantitative studies on the oxygen and nitrogen functionalization of carbon Nanotubes Performed in the Gas Phase Li, C. and Zhao, A. and Xia, W. and Liang, C. and Muhler, M. Journal of Physical Chemistry C 116 20930-20936 (2012) Gas-phase methods were applied for the oxygen and nitrogen functionalization of multiwalled carbon nanotubes (CNTs). The oxygen functionalization was performed by HNO 3 vapor treatment at temperatures from 200 to 250 °C for 12 h up to 120 h. The oxygen-functionalized CNTs were used as the starting material for nitrogen functionalization through thermal treatment under NH 3. The BET surface area increased after the treatment in HNO 3 vapor, which also caused the weight loss due to carbon corrosion. The oxygen content increased with increasing treatment time but decreased with increasing temperature, as disclosed by elemental analysis, X-ray photoelectron spectroscopy, and temperature-programmed desorption (TPD) results. The surface acidity increased with increasing treatment time as shown by TPD using NH 3 as a probe molecule. As to nitrogen functionalization, the amount of nitrogen was correlated with the oxygen amount in the starting CNTs. A higher NH 3 concentration caused a lower BET surface area due to carbon corrosion. The incorporation of both oxygen and nitrogen lowered the thermal resistance of CNTs. The nitrogen-functionalized CNTs showed only a slight decrease, in contrast to a significant decrease observed for O-functionalized CNTs. The formation or removal of coordinatively unsaturated carbon like amorphous carbon or defects was found to be involved in all of the functionalization, desorption, and oxidation processes. © 2012 American Chemical Society.
  	view abstract	doi: 10.1021/jp306866q

• 2012 • 59	Rare-earth substituted HfO2 thin films grown by metalorganic chemical vapor deposition Devi, A. and Cwik, S. and Xu, K. and Milanov, A.P. and Noei, H. and Wang, Y. and Barreca, D. and Meijer, J. and Rogalla, D. and Kahn, D. and Cross, R. and Parala, H. and Paul, S. Thin Solid Films 520 4512-4517 (2012) Thin films of HfGdOx and HfDyOx were deposited by metalorganic chemical vapor deposition (MOCVD) utilizing guanidinate precursors for Hf, Gd and Dy. The close match in the thermal properties of the precursors enabled the MOCVD of rare-earth (RE) substituted HfO2 over a wide temperature window. Film deposition was carried out in the temperature range 300-700 °C in the presence of oxygen on Si(100) substrates. HfGdO x films were analyzed in detail for their structure, composition and morphology using X-ray diffraction, Rutherford backscattering spectrometry, proton induced X-ray emission, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrical properties of HfGdOx in terms of capacitance-voltage and current-voltage characteristics of metal-insulator- semiconductor device structures were evaluated. © 2011 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.tsf.2011.10.141

• 2012 • 58	Stability of platinum nanoparticles supported on SiO2/Si(111): A high-pressure X-ray photoelectron spectroscopy study Porsgaard, S. and Merte, L.R. and Ono, L.K. and Behafarid, F. and Matos, J. and Helveg, S. and Salmeron, M. and Roldan Cuenya, B. and Besenbacher, F. ACS Nano 6 10743-10749 (2012) The stability of Pt nanoparticles (NPs) supported on ultrathin SiO 2 films on Si(111) was investigated in situ under H2 and O2 (0.5 Torr) by high-pressure X-ray photoelectron spectroscopy (HP-XPS) and ex situ by atomic force microscopy (AFM). No indication of sintering was observed up to 600 C in both reducing and oxidizing environments for size-selected Pt NPs synthesized by inverse micelle encapsulation. However, HP-XPS revealed a competing effect of volatile PtOx desorption from the Pt NPs (∼2 and ∼4 nm NP sizes) at temperatures above 450 C in the presence of 0.5 Torr of O2. Under oxidizing conditions, the entire NPs were oxidized, although with no indication of a PtO2 phase, with XPS binding energies better matching PtO. The stability of catalytic NPs in hydrogenation and oxidation reactions is of great importance due to the strong structure sensitivity observed in a number of catalytic processes of industrial relevance. An optimum must be found between the maximization of the surface active sites and metal loading (i.e., minimization of the NP size), combined with the maximization of their stability, which, as it will be shown here, is strongly dependent on the reaction environment. © 2012 American Chemical Society.
  	view abstract	doi: 10.1021/nn3040167

• 2012 • 57	Stabilization of mid-sized silicon nanoparticles by functionalization with acrylic acid Bywalez, R. and Karacuban, H. and Nienhaus, H. and Schulz, C. and Wiggers, H. Nanoscale Research Letters 7 1-16 (2012) We present an enhanced method to form stable dispersions of medium-sized silicon nanoparticles for solar cell applications by thermally induced grafting of acrylic acid to the nanoparticle surface. In order to confirm their covalent attachment on the silicon nanoparticles and to assess the quality of the functionalization, X-ray photoelectron spectroscopy and diffuse reflectance infrared Fourier spectroscopy measurements were carried out. The stability of the dispersion was elucidated by dynamic light scattering and Zeta-potential measurements, showing no sign of degradation for months. © 2012 Bywalez et al.
  	view abstract	doi: 10.1186/1556-276X-7-76

• 2012 • 56	Strontium doping in mullite-type bismuth aluminate: A vacancy investigation using neutrons, photons and electrons Gesing, T.M. and Schowalter, M. and Weidenthaler, C. and Murshed, M.M. and Nénert, G. and Mendive, C.B. and Curti, M. and Rosenauer, A. and Buhl, J.-C. and Schneider, H. and Fischer, R.X. Journal of Materials Chemistry 22 18814-18823 (2012) We report on strontium doped dibismuth-nonaoxoaluminate(iii) produced at 1023 K. Partial substitution of bismuth by strontium in the structure yields oxygen vacancies for charge balance. Introducing oxygen vacancies rearranged the associated Al<inf>2</inf>O<inf>7</inf> double-tetrahedra forming "Al <inf>3</inf>O<inf>10</inf>" tri-clusters which were identified by multi-quantum 27Al MAS NMR. Both STEM-EDX and XPS showed homogeneous distribution of strontium in the bulk and on the surface, respectively. Moreover, XPS confirms the valence state of bismuth after doping. The orientations of bismuth 6s2 lone electron pairs were calculated using DFT methods. The amount of strontium in the crystal structure was further confirmed from the decomposition product SrAl<inf>12</inf>O<inf>19</inf> formed during the temperature-dependent X-ray powder diffraction. The structural proof was carried out by refining the structure of (Bi<inf>0.94</inf>Sr <inf>0.06</inf>)<inf>2</inf>Al<inf>4</inf>O<inf>8.94</inf> from powder neutron and X-ray diffraction data. Rietveld refinements clearly showed the under occupation of one oxygen site and the shift of two aluminum atoms from the double-tetrahedra to two tri-cluster sites. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c2jm33208f

• 2012 • 55	Surface modification of poly(ethylene terephthalate) fabric via photo-chemical reaction of dimethylaminopropyl methacrylamide Mohamed, N.H. and Bahners, T. and Wego, A. and Gutmann, J.S. and Ulbricht, M. Applied Surface Science 259 261-269 (2012) Photo-chemical reactions and surface modifications of poly(ethylene terephthalate) (PET) fabrics with the monomer dimethylaminopropyl methacrylamide (DMAPMA) and benzophenone (BP) as photo-initiator using a broad-band UV lamp source were investigated. The tertiary amino groups of the grafted poly(DMAPMA) chains were subsequently quaternized with alkyl bromides of different chain lengths to establish antibacterial activity. The surface composition, structure and morphology of modified PET fabrics were characterized by Fourier transform infrared spectroscopy (FTIR/ATR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). To evaluate the amount of quaternary and tertiary ammonium groups on the modified surface, PET was dyed with an acid dye which binds to the ammonium groups. Therefore, the color depth is a direct indicator of the amount of ammonium groups. The resulting antibacterial activity of the modified PET fabrics was tested with Escherichia coli. The results of all experiments show that a photochemical modification of PET is possible using DMAPMA, benzophenone and UV light. Also, the quaternization of tertiary amino groups as well as the increase in antibacterial activity of the modified PET by the established quaternary ammonium groups were successful. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2012.07.029

• 2012 • 54	Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis Kundu, S. and Nagaiah, T.C. and Chen, X. and Xia, W. and Bron, M. and Schuhmann, W. and Muhler, M. Carbon 50 4534-4542 (2012) A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells. © 2012 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.carbon.2012.05.037

• 2012 • 53	The Role of Oxygen- and Nitrogen-containing Surface Groups on the Sintering of Iron Nanoparticles on Carbon Nanotubes in Different Atmospheres Sánchez, M.D. and Chen, P. and Reinecke, T. and Muhler, M. and Xia, W. ChemCatChem 4 1997-2004 (2012) The sintering of iron nanoparticles on carbon nanotubes (CNTs) under different atmospheres was investigated. CNTs were first treated with HNO3 vapor at 200°C to obtain O-functionalized CNTs (OCNTs). The OCNTs were treated in ammonia at 400°C to obtain N-doped CNTs (NCNTs). Highly dispersed FeOx nanoparticles were subsequently deposited by chemical vapor deposition from ferrocene under oxidizing conditions. The obtained FeOx/OCNT and FeOx/NCNT samples were allowed to sinter at 500°C under flowing helium, hydrogen, or ammonia. The samples were studied by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. A significant increase in particle size and a decrease in Fe surface atomic concentration were observed in all the sintered samples. The sintering on OCNTs was more severe than on NCNTs, which can be attributed to stronger metal-substrate interactions and a higher amount of surface defects on NCNTs. The applied gas atmosphere had a substantial influence on the sintering behavior of the nanoparticles: treatment in helium led to the growth of particles and a significant widening of particle size distributions, whereas treatment in hydrogen or ammonia resulted in the growth of particles, but not in the widening of particle size distributions. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cctc.201200286

