Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilit...Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilities of various CeO2 （100） termination structures are discussed, and calculated energetics are presented. The most stable Ce〇2 （100） surface was obtained by removing half the outermost full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO2 （100） surface, we determined that the formation of carbonate species competed with CO2 desorption. However, during CO oxidation on the less stable CeO2 （100） surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO2 formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4/ orbitals are directly involved in deter-mining the surface stabilities and reactivities.展开更多
基金supported the National Natural Science Foundation of China(21421004,21573067)~~
文摘Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilities of various CeO2 （100） termination structures are discussed, and calculated energetics are presented. The most stable Ce〇2 （100） surface was obtained by removing half the outermost full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO2 （100） surface, we determined that the formation of carbonate species competed with CO2 desorption. However, during CO oxidation on the less stable CeO2 （100） surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO2 formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4/ orbitals are directly involved in deter-mining the surface stabilities and reactivities.
