Avoiding Self-Poisoning: A Key Feature for the High Activity of Au/Mg(OH)2 Catalysts in Continuous Low-Temperature CO Oxidation.

Au/Mg(OH)2 catalysts have been reported to be far more active in the catalytic low-temperature CO oxidation (below 0 °C) than the thoroughly investigated Au/TiO2 catalysts. Based on kinetic and in situ infrared spectroscopy (DRIFTS) measurements, we demonstrate that the comparatively weak interaction of Au/Mg(OH)2 with CO2 formed during the low-temperature reaction is the main reason for the superior catalyst performance. This feature enables rapid product desorption and hence continuous CO oxidation at temperatures well below 0 °C. At these temperatures, Au/TiO2 also catalyzes CO2 formation, but does not allow for CO2 desorption, which results in self-poisoning. At higher temperatures (above 0 °C), however, CO2 formation is rate-limiting, which results in a much higher activity for Au/TiO2 under these reaction conditions.

Methanol synthesis via CO2 hydrogenation over a Au/ZnO catalyst: an isotope labelling study on the role of CO in the reaction process.

Methanol synthesis for chemical energy storage, via hydrogenation of CO2 with H2 produced by renewable energies, is usually accompanied by the undesired formation of CO via the reverse water-gas shift reaction. Aiming at a better mechanistic understanding of methanol formation from CO2/H2 on highly selective supported Au/ZnO catalysts we have investigated the role of CO in the reaction process using isotope labelling experiments. Using (13)C-labelled CO2, we found for reaction at 5 bar and 240 °C that (i) the methanol formation rate is significantly higher in CO2-containing gas mixtures than in a CO2-free mixture and (ii) in mixtures containing both CO2 and CO methanol formation from CO increases with the CO content up to 1% CO, and then remains at 20% of the total methanol formation up to a CO2/CO ratio of 1/1, making CO2 the preferred carbon source in these mixtures. A shift in the preferred carbon source for MeOH from CO2 towards CO is observed with increasing reaction temperatures between 240 °C and 300 °C. At even higher temperatures CO is expected to become the dominant carbon source. The consequences of these findings for the application of Au/ZnO catalysts for chemical storage of renewable energies are discussed.

Improved Performance of Ru/γ-Al2O3 Catalysts in the Selective Methanation of CO in CO2-Rich Reformate Gases upon Transient Exposure to Water-Containing Reaction Gas.

To better understand the role of water in the selective methanation of CO in CO2-rich reformate gases on Ru/Al2O3 catalysts, the influence of exposing these catalysts to H2O-rich reformate gases on their reaction characteristics in transient experiments was investigated by employing kinetic and in situ spectroscopic measurements as well as ex situ catalyst characterization. Transient exposure of the ruthenium catalyst to wet reaction gas (5 or 15% H2O) results in significantly enhanced activity and selectivity for CO methanation in subsequent reactions in dry reformate compared with activation and reaction in dry reformate directly. Operando X-ray absorption spectroscopy results reveal that this is in accordance with a significant decrease in ruthenium particle size, which is stable during subsequent reaction in dry reformate. The implications of these data and additional results from in situ IR spectroscopy on the role and influence of H2O on the reaction, also in technical applications, are discussed.

Electroluminescence of GeSn/Ge MQW LEDs on Si substrate.

Multi-quantum well light-emitting diodes, consisting of ten alternating GeSn/Ge-layers, were grown by molecular beam epitaxy on Si. The Ge barriers were 10 nm thick, and the GeSn wells were grown with 7% Sn and thicknesses between 6 and 12 nm. The electroluminescence spectra measured at 300 and 80 K yield a broad and intensive luminescence band. Deconvolution revealed three major lines produced by the GeSn wells that can be interpreted in terms of quantum confinement. We interpret that the three lines represent two direct lines, formed by transitions with the light and heavy hole band, respectively, and an indirect line. Biaxial compressive strain causes a splitting of light and heavy holes in the GeSn wells. This interpretation is supported by an effective mass band structure calculation.

Electrically pumped lasing from Ge Fabry-Perot resonators on Si.

Room temperature lasing from electrically pumped n-type doped Ge edge emitting devices has been observed. The edge emitter is formed by cleaving Si-Ge waveguide heterodiodes, providing optical feedback through a Fabry-Perot resonator. The electroluminescence spectra of the devices showed optical bleaching and intensity gain for wavelengths between 1660 nm and 1700 nm. This fits the theoretically predicted behavior for the n-type Ge material system. With further pulsed electrical injection of 500 kA/cm2 it was possible to reach the lasing threshold for such edge emitters. Different lengths and widths of devices have been investigated in order to maintain best gain-absorption ratios.

CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed.

Catalytic activity of nanostructured Au: Scale effects versus bimetallic/bifunctional effects in low-temperature CO oxidation on nanoporous Au.

The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure-activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed.

Direct bandgap narrowing in Ge LED's on Si substrates.

In this paper we investigate the influence of n-type doping in Ge light emitting diodes on Si substrates on the room temperature emission spectrum. The layer structures are grown with a special low temperature molecular beam epitaxy process resulting in a slight tensile strain of 0.13%. The Ge LED's show a dominant direct bandgap emission with shrinking bandgap at the Γ point in dependence of n-type doping level. The emission shift (38 meV at 10²°cm⁻³) is mainly assigned to bandgap narrowing at high doping. The electroluminescence intensity increases with doping concentrations up to 3x10¹9cm⁻³ and decreases sharply at higher doping levels. The integrated direct gap emission intensity increases superlinear with electrical current density. Power exponents vary from about 2 at low doping densities up to 3.6 at 10²°cm⁻³ doping density.