• 2012 • 52	Toward remote-controlled valve functions via magnetically responsive capillary pore membranes Himstedt, H.H. and Yang, Q. and Qian, X. and Ranil Wickramasinghe, S. and Ulbricht, M. Journal of Membrane Science 423-424 257-266 (2012) Polyethyleneterephthalate track-etched membranes with a pore diameter of 650nm were functionalized via surface-initiated atom transfer radical polymerization with grafted poly(2-hydroxyethylmethacrylate). Grafted chain length and density were varied. Superparamagnetic nanoparticles (Fe 3O 4; core diameter 15nm) were selectively covalently coupled to the end groups of the grafted chains. The membranes were characterized by grafting degree, X-ray photoelectron spectroscopy, electron microscopy, zeta potential and pore size in dry state via gas flow/pore dewetting permporometry. The results confirmed that all functionalization steps were well controlled. Water permeability measurements allowed estimation of the hydrodynamic pore diameter of the membranes, and, hence, the hydrodynamic polymer layer thickness on the pore walls. The water permeability of the nanoparticle hybrid membranes was then measured in a static or an alternating external magnetic field. Significant and reversible decreases of permeability were observed, with the largest effects for membranes with high polymer grafting density and long polymer chains (hydrodynamic layer thickness up to 100nm). The maximum change in effective pore diameter was only 6%. However, the estimated change of swollen polymer layer thickness (originally between 60 and 100nm) was up to 13nm. The functionality of the membranes can be tuned by variations of straightforward parameters such as pore size or grafted chain lengths. The study is also relevant as a model system for altering the effective thickness of grafted polymer layers on a surface by an external magnetic field for other applications, for instance in microfluidic systems. © 2012 Elsevier B.V.
  	view abstract	doi: 10.1016/j.memsci.2012.08.015

• 2012 • 51	UV-photo graft functionalization of polyethersulfone membrane with strong polyelectrolyte hydrogel and its application for nanofiltration Bernstein, R. and Antón, E. and Ulbricht, M. ACS Applied Materials and Interfaces 4 3438-3446 (2012) A strong polyelectrolyte hydrogel was graft copolymerized on a polyethersulfone (PES) ultrafiltration (UF) membrane using vinyl sulfonic acid (VSA) as the functional monomer, and N,N′-methylenbisacrylamide (MBAA) as the cross-linker monomer. This was carried out in one simple step using the UV photoirradiation method. The effect of the polymerization conditions on the degree of grafting (DG) was investigated using the gravimetric method which measures the total hydrogel grafted on the membrane, and with ATR-FTIR spectroscopy which indicates the functional monomer fraction in the hydrogel layer. The VSA could not graft polymerize without the cross-linker as comonomer. An increase in the cross-linker fraction from 0.25 to 2.5 mol % (relative to the functional monomer VSA) resulted in a higher DG. Although the surface morphology changed upon modification, the resulting surface roughness as measured by AFM was very low. From the monitoring of DG with UV time (4.5-30 min) at constant conditions, it was deduced that during the early stages of the polymerization mainly the cross-linker was grafted, thus inducing the graft copolymerization of the functional monomer. Polymerization using a higher monomer concentration (12.5-40% VSA) at constant monomer/cross-linker ratio resulted in a higher VSA fraction in the grafted hydrogel, although the gravimetric DG was similar. Ion exchange capacity and X-ray photoelectron spectroscopy measured after modification under the different conditions supported these findings. The new membranes were tested under nanofiltration (NF) conditions. A NF membrane could be obtained when the MBAA fraction was above 0.25%. The Na 2SO 4 rejection was 90-99% and the permeability 10-1 L m -2 h -1 bar -1 when the MBAA fraction increased from 0.75 to 2.5%. The order of rejection of single salts solution was Na 2SO 4 > MgSO 4 ≈ NaCl > CaCl 2, as expected on the basis of Donnan exclusion for negatively charged NF membranes. An increase in the salts rejection with increasing degree of cross-linking and VSA fraction was attributed to an increase in the membrane charge density and to steric exclusion that also resulted in an increase of rejection for uncharged solutes such as sucrose or glucose. The new membrane presented a high, essentially unchanged Na 2SO 4 rejection (>97%) in the range of salt concentrations up to 4 g/L, and only slightly reduced rejection (>92%) at a concentration of 8 g/L; this can be related to its high barrier layer charge density measured by ion exchange capacity. In addition, because poly(vinyl sulfonic acid) (PVSA) is a strong polyelectrolyte the membrane separation performance was stable in the range of pH 1.5 to pH 10. © 2012 American Chemical Society.
  	view abstract	doi: 10.1021/am300426c

• 2011 • 50	A new nanospectroscopy tool with synchrotron radiation: NanoESCA@Elettra Wiemann, C. and Patt, M. and Krug, I.P. and Weber, N.B. and Escher, M. and Merkel, M. and Schneider, C. M. e-Journal of Surface Science and Nanotechnology 9 395-399 (2011) We describe first experiences with a novel spectromicroscopy set-up - NanoESCA@Elettra - which has been installed at the nanospectroscopy soft x-ray beamline at Elettra (Trieste). The system features an energy-filtered photoemission microscope with a 30 kV immersion lens system and a double-hemispherical energy analyzer. The instrument provides both real space and k-space mapping modes. Experiments on nanostructured samples with laboratory gas discharge sources show a lateral resolution of less than 50 nm and an energy resolution of better than 200 meV. We have also performed first tests of the instrument with synchrotron radiation. © 2011 The Surface Science Society of Japan.
  	view abstract	doi: 10.1380/ejssnt.2011.395

• 2011 • 49	Basic investigation of HfO2 based metal-insulator-metal diodes Dudek, P. and Schmidt, R. and Lukosius, M. and Lupina, G. and Wenger, C. and Abrutis, A. and Albert, M. and Xu, K. and Devi, A. Thin Solid Films 519 5796-5799 (2011) Very fast frequency response of metal-insulator-metal (MIM) diodes extends into the terahertz regime making them attractive as key elements as alternative to photovoltaic solar energy harvesting and ultrahigh speed wireless communication systems. The tunnelling phenomena, which is crucial for achieving high performance in these devices is extremely sensitive to the nanoscale structural and chemical quality of interface regions. Modern chemical deposition techniques like Pulsed Injected Metal-Organic Chemical Vapour Deposition (PICVD), Atomic Layer Deposition (ALD) and Atomic Vapour Deposition (AVD®) will be used for the extremely precise growth of thin HfO2 films on TiN bottom electrodes. However, different deposition techniques may give unpredictably different results in terms of film density, surface and interface property and consequently in physical properties of the device. In this work, the influence of deposition techniques on the charge transport characteristics of HfO2 MIM diodes was investigated by Conducting Atomic Force Microscopy (C-AFM) and X-ray Photoelectron Spectroscopy (XPS). © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.tsf.2010.12.195

• 2011 • 48	Comparative study of hydrothermal treatment and thermal annealing effects on the properties of electrodeposited micro-columnar ZnO thin films Lupan, O. and Pauporté, T. and Tiginyanu, I.M. and Ursaki, V.V. and Şontea, V. and Ono, L.K. and Cuenya, B.R. and Chow, L. Thin Solid Films 519 7738-7749 (2011) We report a comparison of the role played by different sample treatments, namely, a low-temperature hydrothermal treatment by hot H2O vapor in an autoclave versus thermal annealing in air on the properties of ZnO films grown by electrochemical deposition (ECD). Scanning electron microscopy studies reveal a homogeneous micro-columnar morphology and changes in the film surface for the two different treatments. It is found that post-growth hydrothermal treatments of ECD ZnO films at 150 °C under an aqueous environment enhance their structural and optical properties (photoluminescence, transmission, Raman spectra, etc.) similar to thermal annealing in air at higher temperatures (> 200 °C). The modifications of the structural and optical properties of ZnO samples after thermal annealing in air in the temperature range of 150-600 °C are discussed. The removal of chlorine from the films by the hydrothermal treatment was evidenced which could be the main reason for the improvement of the film quality. The observation of the enhanced photoluminescence peak at 380 nm demonstrates the superior properties of the hydrothermally treated ZnO films as compared to the films annealed in air ambient at the same or higher temperature. This post-growth hydrothermal treatment would be useful for the realization of high performance optoelectronic devices on flexible supports which might not withstand at high temperature annealing treatments. © 2011 Elsevier B.V. All rights reseved.
  	view abstract	doi: 10.1016/j.tsf.2011.05.072

• 2011 • 47	Evaluation of homoleptic guanidinate and amidinate complexes of gadolinium and dysprosium for MOCVD of rare-earth nitride thin films Thiede, T.B. and Krasnopolski, M. and Milanov, A.P. and De Los Arcos, T. and Ney, A. and Becker, H.-W. and Rogalla, D. and Winter, J. and Devi, A. and Fischer, R.A. Chemistry of Materials 23 1430-1440 (2011) Metal-organic chemical vapor deposition (MOCVD) of thin films of two representative rare-earth nitrides is reported here for the first time. Four homoleptic, all-nitrogen-coordinated, rare-earth (RE) complexes were evaluated as precursors for the respective nitride thin film materials. Two guanidinato complexes [RE{(iPrN)2C(NMe2)}3] [RE = Gd (1), Dy (2)] and two amidinato complexes [RE{(iPrN) 2CMe}3] [RE = Gd (3), Dy (4)] were compared and used either as single source precursors or together with ammonia for MOCVD of gadolinium nitride (GdN) and dysprosium nitride (DyN), respectively. The thermal properties of the precursors were studied and the fragmentation patterns were characterized by high-resolution electron impact-mass spectrometry (HR EI-MS). The obtained nitride films were investigated using a series of techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), nuclear reaction analysis (NRA), Rutherford backscattering (RBS), and X-ray photoelectron spectroscopy (XPS). The films contain preferentially oriented grains of fcc-GdN and DyN and are contaminated with small amounts of carbon and oxygen (significantly below 10 at.-% in the best cases). The temperature-dependent magnetic properties of the films, as measured using a superconducting quantum interference device (SQUID), suggest the existence of small ferromagnetic grains of the rare-earth nitrides that exhibit superparamagnetism. Despite the chemical and structural similarity of the guanidinato and amidinato complexes (1-4), a distinctly different behavior as MOCVD precursors was found for 1 and 2, compared with that for 3 and 4. While the guanidinates operate well as single-source precursors (SSPs), the amidinates are not suited at all as SSPs, but give very good nitride films when used in the presence of ammonia. This characteristic behavior was correlated with the different fragmentation mechanisms, as revealed by EI-MS. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/cm102840v

