Title

Rationale for the Higher Reactivity of Interfacial Sites in Methanol Decomposition on Au-13/TiO2(110)

Authors

Authors

S. Hong;T. S. Rahman

Comments

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Abbreviated Journal Title

J. Am. Chem. Soc.

Keywords

SUPPORTED AU NANOPARTICLES; AUGMENTED-WAVE METHOD; CO OXIDATION; CATALYTIC-ACTIVITY; GOLD NANOPARTICLES; CARBON-MONOXIDE; AU/TIO2; CATALYSTS; POINT-DEFECTS; ACTIVE GOLD; OXYGEN; Chemistry, Multidisciplinary

Abstract

Interfacial and perimeter sites have been known for their high activity in various reactions on supported gold nanoparticles. We find that the higher activity of interfacial sites in Au-13/TiO2(110) toward methanol decomposition originates from charge-transfer-induced Coulomb interaction among the gold, reactant, and reducible TiO2 support, brought about through the formation of an ionic O-Au bond between gold and methoxy in such sites, which turns the participating perimeter gold atom cationic. A direct result of such charge-transfer-induced repulsive interaction between cationic gold and positively charged C moiety of methoxy is activation of the positively charged C moiety of methoxy, as manifested by the pronounced elongation of O-C bond length and the tilting of the methoxy axis, which facilitate reaction of methoxy through C-H scission with the bridge oxygen atoms that are readily available from the reducible support. More generally, our proposed mechanism for the reactivity of the gold/TiO2 interface should hold for oxidation of organic molecules with the structure of R-O-R', where R and R' are (saturated) hydrocarbons.

Journal Title

Journal of the American Chemical Society

Volume

135

Issue/Number

20

Publication Date

1-1-2013

Document Type

Article

Language

English

First Page

7629

Last Page

7635

WOS Identifier

WOS:000319551000036

ISSN

0002-7863

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