What determines the catalyst's selectivity in the ethylene epoxidation reaction

被引：70

作者：

Kokalj, Anton ^{[1
,2
,3
]}

Gava, Paola ^{[2
,3
]}

de Gironcoli, Stefano ^{[2
,3
]}

Baroni, Stefano ^{[2
,3
]}

机构：

[1] Jozef Stefan Inst, SL-1000 Ljubljana, Slovenia

[2] SISSA, I-34014 Trieste, Italy

[3] CNR DEMOCRITOS Theory Electrra Grp, INFM, I-34014 Trieste, Italy

来源：

JOURNAL OF CATALYSIS | 2008年 / 254卷 / 02期

关键词：

ethylene epoxidation; C-H activation; density functional calculations; heterogeneous catalysis; reaction mechanisms;

D O I：

10.1016/j.jcat.2008.01.008

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 selectivity of a catalyst in ethylene epoxidation reaction was addressed using quantum mechanical computer simulations. We found that the catalyst's selectivity in the reaction of oxametallacycle to form ethylene epoxide (EO) rather than the competing acetaldehyde (Ac) is determined in part by the differential bonding affinity of the catalyst toward the O and C atoms of the oxametallacycle. This interplay between O- and C-metal bond strength is due to the different structures of the two transition states. Based on this finding, we introduce a new indicator that determines the difference between the EO and Ac activation energies in the oxametallacycle reaction remarkably well for a number of different materials. (C) 2008 Elsevier Inc. All rights reserved.

引用

页码：304 / 309

页数：6

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