• 2011 • 46	Evolution of the structure and chemical state of Pd nanoparticles during the in situ catalytic reduction of NO with H2 Paredis, K. and Ono, L.K. and Behafarid, F. and Zhang, Z. and Yang, J.C. and Frenkel, A.I. and Cuenya, B.R. Journal of the American Chemical Society 133 13455-13464 (2011) An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO2-supported Pd nanocatalysts (∼5 nm) during the in situ reduction of NO with H2 using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction (≤120 °C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO2 support was observed, and Pd δ+ species were detected. This process parallels the high production of N2O observed at the onset of the reaction (>120 °C), while at higher temperatures (≥150 °C) the selectivity shifts mainly toward N2 (∼80%). Concomitant with the onset of N 2 production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H2-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdOx was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/ja203709t

• 2011 • 45	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 abstract	doi: 10.1021/ja210078d

• 2011 • 44	High-throughput characterization of Pt supported on thin film oxide material libraries applied in the oxygen reduction reaction Schäfer, D. and Mardare, C. and Savan, A. and Sanchez, M.D. and Mei, B. and Xia, W. and Muhler, M. and Ludwig, Al. and Schuhmann, W. Analytical Chemistry 83 1916-1923 (2011) Thin film metal oxide material libraries were prepared by sputter deposition of nanoscale Ti/Nb precursor multilayers followed by ex situ oxidation. The metal composition was varied from 6 at.% Nb to 27 at.% Nb. Additionally, thin wedge-type layers of Pt with a nominal thickness gradient from 0 to 5 nm were sputter-deposited on top of the oxides. The materials libraries were characterized with respect to metallic film composition, oxide thickness, phases, electrical conductivity, Pt thickness, and electrochemical activity for the oxygen reduction reaction (ORR). Electrochemical investigations were carried out by cyclic voltammetry using an automated scanning droplet cell. For a nominal Pt thickness >1 nm, no significant dependence of the ORR activity on the Pt thickness or the substrate composition was observed. However, below that critical thickness, a strong decrease of the surface-normalized activity in terms of reduction currents and potentials was observed. For such thin Pt layers, the conductivity of the substrate seems to have a substantial impact on the catalytic activity. Results from X-ray photoelectron spectroscopy (XPS) measurements suggest that the critical Pt thickness coincides with the transition from a continuous Pt film into isolated particles at decreasing nominal Pt thickness. In the case of isolated Pt particles, the activity of Pt decisively depends on its ability to exchange electrons with the oxide layer, and hence, a dependence on the substrate conductivity is rationalized. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/ac102303u

• 2011 • 43	Highly active metal-free nitrogen-containing carbon catalysts for oxygen reduction synthesized by thermal treatment of polypyridine-carbon black mixtures Xia, W. and Masa, J. and Bron, M. and Schuhmann, W. and Muhler, M. Electrochemistry Communications 13 593-596 (2011) A straight-forward method for the synthesis of metal-free catalysts for oxygen reduction by thermal treatment of a mixture of poly(3,5-pyridine) with carbon black in helium is reported. The catalyst was characterized by X-ray diffraction and photoelectron spectroscopy, cyclic voltammetry and rotating disk electrode measurements. The new catalyst exhibited remarkable activity similar to Pt-based catalysts in alkaline media. © 2011 Elsevier B.V. All Rights Reserved.
  	view abstract	doi: 10.1016/j.elecom.2011.03.018

• 2011 • 42	Highly dispersed MoO 3/Al 2O 3 shell-core composites synthesized by CVD of Mo(CO) 6 under atmospheric pressure Shi, G. and Franzke, T. and Xia, W. and Sanchez, M.D. and Muhler, M. Chemical Vapor Deposition 17 162-169 (2011) MoO 3/γ-Al 2O 3 composites are synthesized by CVD under atmospheric pressure using Mo(CO) 6 as the precursor and porous γ-Al 2O 3 particles in a horizontal, rotating, hot-wall reactor, which is also used for calcination in air. The composites are characterized by N 2 physisorption, atomic absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), and laser Raman spectroscopy (LRS). The synthesized samples exhibit excellent porosity, even at high Mo loadings. A much higher Mo yield is achieved when applying sublimation-adsorption in static air instead of using flowing N 2. A high degree of Mo dispersion on alumina is confirmed by XRD, LRS, and TEM; with a Mo surface density as high as 5.2 atoms nm -2, the sample is X-ray amorphous, there are no polymeric molybdate species detectable by LRS, and the island size of the molybdate species is about 1 nm according to TEM. The XPS analysis shows that exclusively Mo VI species are present on all synthesized samples. Thus, the applied rotating, hot-wall reactor achieves efficient mixing and homogeneous deposition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201106909

• 2011 • 41	Infrared spectroscopic ellipsometry (IRSE) and X-ray photoelectron spectroscopy (XPS) monitoring the preparation of maleimide-functionalized surfaces: From Au towards Si (111) Sun, G. and Hovestädt, M. and Zhang, X. and Hinrichs, K. and Rosu, D.M. and Lauermann, I. and Zielke, C. and Vollmer, A. and Löchel, H. and Ay, B. and Holzhütter, H.-G. and Schade, U. and Esser, N. and Volkmer, R. and Rappich, J. Surface and Interface Analysis 43 1203-1210 (2011) The IR ellipsometric technique was used to identify the surface species and to control the preparation of maleimide-terminated surfaces. Because of higher s/n ratios for metallic substrates, the protocol was initially developed on Au surfaces, was later successfully transferred to technologically more relevant Si (111) substrates. The functionalized surfaces were achieved by electrochemical deposition of diazonium linker films and following chemical adsorption steps. Complementary XPS was also employed to detect the surface species in the process of preparation. The immobilization of different functional molecules was proven by interpreting the specific vibrational bands in IR spectra and additionally confirmed by XPS experiments. The surface homogeneity was investigated by FT-IR synchrotron mapping ellipsometry. This work shows that the proposed protocol is an effective pathway to achieve the desired functionalized surfaces. Copyright © 2010 John Wiley & Sons, Ltd.
  	view abstract	doi: 10.1002/sia.3699

• 2011 • 40	Isolated silicon dangling bonds on a water-saturated n+-doped Si(001)-2 × 1 surface: An XPS and STM study Gallet, J.-J. and Bournel, F. and Rochet, F. and Köhler, U. and Kubsky, S. and Silly, M.G. and Sirotti, F. and Pierucci, D. Journal of Physical Chemistry C 115 7686-7693 (2011) Using Si 2p core-level X-ray photoelectron spectroscopy we have measured the upward band bending at the surface of n+-doped water-saturated Si(001)-2 × 1 and inferred the macroscopic negative surface charge density of the surface. These macroscopic results are in excellent accord with the microscopic view provided by dual-bias scanning tunneling microscopy showing that the isolated silicon dangling bonds (∼1.2 × 10-2 defects per Si atom) bear indeed a negative charge. Noting the structural analogy between isolated dangling bonds on water-saturated Si(001) and H-terminated Si(001), in the final, prospective section of the paper, we raise the question of the possible role that these defects could play in radical chain reactions with π-bonded molecules, in relationship with the hydride/hydroxyl patterns that are resolved in the scanning tunneling images. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/jp201262x

• 2011 • 39	Magnetically activated micromixers for separation membranes Himstedt, H.H. and Yang, Q. and Dasi, L.P. and Qian, X. and Wickramasinghe, S.R. and Ulbricht, M. Langmuir 27 5574-5581 (2011) Presented here is a radically novel approach to reduce concentration polarization and, potentially, also fouling by colloids present in aqueous feeds: magnetically responsive micromixing membranes. Hydrophilic polymer chains, poly(2-hydroxyethyl methacrylate) (PHEMA), were grafted via controlled surface-initiated atom transfer radical polymerization (SI-ATRP) on the surface of polyamide composite nanofiltration (NF) membranes and then end-capped with superparamagnetic iron oxide magnetite (Fe3O4) nanoparticles. The results of all functionalization steps, that is, bromide ATRP initiator immobilization, SI-ATRP, conversion of PHEMA end groups from bromide to amine, and carboxyl-functional Fe3O4 nanoparticle immobilization via peptide coupling, have been confirmed by X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FESEM). These nanoparticles experience a magnetic force as well as a torque under an oscillating external magnetic field. It has been shown, using particle image velocimetry (PIV), that the resulting movement of the polymer brushes at certain magnetic field frequencies induces mixing directly above the membrane surface. Furthermore, it was demonstrated that with such membranes the NF performance could significantly be improved (increase of flux and salt rejection) by an oscillating magnetic field, which can be explained by a reduced concentration polarization in the boundary layer. However, the proof-of-concept presented here for the active alteration of macroscopic flow via surface-anchored micromixers based on polymer-nanoparticle conjugates has much broader implications. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/la200223g

