A theoretic insight into the catalytic activity promotion of CeO2 surfaces by Mn doping

被引:128
作者
Cen, Wanglai [1 ]
Liu, Yue [1 ]
Wu, Zhongbiao [1 ]
Wang, Haiqiang [1 ]
Weng, Xiaole [1 ]
机构
[1] Zhejiang Univ, Dept Environm Engn, Hangzhou 310058, Zhejiang, Peoples R China
关键词
TOTAL-ENERGY CALCULATIONS; MIXED-OXIDE CATALYSTS; WAVE BASIS-SET; ELECTRONIC-STRUCTURE; OXYGEN STORAGE; 1ST PRINCIPLES; CO OXIDATION; REDUCTION; COMBUSTION; CERIA;
D O I
10.1039/c2cp00061j
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this paper, we investigated the primary reduction and oxygen replenishing processes over Mn substitutionally doped CeO2(111) surfaces by density functional theory with the on-site Coulomb correction (DFT + U). The results indicated that Mn doping could make the surface much more reducible and the adsorbed O-2 could be effectively activated to form superoxo (O-2(-)) and/or peroxo species (O-2(2-)). The Mn doping induced the Mn 3d-O 2p gap state instead of Ce 4f acting as an electrons acceptor and donor during the first oxygen vacancy formation and O-2 replenishing, which helped to lower the formation energy of the first and second oxygen vacancies to -0.46 eV and 1.40 eV, respectively. In contrast, the formation energy of a single oxygen vacancy in the pure ceria surface was 2.08 eV and only peroxo species were identified as the O-2 molecule adsorbed. Our work provides a theoretical and electronic insight into the catalytic redox processes of Mn doped ceria surfaces, which may help to understand the enhanced catalytic performances of MnOx-CeO2 oxides, as reported in previous experimental works.
引用
收藏
页码:5769 / 5777
页数:9
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