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High-Pressure XPS of Crotyl Alcohol Selective Oxidation over Metallic and Oxidized Pd(111)

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Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF10 3AT, U.K.
Department of Chemistry, University of York, Heslington, York, YO10 5DD, U.K.
§ Advanced Light Source, Lawrence Berkeley Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
Cite this: ACS Catal. 2012, 2, 11, 2235–2241
Publication Date (Web):September 17, 2012
Copyright © 2012 American Chemical Society

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    Abstract Image

    Here, we report on the first application of high-pressure XPS (HP-XPS) to the surface catalyzed selective oxidation of a hydrocarbon over palladium, wherein the reactivity of metal and oxide surfaces in directing the oxidative dehydrogenation of crotyl alcohol (CrOH) to crotonaldehyde (CrHCO) is evaluated. Crotonaldehyde formation is disfavored over Pd(111) under all reaction conditions, with only crotyl alcohol decomposition observed. In contrast, 2D Pd5O4 and 3D PdO overlayers are able to selectively oxidize crotyl alcohol (1 mTorr) to crotonaldehyde in the presence of co-fed oxygen (140 mTorr) at temperatures as low as 40 °C. However, 2D Pd5O4 ultrathin films are unstable toward reduction by the alcohol at ambient temperature, whereas the 3D PdO oxide is able to sustain catalytic crotonaldehyde production even up to 150 °C. Co-fed oxygen is essential to stabilize palladium surface oxides toward in situ reduction by crotyl alcohol, with stability increasing with oxide film dimensionality.

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