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Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study
Authors:Thomas Bürgi  Fachri Atamny  Axel Knop‐Gericke  Michael Hävecker  Thomas Schedel‐Niedrig  Robert Schlögl  Alfons Baiker
Affiliation:(1) Laboratory of Technical Chemistry, ETH Zentrum, CH‐8092 Zürich, Switzerland;(2) Fritz‐Haber Institut der Max‐Planck Gesellschaft, Faradayweg 4‐6, D‐14195 Berlin, Germany
Abstract:The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.
Keywords:ethyl pyruvate  in situ XANES  enantioselective hydrogenation  platinum
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