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

    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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