Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis

Zope, Bhushan; Hibbitts, David D; Neurock, Matthew; Davis, Robert J

doi:10.1126/science.1195055

Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis

Journal Article · Fri Oct 01 04:00:00 EDT 2010 · Science

DOI:https://doi.org/10.1126/science.1195055· OSTI ID:1028595

Zope, Bhushan; Hibbitts, David D; Neurock, Matthew; Davis, Robert J

The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with {sup 18}O{sub 2} and H{sub 2} {sup 18}O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: DOE Office of Science; USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1028595

Journal Information:: Science, Journal Name: Science Journal Issue: 6000 Vol. 330; ISSN 0193-4511; ISSN SCEHDK

Country of Publication:: United States

Language:: English

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Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis

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