• 2011 • 38	Malonate complexes of dysprosium: Synthesis, characterization and application for LI-MOCVD of dysprosium containing thin films Milanov, A.P. and Seidel, R.W. and Barreca, D. and Gasparotto, A. and Winter, M. and Feydt, J. and Irsen, S. and Becker, H.-W. and Devi, A. Dalton Transactions 40 62-78 (2011) A series of malonate complexes of dysprosium were synthesized as potential metalorganic precursors for Dy containing oxide thin films using chemical vapor deposition (CVD) related techniques. The steric bulkiness of the dialkylmalonato ligand employed was systematically varied and its influence on the resulting structural and physico-chemical properties that is relevant for MOCVD was studied. Single crystal X-ray diffraction analysis revealed that the five homoleptic tris-malonato Dy complexes (1-5) are dimers with distorted square-face bicapped trigonal-prismatic geometry and a coordination number of eight. In an attempt to decrease the nuclearity and increase the solubility of the complexes in various solvents, the focus was to react these dimeric complexes with Lewis bases such as 2,2′-biypridyl and pyridine (6-9). This resulted in monomeric tris-malonato mono Lewis base adduct complexes with improved thermal properties. Finally considering the ease of synthesis, the monomeric nature and promising thermal characteristics, the silymalonate adduct complex [Dy(dsml)3bipy] (8) was selected as single source precursor for growing DySixOy thin films by liquid injection metalorganic chemical vapor deposition (LI-MOCVD) process. The as-deposited films were analyzed for their morphology and composition by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, Rutherford backscattering (RBS) analysis and X-ray photoelectron spectroscopy. © 2011 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c0dt00455c

• 2011 • 37	MBE growth optimization of topological insulator Bi2Te 3 films Krumrain, J. and Mussler, G. and Borisova, S. and Stoica, T. and Plucinski, L. and Schneider, C.M. and Grützmacher, D. Journal of Crystal Growth 324 115-118 (2011) We investigated the growth of the topological insulator Bi 2Te3 on Si(1 1 1) substrates by means of molecular-beam epitaxy (MBE). The substrate temperature as well as the Bi and Te beam-equivalent pressure (BEP) was varied in a large range. The structure and morphology of the layers were studied using X-ray diffraction (XRD), X-ray reflectivity (XRR) and atomic force microscopy (AFM). The layer-by-layer growth mode with quintuple layer (QL) as an unit is accomplished on large plateaus if the MBE growth takes place in a Te overpressure. At carefully optimized MBE growth parameters, we obtained atomically smooth, single-crystal Bi 2Te3 with large area single QL covering about 75% of the layer surface. Angular-resolved photoelectron spectroscopy reveals a linear energy dispersion of charge carriers at the surface, evidencing topologically insulating properties of the Bi2Te3 epilayers. © 2011 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jcrysgro.2011.03.008

• 2011 • 36	Methylated [(arene)(1,3-cyclohexadiene)Ru(0)] complexes as low-melting MOCVD precursor complexes with a controlled follow-up chemistry of the ligands Jipa, I. and Danova, K. and Popovska, N. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Cremer, T. and Maier, F. and Marbach, H. and Steinrück, H.-P. and Heinemann, F.W. and Zenneck, U. Journal of Materials Chemistry 21 3014-3024 (2011) [(Benzene)(2-methyl-1,3-cyclohexadiene)Ru(0)] (1), [(1,3-cyclohexadiene) (toluene)Ru(0)] (2), and [(methyl-cyclohexadiene)(toluene)Ru(0)] (3, mixture of isomers) have been prepared and tested as new metal organic ruthenium precursor complexes for chemical vapor deposition (MOCVD) with favorable properties. 1 is a low-melting precursor complex (mp = 29 °C) and the isomeric mixture 3 forms a liquid at room temperature. X-ray diffraction studies of single crystals of complexes 1 and 2 are characteristic for true Ru(0) π-complexes without molecular structure peculiarities or significant intermolecular interactions in the solid state, which could hinder undecomposed evaporation. Differential thermal analysis (DTA), differential scanning calorimetry (DSC) and vapor pressure data qualify the compounds as almost ideal MOCVD precursors. Thin ruthenium films have been deposited successfully on silicon wafers and substrate temperatures between 200 and 450 °C in inert gas atmospheres. Film growth and properties were evaluated by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and four-point probe conductivity measurements. All films consist of polycrystalline metallic ruthenium with a low surface roughness. © The Royal Society of Chemistry 2011.
  	view abstract	doi: 10.1039/c0jm02652b

• 2011 • 35	Methylated [(benzene)(1,3-butadiene)Ru0] derivatives as novel MOCVD precursors with favorable properties Jipa, I. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Marbach, H. and Cremer, T. and Maier, F. and Steinrück, H.-P. and Danova, K. and Popovska, N. and Heinemann, F.W. and Zenneck, U. Chemical Vapor Deposition 17 15-21 (2011) [(Benzene)(2-methyl-1,3-butadiene)Ru0] (1), [(benzene)(2,3- dimethyl-1,3-butadiene)Ru0] (2), and [(2,3-dimethyl-1,3-butadiene) (toluene)Ru0] (3) are prepared and tested as new metal-organic (MO) ruthenium precursor complexes with favorable deposition properties for the CVD of thin ruthenium films. X-ray diffraction (XRD) studies of single crystals of the complexes are characteristic for true Ru0 π-complexes without molecular structure peculiarities or significant intermolecular interactions in the solid state, which can hinder undecomposed evaporation. Differential thermal analysis (DTA) and vapor pressure data qualify the compounds as almost ideal MOCVD precursors. Thin ruthenium films are deposited successfully on silicon wafers at substrate temperatures between 200 and 400°C in a nitrogen gas atmosphere. X-ray photoelectron spectroscopy (XPS), four-point probe conductivity measurements, and atomic force microscopy (AFM) are used to characterize the films. All films consist of polycrystalline metallic ruthenium with a low surface roughness. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201006853

• 2011 • 34	MOCVD of ZnO films from bis(ketoiminato)Zn(II) precursors: Structure, morphology and optical properties Bekermann, D. and Ludwig, Ar. and Toader, T. and MacCato, C. and Barreca, D. and Gasparotto, A. and Bock, C. and Wieck, A.D. and Kunze, U. and Tondello, E. and Fischer, R.A. and Devi, A. Chemical Vapor Deposition 17 155-161 (2011) Two closely related bis(ketoiminato) zinc precursors, which are air stable and possess favorable properties for metal-organic (MO)CVD, are successfully employed for the growth of ZnO films on silicon and borosilicate glass substrates at temperatures between 400 and 700 °C. The as-deposited films are investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), nuclear reaction analysis (NRA), as well as by UV-vis absorption spectroscopy and photoluminescence (PL) measurements. The structure, morphology, and composition of the as-grown films show a strong dependence on the substrate temperature. The formation of pure and (001)-oriented wurtzite-type stoichiometric ZnO is observed. PL measurements are performed both at room temperature and 77 K, revealing a defect-free emission of ZnO films. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201006898

• 2011 • 33	Oxygen chemisorption, formation, and thermal stability of Pt oxides on Pt nanoparticles supported on SiO2/Si(001): Size effects Ono, L.K. and Croy, J.R. and Heinrich, H. and Roldan Cuenya, B. Journal of Physical Chemistry C 115 16856-16866 (2011) The changes induced in the structure and chemical state of size-selected Pt nanoparticles (NPs) supported on ultrathin SiO2 films upon exposure to oxygen have been investigated by atomic force microscopy (AFM), transmission electron microscopy (TEM), in situ X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption (TPD). For low atomic oxygen exposures, chemisorbed oxygen species were detected on all samples. Exposure to higher atomic oxygen coverages at room temperature leads to the formation and stabilization of PtOx species (PtO2 and PtO). On all samples, a two-step thermal decomposition process was observed upon annealing in ultrahigh vacuum: PtO2 → PtO → Pt. For NPs in the 2-6 nm range, the NP size was found to affect the strength of the O binding. Contrary to the case of Pt(111), where no oxides were detected above 700 K, 10-20% PtO was detected on the NP samples via XPS at the same temperature, suggesting the presence of strongly bound oxygen species. In addition, for identical atomic oxygen exposures, decreasing the NP size was found to favor their ability to form oxides. Interestingly, regardless of whether the desorption of chemisorbed oxygen species or that of oxygen in PtOx species was considered, our TPD data revealed higher O2-desorption temperatures for the Pt NPs as compared with the Pt(111) surface. Furthermore, a clear size-dependent trend was observed, with an increase in the strength of the oxygen bonding with decreasing NP size. © 2011 American Chemical Society.
  	view abstract	doi: 10.1021/jp204743q

• 2011 • 32	p-Co3O4/n-ZnO, Obtained by PECVD, Analyzed by X-ray Photoelectron Spectroscopy Bekermann, D. and Gasparotto, A. and Barreca, D. and Devi, A. and Fischer, R.A. Surface Science Spectra 18 36-45 (2011) The present work focuses on the X-ray Photoelectron Spectroscopy (XPS) and X-ray Excited Auger Electron Spectroscopy (XE-AES) of a Co3O4/ZnO nanosystem. The composite material was obtained via a two-step Plasma Enhanced-Chemical Vapor Deposition (PECVD) process in Ar/O2 mixtures, consisting in the initial deposition of ZnO and the subsequent growth of Co3O4 onto the pristine matrices. Zn(ketoimi)2 (ketoimi = [CH3O(CH2)3NC(CH3)=C(H)C(CH3)=O]) and Co(dpm)2 (dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) were used as zinc and cobalt precursors, respectively. In particular, strongly 〈001〉 oriented ZnO was grown at 300 °C, followed by the deposition of Co3O4 at 200 °C, applying a radio-frequency (RF) power of 20 W. Structural, morphological and compositional investigations were performed by Glancing Incidence X-ray Diffraction (GIXRD), Field Emission-Scanning Electron Microscopy (FE-SEM) and Energy Dispersive X-ray Spectroscopy (EDXS). Surface XPS and XE-AES analyses were carried out to study in detail the system O 1s, Zn 2p3/2, Zn 3p and Co 2p core levels, as well as the Zn and Co Auger peaks. The obtained results evidenced the formation of a composite material, in which ZnO and Co3O4 preserved their chemical identity. © 2011 American Vacuum Society.
  	view abstract	doi: 10.1116/11.20111003

