Adsorption and Oxidation of CO over CeO2(111) Surface

被引:16
|
作者
Jiang Shi-Yu [1 ]
Teng Bo-Tao [1 ]
Yuan Jin-Huan [1 ]
Guo Xiao-Wei [1 ]
Luo Meng-Fei [1 ]
机构
[1] Zhejiang Normal Univ, Inst Phys Chem, Zhejiang Key Lab React Chem Solid Surfaces, Jinhua 321004, Zhejiang, Peoples R China
关键词
Adsorption; CO; CeO2(111) surface; Oxidation; Density functional theory; TRANSFORM INFRARED-SPECTROSCOPY; DENSITY-FUNCTIONAL THEORY; ELASTIC BAND METHOD; CARBON-MONOXIDE; ELECTRONIC-STRUCTURE; CERIA SURFACES; CEO2; SURFACES; REDUCED CEO2; DIOXIDE; OXIDE;
D O I
10.3866/PKU.WHXB20090807
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
Adsorption and oxidation of CO on a CeO2(111) surface terminated by bridging oxygen atoms were systematically investigated using density functional theory (DFT). We found that O-2 adsorption on a clean CeO2(111) surface was weak physisorption; while strong chemical adsorption occurred and the O-O bond was activated with a bond length of 0.143 nm in the present of surface oxygen vacancy. CO adsorption onto a clean CeO2(111) surface and a surface with oxygen vacancies occurred through physisorption with both adsorption energies being less than 0.42 eV. With O-2 adsorption onto a surface with oxygen vacancies (O-2/O-v), CO might absorb strongly on the surface to form a bidentate carbonate intermediate or directly produce CO2 without an energy barrier. The carbonate intermediate might desorb as CO2 with an energy barrier of 0.28 eV using a climbing nudged elastic band (CNEB). We also found that the values of the Hubbard U parameter affected the CO adsorption energy in the presence of surface oxygen vacancies. Our results indicate that a possible effect of the ceria support on catalytic oxidation consists of O-2 adsorbing onto the CeO2(111) surface with oxygen vacancies which can be easily activated to form reactive oxygen species and then take part in the CO oxidation reaction.
引用
收藏
页码:1629 / 1634
页数:6
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