Mechanistic Study of Ethanol Dehydrogenation over Silica-Supported Silver

被引：112

作者：

Sushkevich, Vitaly L. ^{[1
]}

Ivanova, Irina I. ^{[1
,2
]}

Taarning, Esben ^{[3
]}

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[2] Russian Acad Sci, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

[3] Haldor Topsoe Res Labs, DK-2800 Lyngby, Denmark

来源：

CHEMCATCHEM | 2013年 / 5卷 / 08期

关键词：

dehydrogenation; IR spectroscopy; silver; reaction mechanisms; supported catalysts; COPPER-CATALYSTS; ISOPROPANOL DEHYDROGENATION; AEROBIC OXIDATION; MOLECULAR-OXYGEN; SOLID CATALYSTS; LIQUID-PHASE; ALCOHOLS; METAL; OXIDE; FTIR;

D O I：

10.1002/cctc.201300033

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 silica-supported Ag catalyst has been shown to be an efficient heterogeneous catalyst for the oxidant-free dehydrogenation of ethanol into acetaldehyde. The reaction mechanism has been investigated by in situ FTIR spectroscopy. The kinetic isotope effects for proton and hydride abstraction have been studied by using CH3CD2OH and CH3CH2OD as labeled reactants. The results indicate that O-H bond activation and the formation of a hydrogen-bonded complex take place on the silica support and that the Ag particles are necessary for the activation of the C-H bond. The kinetic isotope effect (k(H)/k(D)) is 1.9 for CH3CD2OH and 1.8 for CH3CH2OD. The concerted mechanism of C-H cleavage on the Ag sites and proton abstraction on the silica sites is proposed to account for the results of the spectroscopic and kinetic experiments.

引用

页码：2367 / 2373

页数：7

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