Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis

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 ¹⁸O₂ and H₂¹⁸O demonstrate...

Full description

Saved in:
Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2010-10, Vol.330 (6000), p.74-78
Main Authors: Zope, Bhushan N, Hibbitts, David D, Neurock, Matthew, Davis, Robert J
Format: Article
Language:English
Subjects:
Alcohols
Aqueous chemistry
Atoms
Catalysis
Catalysts
Catalytic oxidation
Chemical bases
Chemical reactions
Density functional theory
Ethanol
Ethyl alcohol
Gold
Hydroxides
Liquids
Oxidation
Peroxides
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 ¹⁸O₂ and H₂¹⁸O 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.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1195055