Effect of electronic structures of au clusters stabilized by poly(N-vinyl-2-pyrrolidone) on aerobic oxidation catalysis

Hironori Tsunoyama, Nobuyuki Ichikuni, Hidehiro Sakurai, Tatsuya Tsukuda

Research output: Contribution to journalArticle

457 Citations (Scopus)

Abstract

Au clusters smaller than 1.5 nm and stabilized by poly(N-vinyl-2- pyrrolidone) (PVP) showed higher activity for aerobic oxidation of alcohol than those of larger size or stabilized by poly(allylamine) (PAA). X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy of adsorbed CO, and X-ray absorption near edge structure measurements revealed that the catalytically active Au clusters are negatively charged by electron donation from PVP, and the catalytic activity Is enhanced with increasing electron density on the Au core. Based on similar observations of Au cluster anions In the gas phase, we propose that electron transfer from the anionic Au cores of Au:PVP into the LUMO (π*) of O2 generates superoxoor peroxo-like species, which plays a key role in the oxidation of alcohol. On the basis of these results, a simple principle Is presented for the synthesis of Au oxidation catalysts stabilized by organic molecules.

Original languageEnglish
Pages (from-to)7086-7093
Number of pages8
JournalJournal of the American Chemical Society
Volume131
Issue number20
DOIs
Publication statusPublished - 2009 May 27
Externally publishedYes

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Catalysis
Electronic structure
Electrons
Oxidation
Alcohols
Allylamine
Photoelectron Spectroscopy
X ray absorption
Fourier Transform Infrared Spectroscopy
Carbon Monoxide
Fourier transform infrared spectroscopy
Anions
Carrier concentration
Catalyst activity
Negative ions
X ray photoelectron spectroscopy
Gases
X-Rays
Catalysts
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Effect of electronic structures of au clusters stabilized by poly(N-vinyl-2-pyrrolidone) on aerobic oxidation catalysis. / Tsunoyama, Hironori; Ichikuni, Nobuyuki; Sakurai, Hidehiro; Tsukuda, Tatsuya.

In: Journal of the American Chemical Society, Vol. 131, No. 20, 27.05.2009, p. 7086-7093.

Research output: Contribution to journalArticle

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