• 2011 • 31	Plasma enhanced-CVD of undoped and fluorine-doped Co3O 4 nanosystems for novel gas sensors Barreca, D. and Bekermann, D. and Comini, E. and Devi, A. and Fischer, R.A. and Gasparotto, A. and Gavagnin, M. and MacCato, C. and Sada, C. and Sberveglieri, G. and Tondello, E. Sensors and Actuators, B: Chemical 160 79-86 (2011) Co3O4-based nanosystems were prepared on polycrystalline Al2O3 by plasma enhanced-chemical vapor deposition (PE-CVD), at temperatures ranging between 200 and 400 °C. The use of two different precursors, Co(dpm)2 (dpm = 2,2,6,6-tetramethyl-3, 5-heptanedionate) and Co(hfa)2·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′- tetramethylethylenediamine) enabled the synthesis of undoped and fluorine-doped Co3O4 specimens, respectively. A thorough characterization of their properties was performed by glancing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), field emission-scanning electron microscopy (FE-SEM), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). For the first time, the gas sensing properties of such PE-CVD nanosystems were investigated in the detection of ethanol and acetone. The results show an appreciable response improvement upon doping and functional performances directly dependent on the fluorine content in the Co3O4 system. © 2011 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.snb.2011.07.016

• 2011 • 30	Prevention of catalyst deactivation in the hydrogenolysis of glycerol by Ga 2O 3-modified copper/zinc oxide catalysts Bienholz, A. and Blume, R. and Knop-Gericke, A. and Girgsdies, F. and Behrens, M. and Claus, P. Journal of Physical Chemistry C 115 999-1005 (2011) Copper/zinc oxide catalysts prepared by coprecipitation were proved to be highly active and selective in the hydrogenolysis of glycerol. However, they suffer from strong deactivation in the course of reaction. Modifying the CuO/ZnO catalyst with Ga 2O 3 extremely enhances the stability of the catalyst as even after four consecutive experiments over a Cu/ZnO/Ga 2O 3 catalyst no deactivation is observed. The catalysts were characterized by temperature-programmed reduction, powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy coupled with energy-dispersive X-ray analysis, and inductively coupled plasma optical emission spectrometry. As the Cu/ZnO/Ga 2O 3 catalyst is stable even under harsh reaction conditions of 220 °C and in the presence of water, a space-time-yield as high as 22.1 g propylene glycol/(g Cu h) can be obtained. © 2010 American Chemical Society.
  	view abstract	doi: 10.1021/jp104925k

• 2011 • 29	Stimuli-responsive track-etched membranes via surface-initiated controlled radical polymerization: Influence of grafting density and pore size Tomicki, F. and Krix, D. and Nienhaus, H. and Ulbricht, M. Journal of Membrane Science 377 124-133 (2011) The surface-functionalization of poly(ethylene terephthalate) track-etched membranes of different nominal pore sizes (400, 1000 and 3000. nm) with stimuli-responsive poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) via surface-initiated (SI) atom transfer radical polymerization (ATRP) was performed. Variations of grafting density and grafted chain length were achieved by variation of synthesis conditions. It could be clearly demonstrated that mixtures of reaction solutions containing different ratios of acyl bromides, only one bearing the initiator group necessary for the SI ATRP, led to different initiator group densities on the resulting track-etched membrane surface which had been verified by X-ray photoelectron spectroscopy. Moreover the mass increase as function of reaction time strongly correlated with the amount of initiator bound to the membrane surface indicating that the ATRP reaction was not limited by monomer diffusion into the pores. Scanning electron microscopy images and permporometry measurements indicated an even functionalization on the entire membrane surface which was the basis for further investigations. The stimuli-responsive properties of PDMAEMA grafted track-etched membranes were studied by permeability measurements with citrate and glycine buffers as function of pH (2 and 10) and temperature (25 and 60 °C). By that the barrier properties of the membranes could be effectively changed in two steps. The results agree with the expectation that a change in grafting density and chain length has an effect on the stimuli-responsive properties of the membrane. Results for membranes having similar degrees of grafting clearly showed that the reversible swelling of grafted polymeric layers was more pronounced for lower grafting density. © 2011 Elsevier B.V.
  	view abstract	doi: 10.1016/j.memsci.2011.04.028

• 2011 • 28	Structural characteristics and catalytic performance of alumina-supported nanosized ceria-lanthana solid solutions Katta, L. and Thrimurthulu, G. and Reddy, B.M. and Muhler, M. and Grünert, W. Catalysis Science and Technology 1 1645-1652 (2011) Alumina-supported nanosized ceria-lanthana solid solutions (CeO <inf>2</inf>-La<inf>2</inf>O<inf>3</inf>/Al<inf>2</inf>O<inf>3</inf> (CLA) = 80:20:100 mol% based on oxides) were synthesized by a modified deposition coprecipitation method from ultra-high dilute aqueous solutions. The synthesized materials were subjected to various calcination temperatures from 773 to 1073 K to understand the surface structure and the thermal stability. Structural and redox properties were deeply investigated by different characterization techniques, namely, X-ray diffraction (XRD), Raman spectroscopy (RS), transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (H<inf>2</inf>-TPR), and Brunauer-Emmett-Teller (BET) surface area. The catalytic efficiency was evaluated for CO oxidation at normal atmospheric pressure. BET surface area measurements revealed that synthesized samples exhibit reasonably high specific surface area. As revealed by XRD measurements, samples maintain structural integrity up to 1073 K without any disproportionation of phases. XPS results suggested that there is no significant change in the Ce3+ amount during thermal treatments due to the absence of undesirable cerium aluminate formation. A significant number of oxygen vacancies were confirmed from Raman and UV-vis DRS measurements. The CLA 773 sample exhibited superior CO oxidation activity. The better activity of the catalyst was proved to be due to a high dispersion in the form of nanosized ceria-lanthana solid solutions over the alumina support, facile reduction, and a high oxygen storage capacity. © The Royal Society of Chemistry 2011.
  	view abstract	doi: 10.1039/c1cy00312g

• 2011 • 27	The synthesis of Nb-doped TiO2 nanoparticles by spray drying: An efficient and scalable method Mei, B. and Sánchez, M.D. and Reinecke, T. and Kaluza, S. and Xia, W. and Muhler, M. Journal of Materials Chemistry 21 11781-11790 (2011) Nb-doped TiO2 nanoparticles were prepared by a continuous spray drying process using ammonium niobate (V) oxalate and titanium oxysulfate as water-soluble precursors. The structural and electronic properties were investigated using thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Nb was found to be mainly incorporated as Nb5+ into the TiO2 lattice resulting in a charge compensation by Ti vacancies. The characterization results indicate that Nb was homogeneously distributed within the titania lattice, and that the surface segregation of Nb, which is commonly observed for Nb-doped TiO 2, was significantly less pronounced. The high homogeneity and the lower extent of surface segregation originate from the efficient atomization of homogeneous precursor solutions and the fast evaporation of the solvent in the spray drying process. As a result, the ion mobility is diminished and spheres of well-mixed precursor materials are formed. Using the continuous spray drying process followed by a controlled heat treatment, the phase composition, the crystal size and the surface area of the Nb-doped TiO2 nanoparticles are easily adjustable. © The Royal Society of Chemistry 2011.
  	view abstract	doi: 10.1039/c1jm11431j

• 2011 • 26	TiO 2 coating of high surface area silica gel by chemical vapor deposition of TiCl 4 in a fluidized-bed reactor Xia, W. and Mei, B. and Sánchez, M.D. and Strunk, J. and Muhler, M. Journal of Nanoscience and Nanotechnology 11 8152-8157 (2011) TiO 2 was deposited on high surface area porous silica gel (400 m 2g -1) in a fluidized bed reactor. Chemical vapor deposition was employed for the coating under vacuum conditions with TiCl 4 as precursor. Nitrogen physisorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy were applied to characterize the obtained TiO 2-SiO 2 composites with different Ti loadings up to 5 wt%. Only a slight decrease in the specific surface area was detected at low Ti loadings. At a Ti loading of 2 wt%, TiO 2 was found to be highly dispersed on the SiO 2 surface likely in form of a thin film. At higher Ti loadings, two weak reflections corresponding to anatase TiO 2 were observed in the diffraction patterns indicating the presence of crystalline bulk TiO 2. High resolution XPS clearly distinguished two types of Ti species, i.e., Ti-O-Si at the interface and Ti-O-Ti in bulk TiO 2. The presence of polymeric TiOx species at low Ti loadings was confirmed by a blue shift in the UV-vis spectra as compared to bulk TiO 2. All these results point to a strong interaction between the TiO 2 deposit and the porous SiO 2 substrate especially at low Ti loadings. Copyright © 2011 American Scientific Publishers All rights reserved.
  	view abstract	doi: 10.1166/jnn.2011.5107

