文献类型：期刊文献

英文题名：Origin of the High Activity of Mesoporous CeO2 Supported Monomeric VOx for Low-Temperature Gas-Phase Selective Oxidative Dehydrogenation of Benzyl Alcohol: Role As an Electronic "Hole"

作者：Liu, Juanjuan[1];Wu, Xin-Ping[2,3];Zou, Shihui[1];Dai, Yihu[1];Xiao, Liping[1];Gong, Xue-Qing[2,3];Fan, Jie[1]

机构：[1]Zhejiang Univ, Dept Chem, Key Lab Appl Chem Zhejiang Prov, Hangzhou 310027, Peoples R China;[2]E China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, Shanghai 200237, Peoples R China;[3]E China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2014

卷号：118

期号：43

起止页码：24950

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20144600179745);WOS:【SCI-EXPANDED(收录号:WOS:000344135500017)】；

基金：We are grateful for financial support from the National Science Foundation of China (20873122, 21003106, 21222307, 21322307, and 51222202), the Zhejiang Provincial Natural Science Foundation of China (R12B030002, 2010R50014-06, and Y4090097), Fok Ying Tung Education Foundation (131015), and the Fundamental Research Funds from the Central Universities (2014XZZX003-02). The ECUST group also thanks the Shanghai Rising-Star Program (12QH1400700) and the National Super Computing Centre in Jinan for computing time.

语种：英文

外文关键词：Dehydrogenation - Gases - Transition metals - Temperature - Molecular oxygen - Density functional theory - Catalyst activity - Transition metal oxides

摘要：Herein, we report a newly developed mesoporous VOx-CeO2 catalyst with dominant monomeric VOx species, which can promote the gas-phase ODH reaction of benzyl alcohol-to-benzaldehyde (BA-to-BAD) by molecular oxygen at a surprisingly low temperature range of 203243 degrees C, with a high mass-specific activity of similar to 25 mmol.gcat1.h1 and TOF of 1367 h1. To the best of our knowledge, it appears to be the most effective transition metal oxides catalyst for the BA-to-BAD reaction in the gas phase. Experimental measurements and density functional theory (DFT) calculations suggest that the activities of VOx-CeO2 catalysts strongly depend on the polymeric states of surface VOx, with monomeric VOx giving much better performance than bigger VOx clusters. It is important to highlight that a specific monomeric VO3 species, only occurring under the reaction conditions, is identified for the first time to have the key influence on BA oxidation. Moreover, it has been found that the origin for the unique activity of such monomeric VOx-CeO2 can be attributed to its electronic hole structure.