Influence of Cl substitution on the electronic structure and catalytic activity of ceria  

作　　者：Li-Li Yin Xue-Qing Gong 

机构地区：[1]Key Laboratory for Advanced Materials [2]Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology

出　　处：《Science China Chemistry》2015年第4期601-606,共6页中国科学（化学英文版）

基　　金：supported by the National Basic Research Program of China(2011CB808505);the National Natural Science Foundation of China(21322307,21421004);the"Shu Guang"project of Shanghai Municipal Education Commission;Shanghai Education Development Foundation(13SG30)for financial support

摘　　要：Cl-containing cerium dioxide(Ce O2) catalysts have been found to exhibit unique catalytic activities. In the present work, using density functional theory calculations with the inclusion of on-site Coulomb correction, we systematically studied the effect of Cl on the physicochemical properties of Ce O2 surfaces by substituting one subsurface O with Cl. The calculated results show that substituting an O atom with a Cl atom results in structural distortion and the reduction of one surface Ce4+ cation to Ce3+. The protruding Ce3+ cation greatly improves the adsorption energy of O2 to produce an active O2- species, and maintains the catalytic oxidation cycle of CO on Ce O2(110). These results may help us obtain a better understanding of Cl-ceria interacting systems and provide some guidance for the design of effective Ce O2-based catalysts.Cl-containing cerium dioxide （CeO2） catalysts have been found to exhibit unique catalytic activities. In the present work, using density functional theory calculations with the inclusion of on-site Coulomb correction, we systematically studied the effect of Cl on the physicochemical properties of CeO2 surfaces by substituting one subsurface O with Cl. The calculated results show that substituting an O atom with a Cl atom results in structural distortion and the reduction of one surface Ce4＋ cation to Ce3＋. The protruding Ce3＋ cation greatly improves the adsorption energy of O2 to produce an active O2- species, and maintains the catalytic oxidation cycle of CO on CeO2（110）. These results may help us obtain a better understanding of Cl-ceria interacting systems and provide some guidance for the design of effective CeO2-based catalysts.

关 键 词：cerium dioxide Cl substitution DFT＋U O2 adsorption CO oxidation 

分 类 号：O614.332[理学—无机化学]