• 2011 • 25	Visualization and functions of surface defects on carbon nanotubes created by catalytic etching Xia, W. and Yin, X. and Kundu, S. and Sánchez, M. and Birkner, A. and Wöll, C. and Muhler, M. Carbon 49 299-305 (2011) Surface defects were created on carbon nanotubes (CNTs) by catalytic steam gasification or catalytic etching with iron as catalysts. The structure and morphology of the etched CNTs were studied by transmission electron microscopy (TEM) and scanning tunneling microscopy (STM). The electronic structure of the etched CNTs was investigated by ultraviolet photoelectron spectroscopy (UPS). The etched CNTs were treated by nitric acid to obtain oxygen-containing functional groups. The amount and the thermal stability of these groups were studied by temperature-resolved X-ray photoelectron spectroscopy (XPS). Temperature-programmed desorption with ammonia as a probe molecule (NH 3-TPD) was employed to investigate the interaction of the surface defects with foreign molecules in gas phase. TEM and STM studies disclosed the presence of surface defects especially edge planes on the etched CNTs. Etching of CNTs led to a less pronounced p-π band than the as-is CNTs, as evidenced by UPS studies. The XPS and NH 3-TPD studies demonstrated that the defects on the CNTs enhanced the reactivity of the exposed surfaces allowing obtaining a higher degree of oxygen functionalization and more active adsorption sites. © 2010 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.carbon.2010.09.025

• 2011 • 24	X-ray photoelectron spectroscopy on implanted argon as a tool to follow local structural changes in thin films Lahrood, A. R. and de los Arcos, T. and Prenzel, M. and von Keudell, A. and Winter, J. Thin Solid Films 520 1625--1630 (2011) Argon ions were implanted in metallic, semiconducting or insulating substrates, and investigated with X-ray photoelectron spectroscopy. Analysis of the Ar2p core level of argon showed clear differences in binding energy position and width as function of the matrix material, implantation energy, and post-annealing treatment. Although argon is not expected to form chemical bonds with the host matrix, the electronic shells within the gas atom can react to their environment according to different effects. It is shown that the precise determination and correct interpretation of the binding energy levels of the embedded gas atoms provides information about the local environment of the matrix such as amorphization of the crystalline structure, defect healing or gas bubble formation. (C) 2011 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.tsf.2011.07.040

• 2010 • 23	1D ZnO nano-assemblies by Plasma-CVD as chemical sensors for flammable and toxic gases Barreca, D. and Bekermann, D. and Comini, E. and Devi, A. and Fischer, R.A. and Gasparotto, A. and MacCato, C. and Sberveglieri, G. and Tondello, E. Sensors and Actuators, B: Chemical 149 1-7 (2010) In this work, 1D ZnO nano-assemblies were prepared on Al2O 3 substrates by plasma enhanced-chemical vapor deposition (PE-CVD), and characterized in their morphology and chemical composition by field emission-scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDXS) and X-ray photoelectron spectroscopy (XPS). For the first time, the sensing performances of PE-CVD ZnO nanosystems were tested in the detection of toxic/combustible gases (CO, H2 and CH4), revealing very good responses already at moderate working temperatures. In particular, carbon monoxide and hydrogen detection was possible already at 100 °C, whereas methane sensing required a minimum temperature of 200 °C. The performances of the present ZnO nanosystems, that make them attractive candidates for technological applications, are presented and discussed in terms of their unique and controllable morphological organization. © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.snb.2010.06.048

• 2010 • 22	Carbon-stabilized mesoporous MoS2 - Structural and surface characterization with spectroscopic and catalytic tools Polyakov, M. and Poisot, M. and Van Den Berg, M.W.E. and Drescher, T. and Lotnyk, A. and Kienle, L. and Bensch, W. and Muhler, M. and Grünert, W. Catalysis Communications 12 231-237 (2010) Structural and surface properties of carbon-containing mesoporous MoS 2 and of a reference MoS2 were studied with various techniques including XRD, elemental analysis, TEM, XPS, EXAFS, nitrogen physisorption, oxygen chemisorption (OCS), determination of exchangeable surface hydrogen, and kinetic study of test reactions like ethene hydrogenation and H2/D2 exchange. The study was made before and after use of these catalysts in the hydrodesulfurization of dibenzothiophene. The microstructure of carbon-stabilized MoS2 is characterized by nanoslabs of 2 nm average stacking height embedded in an amorphous matrix with a very broad pore-size distribution. Thermal stress induced a collapse of the microporous structure leading to the formation of mainly mesopores. The carbon is well-distributed over the bulk, without any signature of carbide species detected neither in XPS nor in EXAFS measurements. The activity patterns of both materials (related to the OCS capacity) were similar despite the differing sulfur content, with the carbon-stabilized MoS2 being more sulfur deficient. This suggests that the catalytic properties of the latter material were caused by near-stoichiometric MoS2 apparently present in the nanoslabs, whereas the sulfur vacancies in the sulfur-deficient amorphous phase were blocked by strongly adsorbed carbon residues. Interestingly, the HDS reaction did not cause significant changes of the properties of the carbon-stabilized MoS2. Conversely, the reference MoS2 was strongly activated, in particular with respect to ethene hydrogenation, which can be explained by a pronounced sulfur loss during the HDS reaction, without significant site blockage by the coke deposited. © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.catcom.2010.09.011

• 2010 • 21	Dissolution kinetics of Si into Ge (111) substrate on the nanoscale Balogh, Z. and Erdélyi, Z. and Beke, D.L. and Wiedwald, U. and Pfeiffer, H. and Tschetschetkin, A. and Ziemann, P. Thin Solid Films 519 952-955 (2010) In this paper we present experiments and simulations on the dissolution of Si into single crystalline Ge(111) substrates. The interface shift during the dissolution was tracked by X-ray Photoelectron Spectroscopy. It was obtained that the interface remained sharp and shifted according to anomalous kinetics similarly to our previous measurement in the Si/amorphous-Ge system. The interface shift, x, can be described by a power function of time x ∞ t kc with a kinetic exponent, kc, of 0.85 ± 0.1, larger than the one measured for the amorphous system (0.7 ± 0.1). Both exponents, however, are different from the kc = 0.5 Fickian (parabolic) value and it is interpreted as a nanoscale diffusional anomaly caused by the strong composition dependence of the diffusion coefficients. © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.tsf.2010.08.146

• 2010 • 20	Field effects on SnOx and SnO2 nanoparticles synthesized in the gas phase Roy Chowdhury, D. and Ivaturi, A. and Nedic, A. and Einar Kruis, F. and Schmechel, R. Physica E: Low-Dimensional Systems and Nanostructures 42 2471-2476 (2010) The present study reports for the first time the influence of stoichiometry of SnO2 nanoparticles synthesized in the gas phase at atmospheric pressure towards the field effect behaviour. The field effect was measured by using the nanoparticles as active material in a transistor channel. The transistors fabricated from the stoichiometric SnO2 nanoparticles (∼20 nm) obtained by post-deposition low-temperature (300 °C) oxidation of the SnO nanoparticles clearly demonstrate n-type behaviour in contrast to the high electrical conductance exhibited by the non-stoichiometric SnOx nanoparticles obtained by high temperature (650 °C) in-flight oxidation. X-ray Photoelectron Spectroscopy (XPS) studies confirm the stoichiometry of the in-flight as well as the post-oxidized nanoparticles.
  	view abstract	doi: 10.1016/j.physe.2010.06.005

• 2010 • 19	Formation and thermal stability of platinum oxides on size-selected platinum nanoparticles: Support effects Ono, L.K. and Yuan, B. and Heinrich, H. and Roldan Cuenya, B. Journal of Physical Chemistry C 114 22119-22133 (2010) This article presents a systematic study of the formation and thermal stability of Pt oxide species on sizeselected Pt nanoparticles (NPs) supported on SiO2, ZrO2, and TiO2 thin films. The studies were carried out in ultrahigh vacuum (UHV) by temperature-dependent X-ray photoelectron spectroscopy (XPS) measurements and ex situ transmission electron microscopy and atomic force microscopy. The NPs were synthesized by inverse micelle encapsulation and oxidized in UHV at room temperature by an oxygen plasma treatment. For a given particle size distribution, the role played by the NP support on the stability of Pt oxides was analyzed. PtO2 species are formed on all supports investigated after O2-plasma exposure. A two-step thermal decomposition (PtO2 → PtO → Pt) is observed from 300 to 600 K upon annealing in UHV. The stability of oxidized Pt species was found to be enhanced on ZrO2 under annealing treatments in O2. Strong NP/support interactions and the formation of Pt-Ti-O alloys are detected for Pt/TiO2 upon annealing in UHV above 550 K but not under an identical treatment in O2. Furthermore, thermal treatments in both environments above 700 K lead to the encapsulation of Pt by TiOx. The final shape of the micellar Pt NPs is influenced by the type of underlying support as well as by the post-deposition treatment. Spherical Pt NPs are stable on SiO2, ZrO2, and TiO 2 after in situ ligand removal with atomic oxygen at RT. However, annealing in UHV at 1000 K leads to NP flattening on ZrO2 and to the diffusion of Pt NPs into TiO2. The stronger the nature of the NP/support interaction, the more dramatic is the change in the NP shape (TiO2 > ZrO2 > SiO2). © 2010 American Chemical Society.
  	view abstract	doi: 10.1021/jp1086703

• 2010 • 18	Gas-phase synthesis of gradient catalyst libraries consisting of nanoparticles supported on high surface area porous substrates Xia, W. and Mei, B. and Muhler, M. Nanoscience and Nanotechnology Letters 2 1-6 (2010) Despite the advances in high throughput experimentation in recent years the synthesis of realistic catalyst libraries especially gradient catalyst libraries remains as a challenge in material science. Recently, we have developed a method for the synthesis of gradient catalyst libraries consisting of nanoparticles supported on high surface area porous substrates. Chemical vapor deposition (CVD) was employed as a gas-phase method for the synthesis. The method made use of the lateral concentration profile of the precursor-loaded carrier gas stream during CVD, resulting in concentration profile of the deposits on porous substrates. In this report, high surface area materials of both powders (e.g., silica) and bulk composites (e.g., hierarchical carbon structures) were successfully employed as substrates for the deposition of single metal or bimetallic catalyst libraries. The synthesis was achieved by controlling the flow behavior of the effluent precursor stream. The resulting effusion cone led to a radial deposition gradient on the substrate. Different from thin film-type model catalyst libraries, the obtained catalysts can be tested under realistic reaction conditions. Methanol oxidation was studied as a test reaction using scanning mass spectrometry. Copyright © 2010 American Scientific Publishers.
  	view abstract	doi: 10.1166/nnl.2010.1046

