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,...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.展开更多
基金supported by the National Basic Research Program of China(2011CB808505)the National Natural Science Foundation of China(21322307,21421004)+1 种基金the"Shu Guang"project of Shanghai Municipal Education CommissionShanghai Education Development Foundation(13SG30)for financial support
文摘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.
