Title

Rationale For The Higher Reactivity Of Interfacial Sites In Methanol Decomposition On Au13/Tio2(110)

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 Au13/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. © 2013 American Chemical Society.

Publication Date

5-22-2013

Publication Title

Journal of the American Chemical Society

Volume

135

Issue

20

Number of Pages

7629-7635

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/ja4010738

Socpus ID

84878232801 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/84878232801

This document is currently not available here.

Share

COinS