• 2010 • 17	Growth and characterization of ti-ta-o thin films on si substrates by liquid injection MOCVD for high-k applications from modified titanium and tantalum precursors Devi, A. and Hellwig, M. and Barreca, D. and Parala, H. and Thomas, R. and Becker, H.-W. and Katiyar, R.S. and Fischer, R.A. and Tondello, E. Chemical Vapor Deposition 16 157-165 (2010) Titanium oxide (TiO2) and titanium-tantalum oxide (Ti-Ta-O) thin films are deposited by liquid injection (LI) metal-organic (MO) CVD using metal amide-malonate complexes, [Ti(NR2)2 (dbml) 2], and tantalum, [Ta(NMe2)2 (dbml)] (R Me, Et; dbml di-tert-butylmalonato). TiO2 and Ti-Ta-O films are deposited on Si(100) in the temperature ranges 350-650°C and 500-700°C, respectively. The structure, morphology, and chemical composition of the films are evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Rutherford backscattering spectroscopy (RBS), and X-ray photoelectron spectroscopy (XPS). The electrical properties of the films, namely the dielectric properties, are assessed by carrying out capacitance-voltage (C-V) measurements on metal-oxide-semiconductor (MOS) capacitor structures.
  	view abstract	doi: 10.1002/cvde.200906813

• 2010 • 16	Ion-enhanced oxidation of aluminum as a fundamental surface process during target poisoning in reactive magnetron sputtering Kuschel, T. and von Keudell, A. Journal of Applied Physics 107 103302 (2010) Plasma deposition of aluminum oxide by reactive magnetron sputtering (RMS) using an aluminum target and argon and oxygen as working gases is an important technological process. The undesired oxidation of the target itself, however, causes the so-called target poisoning, which leads to strong hysteresis effects during RMS operation. The oxidation occurs by chemisorption of oxygen atoms and molecules with a simultaneous ion bombardment being present. This heterogenous surface reaction is studied in a quantified particle beam experiment employing beams of oxygen molecules and argon ions impinging onto an aluminum-coated quartz microbalance. The oxidation and/or sputtering rates are measured with this microbalance and the resulting oxide layers are analyzed by x-ray photoelectron spectroscopy. The sticking coefficient of oxygen molecules is determined to 0.015 in the zero coverage limit. The sputtering yields of pure aluminum by argon ions are determined to 0.4, 0.62, and 0.8 at 200, 300, and 400 eV. The variation in the effective sticking coefficient and sputtering yield during the combined impact of argon ions and oxygen molecules is modeled with a set of rate equations. A good agreement is achieved if one postulates an ion-induced surface activation process, which facilitates oxygen chemisorption. This process may be identified with knock-on implantation of surface-bonded oxygen, with an electric-field-driven in-diffusion of oxygen or with an ion-enhanced surface activation process. Based on these fundamental processes, a robust set of balance equations is proposed to describe target poisoning effects in RMS. (C) 2010 American Institute of Physics. [doi:10.1063/1.3415531]
  	view abstract	doi: 10.1063/1.3415531

• 2010 • 15	Metal-free and electrocatalytically active nitrogen-doped carbon nanotubes synthesized by coating with polyaniline Jin, C. and Nagaiah, T.C. and Xia, W. and Spliethoff, B. and Wang, S. and Bron, M. and Schuhmann, W. and Muhler, M. Nanoscale 2 981-987 (2010) Nitrogen doping of multi-walled carbon nanotubes (CNTs) was achieved by the carbonization of a polyaniline (PANI) coating. First, the CNTs were partially oxidized with KMnO4 to obtain oxygen-containing functional groups. Depending on the KMnO4 loading, thin layers of birnessite-type MnO2 (10 wt% and 30 wt%) were obtained by subsequent thermal decomposition. CNT-supported MnO2 was then used for the oxidative polymerization of aniline in acidic solution, and the resulting PANI-coated CNTs were finally heated at 550 °C and 850 °C in inert gas. The samples were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. A thin layer of carbonized PANI was observed on the CNT surface, and the surface nitrogen concentration of samples prepared from 30% MnO 2 was found to amount to 7.6 at% and 3.8 at% after carbonization at 550 °C and 850 °C, respectively. These CNTs with nitrogen-containing shell were further studied by electrochemical impedance spectroscopy and used as catalysts for the oxygen reduction reaction. The sample synthesized from 30 wt% MnO2 followed by carbonization at 850 °C showed the best electrochemical performance indicating efficient nitrogen doping. © 2010 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/b9nr00405j

• 2010 • 14	Modification of GaAs surface by low-current Townsend discharge Gurevich, E.L. and Kittel, S. and Hergenröder, R. and Astrov, Y.A. and Portsel, L.M. and Lodygin, A.N. and Tolmachev, V.A. and Ankudinov, A.V. Journal of Physics D: Applied Physics 43 (2010) The influence of stationary spatially homogeneous Townsend discharge on the (1 0 0) surface of semi-insulating GaAs samples is studied. Samples exposed to both electrons and ions in a nitrogen discharge at a current density j = 60 μA cm-2 are studied by means of x-ray photoelectron spectroscopy, ellipsometry and atomic force microscopy. It is shown that an exposure to low-energy ions (< 1 eV) changes the crystal structure of the semiconductor for a depth of up to 10-20 nm, although the stoichiometric composition does not change. The exposure to low-energy electrons (< 10 eV) forms an oxide layer, which is 5-10 nm thick. Atomic force microscopy demonstrates that the change in the surface potential of the samples may exceed 100 mV, for both discharge polarities, while the surface roughness does not increase. © 2010 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0022-3727/43/27/275302

• 2010 • 13	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 abstract	doi: 10.1016/j.elecom.2009.12.021

• 2010 • 12	Optimization of mesh-based anodes for direct methanol fuel cells Chetty, R. and Scott, K. and Kundu, S. and Muhler, M. Journal of Fuel Cell Science and Technology 7 0310101-0310119 (2010) Platinum based binary and ternary catalysts were prepared by thermal decomposition onto a titanium mesh and were evaluated for the anodic oxidation of methanol. The binary Pt:Ru catalyst with a composition of 1:1 gave the highest performance for methanol oxidation at 80° C. The effect of temperature and time for thermal decomposition was optimized with respect to methanol oxidation, and the catalysts were characterized by cyclic voltammetry, linear sweep voltammetry, scanning electron microscopy, X-ray diffraction studies, and X-ray photoelectron spectroscopy. The best catalyst was evaluated in a single fuel cell, and the effect of methanol concentration, temperature, and oxygen/air flow was studied. The mesh-based fuel cell, operating at 80°C with 1 mol dm 3 methanol, gave maximum power densities of 38 mWcm -2 and 22 mWcm -2 with 1 bar (gauge) oxygen and air, respectively. © 2010 by ASME.
  	view abstract	doi: 10.1115/1.3117605

• 2010 • 11	Passivation of Si(111) surfaces with electrochemically grafted thin organic films Roodenko, K. and Yang, F. and Hunger, R. and Esser, N. and Hinrichs, K. and Rappich, J. Surface Science 604 1623-1627 (2010) Ultra thin organic films (about 5 nm thick) of nitrobenzene and 4-methoxydiphenylamine were deposited electrochemically on p-Si(111) surfaces from benzene diazonium compounds. Studies based on atomic force microscopy, infrared spectroscopic ellipsometry and x-ray photoelectron spectroscopy showed that upon exposure to atmospheric conditions the oxidation of the silicon interface proceed slower on organically modified surfaces than on unmodified hydrogen passivated p-Si(111) surfaces. Effects of HF treatment on the oxidized organic/Si interface and on the organic layer itself are discussed. © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.susc.2010.06.005

• 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 abstract	doi: 10.1021/ja106568t

• 2010 • 9	Photoluminescence studies on structural defects and room temperature ferromagnetism in Ni and Ni-H doped ZnO nanoparticles Tong, L.-N. and Cheng, T. and Han, H.-B. and Hu, J.-L. and He, X.-M. and Tong, Y. and Schneider, C.M. Journal of Applied Physics 108 (2010) We explore the effects of hydrogenated annealing on the crystal structure, room temperature ferromagnetism (RT-FM) and photoluminescence (PL) properties of Ni-doped ZnO (Zn1-xNixO, x=0.0 to 0.2) nanoparticles prepared by a sol-gel method. The x-ray photoelectron spectra and x-ray diffraction data provide evidence that Ni has been incorporated into the wurtzite ZnO lattice as Ni2+ ions substituting for Zn2+ ions at x0.05. A secondary phase of NiO type begins to form inside ZnO when x≤0.05 and segregates from ZnO host lattice at x=0.2, leading to a large variation in the lattice constants of ZnO. The magnetization measurements show that the saturation magnetization (Ms) increases with increasing Ni concentration in the single-phase Zn1-xNixO (x≤0.05) nanoparticles. The secondary phase formation reduces the magnetization of Zn1-xNixO (x=0.1 and 0.15), while the segregation of NiO from the ZnO lattice at x=0.2 is accompanied by a large increase in M s again. The PL measurements show that the UV emission intensity of single-phase Zn1-xNixO (x≤0.05) nanoparticles increases with a blueshift in the UV emission line when the Ni concentration increases, while the dominant green emission intensity decreases with increasing Ni dopant. The PL data strongly suggest that the FM in single-phase Zn 1-xNixO (x≤0.05) nanoparticles is intrinsically correlated with a doping induced increase in the electron concentration in the conduction band of Ni-doped ZnO. After H2 -annealing, the single-phase Zn1-x NixO:H (x≤0.05) nanoparticles show increases in both coercivity and saturation magnetization. The PL and diffuse reflectance spectra suggest that hydrogen-related shallow donors and an improved sample quality may be responsible for the H2-annealing induced enhancement of the RT-FM. The obvious correlation between FM and carrier concentration in Ni and Ni-H doped ZnO points towards a mechanism of carrier-mediated FM for Ni-doped ZnO diluted magnetic semiconductors. © 2010 American Institute of Physics.
  	view abstract	doi: 10.1063/1.3460644

