A molecular orbital study of surface-adsorbate interactions during the oxidation of CO on the Pt(111) surface

被引：16

作者：

Glassey, WV ^{[1
]}

Hoffmann, R ^{[1
]}

机构：

[1] Cornell Univ, Dept Chem & Biol Chem, Ithaca, NY 14853 USA

来源：

SURFACE SCIENCE | 2001年 / 475卷 / 1-3期

基金：

美国国家科学基金会;

关键词：

carbon monoxide; chemisorption; oxidation; catalysis; adsorption kinetics;

D O I：

10.1016/S0039-6028(00)01062-1

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A Langmuir-Hinshelwood type pathway for the oxidation of CO on the Pt(1 1 1) surface is analysed within a tight binding scheme based on the extended Huckel method. A partitioning of the total electronic energy serves to highlight both CO and O derived contributions to the reaction barrier, the extent to which the surface mediates interactions between the adsorbates and the roles of the individual CO and O orbitals in OC-O bond formation. The reaction barrier is interpreted to be the result of a surface-mediated coactivation of CO and O on the surface. In the initial stages of OC-O bond formation a "side-on" donation of electron density from the p-orbitals on O to the empty CO(2 pi) orbitals on CO occurs. The transition from reactants to products is characterized by the formation of a carboxylate (CO;) moiety on the surface. The role of the O s and p orbitals in OC-O bonding is discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：47 / 60

页数：14

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