CO self-promoting oxidation on nanosized gold clusters : Triangular Au 3 active site and CO induced O-O scission

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Chunyan Liu
  • Yingzi Tan
  • Sisi Lin
  • Hui Li
  • Xiaojun Wu
  • Lei Li
  • Yong Pei

Detail(s)

Original languageEnglish
Pages (from-to)2583-2595
Journal / PublicationJournal of the American Chemical Society
Volume135
Issue number7
Publication statusPublished - 20 Feb 2013
Externally publishedYes

Abstract

We have systematically studied the CO oxidation on various nanosized gold clusters with sizes ranging from 0.3 to 0.8 nm on the basis of density functional theory (DFT) calculations. A hitherto unreported trimolecular Langmuir-Hinshelwood (LH) mechanism is proposed, which offers new insights into the fundamental mechanism for CO oxidation on nanosized gold clusters. Specifically, we find that the coadsorbed CO molecule at a unique triangular Au3 active site can act as a promoter for the scission of an O-O bond, leading to the spontaneous formation (due to extremely low energy barrier) of two CO2 molecules as product. The key step to the O-O bond scission in the OCOO* intermediate is significantly accelerated due to the electrophilic attack of the coadsorbed neighboring CO molecule on the triangular Au3 site. This new mechanism is called CO self-promoting oxidation, which can be visualized in real time from the trajectory of a Born-Oppenheimer molecular dynamics (BOMD) simulation. We also find that such CO self-promoting oxidation is quite universal, as long as the triangular Au 3 reaction site is available. This is demonstrated in two prototype metal oxide supported gold nanostructure systems: namely, Aun/MgO and bilayer-Au/TiO2. The coadsorbed CO can not only serve as a promoter for its own oxidation but also promote other oxidation reactions such as styrene oxidation through expediting O-O scission on gold nanostructures. © 2013 American Chemical Society.

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Citation Format(s)

CO self-promoting oxidation on nanosized gold clusters : Triangular Au 3 active site and CO induced O-O scission. / Liu, Chunyan; Tan, Yingzi; Lin, Sisi et al.

In: Journal of the American Chemical Society, Vol. 135, No. 7, 20.02.2013, p. 2583-2595.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review