文献类型：期刊文献

英文题名：Structures and reactivities of the CeO2/Pt(111) reverse catalyst: A DFT+U study

作者：Zheng, Zhu-Yuan[1]; Wang, Dong[1]; Zhang, Yi[2]; Yang, Fan[2]; Gong, Xue-Qing[1]

机构：[1] Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China; [2] State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, China

年份：2020

卷号：41

期号：9

起止页码：1360

外文期刊名：Chinese Journal of Catalysis

收录：EI(收录号：20201808587067)

语种：英文

外文关键词：Oxidation - Oxygen vacancies - Structural optimization - Catalyst activity - Monolayers - Oxygen - Cerium oxide - Platinum compounds - Surface reactions - Metals

摘要：For heterogeneous catalysts, the build-up of interface contacts can influence markedly their activities. Being different from the conventional supported metal/oxide catalysts, the reverse type of oxide/metal structures, e.g. the ceria/Pt composite, have emerged as novel catalytic materials in many fields. However, it remains challenging to determine the optimal interface structure and/or the metal-oxide synergistic effect that can boost catalytic activities. In this work, we conducted density functional theory calculations with on-site Coulomb interaction correction to determine the optimal structures and investigate the physical as well as catalytic properties of various CeO2/Pt(111) composites containing CeO2(111) monolayer, bilayer, and trilayer at Pt(111). We found that the interaction strength between CeO2(111) and Pt(111) substrate first reduces as the ceria slab grows from monolayer to bilayer, and then largely gets converged when the trilayer occurs. Such trend was well rationalized by analyzing the number and distances of O–Pt bonds at the interface. Calculated Bader charges uncovered the significant charge redistribution occurring around the interface, whereas the net electron transfer across the interface is non-significant and decreases as ceria thickness increases. Moreover, comparative calculations on oxygen vacancy formation energies clarified that oxygen removal can be promoted on the CeO2/Pt(111) composites, especially at the interface. We finally employed CO oxidation as a model reaction to probe the surface reactivity, and determined an intrinsic activity order of monolayer CeO2(111) > monolayer CeO2(111)/Pt(111) > regular CeO2(111). More importantly, we emphasized the significant role of the moderate ceria-Pt interaction at the interface that endows the CeO2/Pt reverse catalyst both good thermostability and high catalytic activity. The monolayer CeO2(111)/Pt(111) composite was theoretically predicted highly efficient for catalyzing CO oxidation. ? 2020 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences