文献类型：期刊文献

英文题名：A DFT plus U study of CO oxidation at CeO₂(110) and (111) surfaces with oxygen vacancies

作者：Song, Ya-Ling;Yin, Li-Li;Zhang, Jie;Hu, P.;Gong, Xue-Qing[1];Lu, Guanzhong

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

年份：2013

卷号：618

起止页码：140

外文期刊名：SURFACE SCIENCE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000326614500022)】；

基金：The authors thank the financial support from National Basic Research Program (2010CB732300, 2011CB808505), National Natural Science Foundation of China (21073060), Shanghai Rising-Star Program (12QH1400700) and National High Technology Research and Development Program of China (2012AA062703). P.H. thanks the Chinese Government for the program of "Thousands Talents". Computing time in the National Super Computing Center in Jinan is acknowledged.

语种：英文

外文关键词：Cerium dioxide; DFT plus U; CO oxidation; Oxygen vacancy; Electron localization; Reaction mechanism

摘要：Density functional theory calculations corrected by on-site Coulomb interaction have been conducted to illuminate the effect of O vacancies on the surface reactivities toward direct CO oxidation at CeO2(110) and (111). CO adsorption at and further reaction with various surface O at the vacancy were systematically calculated, and extensive geometric and electronic analyses were also performed to understand the calculation results. It has been shown that though the existence of O vacancy can reduce the activities of neighboring O as the barriers of elementary steps are generally higher than those at stoichiometric surfaces, the relative preference for CO2 desorption is also increased due to the missing of nearby O for carbonate formation. Moreover, our calculation results also showed that the characteristic localized 4f orbitals/electrons of Ce still play the key role in determining the surface reactivities as the vacancy induced localized electrons can hinder their further occurrence and the corresponding reactions. (C) 2013 Elsevier B.V. All rights reserved.