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

文献情報

出版日 2012-03-01

DOI 10.1039/C2CP00061J

インパクトファクター 3.676

著者

Wanglai Cen, Yue Liu, Zhongbiao Wu, Haiqiang Wang, Xiaole Weng

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要旨

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 O2 could be effectively activated to form superoxo (O2−) and/or peroxo species (O22−). 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 O2 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 O2 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.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.