Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water

Hironori Tsunoyama; Hidehiro Sakurai; Yuichi Negishi; Tatsuya Tsukuda

doi:10.1021/ja052161e

Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water

Hironori Tsunoyama, Hidehiro Sakurai, Yuichi Negishi, Tatsuya Tsukuda

Research output: Contribution to journal › Article › peer-review

819 Citations (Scopus)

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.

Original language	English
Pages (from-to)	9374-9375
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	26
DOIs	https://doi.org/10.1021/ja052161e
Publication status	Published - 2005 Jul 6
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja052161e

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title = "Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water",

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.",

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T1 - Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water

AU - Tsunoyama, Hironori

AU - Sakurai, Hidehiro

AU - Negishi, Yuichi

AU - Tsukuda, Tatsuya

PY - 2005/7/6

Y1 - 2005/7/6

N2 - 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.

AB - 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.

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Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water

Abstract

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