Mechanistic insight into the heterogeneous catalytic transfer hydrogenation over Cu/Al2O3:: Direct evidence for the assistant role of support

被引：39

作者：

Huang, Long ^{[1
,2
]}

Zhu, Yulei ^{[1
]}

Huo, Chunfang ^{[1
]}

Zheng, Hongyan ^{[1
,2
]}

Feng, Gang ^{[1
,2
]}

Zhang, Chenghua ^{[1
]}

Li, Yongwang ^{[1
]}

机构：

[1] Chinese Acad Sci, Inst Coal Chem, State Key Lab Coal Convers, Taiyuan 03000, Peoples R China

[2] Chinese Acad Sci, Grad Univ, Beijing 10039, Peoples R China

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2008年 / 288卷 / 1-2期

基金：

中国国家自然科学基金;

关键词：

catalytic transfer hydrogenation; Cu/Al2O3; support effect; hydrogen spillover; reaction mechanism;

D O I：

10.1016/j.molcata.2008.03.026

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：

The catalytic transfer hydrogenation (CTH) between alcohol and alkene was investigated over Cu/Al2O3 catalyst via mechanical mixture of the supported catalyst and the pure support. it is found that the CTH activities are highly depended on the amount and acid/basic properties of the mechanically mixed support, clearly indicating the assistant role of support. in addition, only alkene with high activity of hydrogenation can really act as hydrogen acceptor. Based on these, a new bifunctional reaction pathway is proposed. Alcohol dehydrogenates to form alkoxide on Al2O3 surface (Ri CH(OH)R-2 -> R-1 CH(O)R-2 + H), and H atom migrates to the metallic Cu patches via reverse hydrogen spillover, while extraction of alpha-hydrogen forming ketone (Ri CH(O)R-2 R, C(O)R-2 + H) occurs on Cu or Cu-Al2O3 interface. On the metallic Cu patches, alkene hydrogenates yielding alkane (R3CH = CHR4 + 2H, R3CH2CH2R4). This mechanism can give a better explanation for the observed acceleration or deceleration role of hydrogen acceptor to alcohol dehydrogenation. (C) 2008 Elsevier B.V. All rights reserved.

引用

页码：109 / 115

页数：7

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