• 2010 • 8	Rh-RhSx nanoparticles grafted on functionalized carbon nanotubes as catalyst for the oxygen reduction reaction Jin, C. and Xia, W. and Nagaiah, T.C. and Guo, J. and Chen, X. and Li, N. and Bron, M. and Schuhmann, W. and Muhler, M. Journal of Materials Chemistry 20 736-742 (2010) Rhodium-rhodium sulfide nanoparticles supported on multi-walled carbon nanotubes (CNTs) were synthesized via a multi-step colloid route. The CNTs were first exposed to nitric acid to generate oxygen-containing functional groups, and then treated with thionyl chloride to generate acyl chloride groups. The grafting of thiol groups was subsequently carried out by reaction with 4-aminothiophenol. Colloidal rhodium nanoparticles were synthesized using rhodium chloride as metal source, sodium citrate as stabilizer, and sodium borohydride as reducing agent. The immobilization of the generated colloidal rhodium nanoparticles was achieved by adding the thiolated CNTs to the colloidal suspension. All these steps were monitored by X-ray photoelectron spectroscopy, which disclosed the presence of rhodium sulfide, whereas metallic rhodium was detected by X-ray diffraction, suggesting that the nanoparticles probably consist of a metallic Rh core covered by a sulfide layer. Scanning and transmission electron microscopy studies showed that the diameter of the catalyst particles was about 7 nm even at high Rh loadings. Rotating disc electrode measurements and cyclic voltammetry were employed to test the electrocatalytic activity in the oxygen reduction reaction in hydrochloric acid. Among all the synthesized catalysts with different rhodium loadings (4.3-21.9%), the 16.1% rhodium catalyst was found to be the most active catalyst. In comparison to the commercial E-TEK Pt/C catalyst, the 16.1% catalyst displayed a higher electrochemical stability in the highly corrosive electrolyte, as determined by stability tests with frequent current interruptions. © 2010 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/b916192a

• 2010 • 7	Small gold particles supported on MgFe2O4 nanocrystals as novel catalyst for CO oxidation Jia, C.-J. and Liu, Y. and Schwickardi, M. and Weidenthaler, C. and Spliethoff, B. and Schmidt, W. and Schüth, F. Applied Catalysis A: General 386 94-100 (2010) We present the study on the catalytic performance of gold particles supported on spinel type MgFe2O4 nanocrystals (Au/MgFe2O4) which exhibit high activity for low temperature CO oxidation. Using XRD, TEM, XPS and CO titration techniques, we investigated the effect of the pretreatment atmosphere on the structure and catalytic properties of the Au/MgFe2O4 catalyst in CO oxidation. TEM, XPS and XRD showed that the pretreatment atmosphere had a negligible effect on the particle size distribution, chemical states of the gold, and the structure of the support. Among the various pretreated catalysts, O2-Au/MgFe2O4 exhibits superior activity, indicating that pretreatment in oxidative atmosphere induced the high capability of the catalyst to activate CO and supply active oxygen for CO oxidation as confirmed by CO titration experiments. © 2010 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.apcata.2010.07.036

• 2010 • 6	Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition Lu, A.-H. and Nitz, J.-J. and Comotti, M. and Weidenthaler, C. and Schlichte, K. and Lehmann, C.W. and Terasaki, O. and Schüth, F. Journal of the American Chemical Society 132 14152-14162 (2010) Uniform and highly dispersed γ-Fe 2O 3 nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe 2O 3 nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe 2O 3/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60 000 cm 3 g cat -1 h -1. At a space velocity of 7500 cm 3 g cat -1 h -1, complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe 2O 3 nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe 2O 3 and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe 2O 3/CMK-5 catalyst is much more active than the benchmark NiO/Al 2O 3 catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe 2O 3 nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity. © 2010 American Chemical Society.
  	view abstract	doi: 10.1021/ja105308e

• 2010 • 5	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 abstract	doi: 10.1016/j.tsf.2010.01.018

• 2010 • 4	Synthesis and characterization of ag- or sb-doped zno nanorods by a facile hydrothermal route Lupan, O. and Chow, L. and Ono, L.K. and Cuenya, B.R. and Chai, G. and Khallaf, H. and Park, S. and Schulte, A. Journal of Physical Chemistry C 114 12401-12408 (2010) ZnO nanorods doped with Ag and Sb have been synthesized by a facile hydrothermal technique. Crystal quality, morphology, chemical/electronic composition, local structure, and vibrational mode properties are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and micro-Raman spectroscopy. Evidence of dopant incorporation is demonstrated in the XPS measurements of both Sb-doped and Ag-doped ZnO nanorods. From XRD data, it was found that the doped ZnO nanorods have a lower degree of crystallinity. The lattice constants of doped ZnO nanorods were slightly larger than that of the pure samples. © 2010 American Chemical Society.
  	view abstract	doi: 10.1021/jp910263n

• 2010 • 3	Synthesis and characterization of ZnO nanowires for nanosensor applications Lupan, O. and Emelchenko, G.A. and Ursaki, V.V. and Chai, G. and Redkin, A.N. and Gruzintsev, A.N. and Tiginyanu, I.M. and Chow, L. and Ono, L.K. and Roldan Cuenya, B. and Heinrich, H. and Yakimov, E.E. Materials Research Bulletin 45 1026-1032 (2010) In this paper we report the synthesis of ZnO nanowires via chemical vapor deposition (CVD) at 650 °C. It will be shown that these nanowires are suitable for sensing applications. ZnO nanowires were grown with diameters ranging from 50 to 200 nm depending on the substrate position in a CVD synthesis reactor and the growth regimes. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Raman spectroscopy (RS) have been used to characterize the ZnO nanowires. To investigate the suitability of the CVD synthesized ZnO nanowires for gas sensing applications, a single ZnO nanowire device (50 nm in diameter) was fabricated using a focused ion beam (FIB). The response to H2 of a gas nanosensor based on an individual ZnO nanowire is also reported. © 2010 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.materresbull.2010.03.027

• 2010 • 2	Wear mechanisms in metal-on-metal bearings: The importance of tribochemical reaction layers Wimmer, M.A. and Fischer, A. and Büscher, R. and Pourzal, R. and Sprecher, C. and Hauert, R. and Jacobs, J.J. Journal of Orthopaedic Research 28 436-443 (2010) Metal-on-metal (MoM) bearings are at the forefront in hip resurfacing arthroplasty. Because of their good wear characteristics and design flexibility, MoM bearings are gaining wider acceptance with market share reaching nearly 10% worldwide. However, concerns remain regarding potential detrimental effects of metal particulates and ion release. Growing evidence is emerging that the local cell response is related to the amount of debris generated by these bearing couples. Thus, an urgent clinical need exists to delineate the mechanisms of debris generation to further reduce wear and its adverse effects. In this study, we investigated the microstructural and chemical composition of the tribochemical reaction layers forming at the contacting surfaces of metallic bearings during sliding motion. Using X-ray photoelectron spectroscopy and transmission electron microscopy with coupled energy dispersive X-ray and electron energy loss spectroscopy, we found that the tribolayers are nanocrystalline in structure, and that they incorporate organic material stemming from the synovial fluid. This process, which has been termed "mechanical mixing," changes the bearing surface of the uppermost 50 to 200 nm from pure metallic to an organic composite material. It hinders direct metal contact (thus preventing adhesion) and limits wear. This novel finding of a mechanically mixed zone of nanocrystalline metal and organic constituents provides the basis for understanding particle release and may help in identifying new strategies to reduce MoM wear. © 2009 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.
  	view abstract	doi: 10.1002/jor.21020

• 2010 • 1	[cis-(1,3-diene) 2W(CO) 2] complexes as MOCVD precursors for the deposition of thin tungsten - Tungsten carbide films Jipa, I. and Heinemann, F.W. and Schneider, A. and Popovska, N. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Marbach, H. and Papp, C. and Steinrück, H.-P. and Zenneck, U. Chemical Vapor Deposition 16 239-247 (2010) Tungsten - tungsten carbide thin films are deposited by metal-organic (MO)CVD on silica-coated silicon wafers using [cis-(1,3-butadiene) 2W(CO) 2] and [cis-(1,3-cyclohexadiene) 2W(CO) 2], respectively, as tunable precursor complexes. The compounds are prepared through photochemical ligand exchange reactions from [W(CO) 6] and fully characterized, including X-ray structure determination and detailed differential thermal analysis (DTA)/thermogravimetry (TG) investigations. Gas-phase diffusion coefficients and the vapor pressure of the compounds are calculated. The MOCVD experiments are performed in a vertical cold-wall reactor and the exhaust gas is analyzed by gas chromatography (GC). X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) measurements are utilized for film characterization. Consequences of the high oxophilicity of freshly formed tungsten surfaces, consecutive surface reactions of the complex ligands, film growth, and film properties are discussed. Inside the layers, tungsten carbide is identified as the main component. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cvde.201006852