文献类型：期刊文献

英文题名：Unique Electronic and Structural Effects in Vanadia/Ceria-Catalyzed Reactions

作者：Wu, Xin-Ping;Gong, Xue-Qing[1]

机构：[1]E China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China; E China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2015

卷号：137

期号：41

起止页码：13228

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20154401469837);WOS:【SCI-EXPANDED(收录号:WOS:000363438600005)】；

基金：We are grateful for financial support from the National Natural Science Foundation of China (21421004, 21322307), "Shu Guang" project of Shanghai Municipal Education Commission and Shanghai Education Development Foundation (13SG30), and the Fundamental Research Funds for the Central Universities (WD1313009). We also thank the computing time in the National Super Computing Center in Jinan.

语种：英文

外文关键词：Catalyst supports - Catalyst activity - Dehydrogenation - Density functional theory - Oxygen - Catalytic oxidation

摘要：Vanadia/ceria supported catalysts exhibit ultrahigh catalytic activities in oxidative dehydrogenation (ODH) reactions. Here, we performed systematic density functional theory calculations to illustrate the underlying mechanisms. It is found that unique electronic and structural effects are both crucial in the catalytic processes. Calculations of the catalytic performance of different oxygen species in oxidation of methanol to formaldehyde suggested that the oxygen of the interface V-O-Ce group is catalytically more active, especially when H adsorption energy is small, indicating the strong structural effect in the vanadia/ceria supported catalyst. In addition, new empty localized states of O 2p generated in a ceria-supported system through depositing VO3- and VO4-type monomeric vanadia species are determined to participate in the whole ODH reaction processes and help to reduce the barriers at various steps.