Oxidative Dehydrogenation of Methanol to Formaldehyde by a Vanadium Oxide Cluster Supported on Rutile TiO2(110): Which Oxygen is Involved?

被引：30

作者：

Kim, Hyun You ^{[2
]}

Lee, Hyuck Mo ^{[2
]}

Metiu, Horia ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[2] Korea Adv Inst Sci & Technol, Dept Mat Sci & Engn, Taejon 305701, South Korea

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2010年 / 114卷 / 32期

基金：

美国国家科学基金会;

关键词：

INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; SELECTIVE OXIDATION; METAL; TRANSITION; REACTIVITY; CATALYSTS; VACANCIES; SURFACES; SCIENCE;

D O I：

10.1021/jp103361v

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：

Isolated vanadia clusters supported on titania catalyze the oxidation of methanol to formaldehyde. We used density functional theory to determine the mechanism of this reaction and found a new pathway for the dissociative adsorption of methanol and the dehydrogenation of the methyl group. In this mechanism, methanol adsorbs dissociatively, by inserting into the double bond of the vanadyl group; the methoxy radical binds to the vanadium atom, whereas the hydrogen binds to the oxygen atom of the vanadyl. The dehydrogenation of the methyl group, which is the rate-limiting step, takes place by moving a H atom from CH3 onto an oxygen atom in the -V-O-Ti- group. The V-O bond is broken, and a HO-Ti group is formed.

引用

页码：13736 / 13738

页数：3

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