Size-Specific Catalytic Activity of Polymer-Stabilized Gold Nanoclusters for Aerobic Alcohol Oxidation in Water
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- 14 June 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (26) , 9374-9375
- https://doi.org/10.1021/ja052161e
Abstract
Gold nanoclusters (φ = 1.3 nm) stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP NCs) readily oxidize benzylic alcohols to the corresponding aldehydes and/or carboxylic acids under ambient temperature in water. Kinetic measurement revealed that smaller Au:PVP NCs exhibit higher catalytic activity than larger (9.5 nm) homologues and, more surprisingly, than Pd:PVP NCs of comparable size (1.5 and 2.2 nm). On the basis of the marked difference in the kinetic isotope effect and activation energy between Au:PVP and Pd:PVP NCs, a reaction mechanism for alcohol oxidation catalyzed by Au:PVP NCs is proposed in which a superoxo-like molecular oxygen species adsorbed on the surface of the small Au NCs abstracts a hydrogen atom from the alkoxide.Keywords
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