CO adsorption and oxidation on ceria surfaces from DFT+U calculations

被引:261
|
作者
Huang, Min
Fabris, Stefano
机构
[1] CNR, INFM, DEMOCRITOS Theory Elettra Grp, I-34014 Trieste, Italy
[2] SISSA, I-34014 Trieste, Italy
来源
JOURNAL OF PHYSICAL CHEMISTRY C | 2008年 / 112卷 / 23期
关键词
D O I
10.1021/jp709898r
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
The limiting steps of CO oxidation catalyzed by ceria via the Mars-van Krevelen reaction mechanism are identified and investigated by means of density functional theory calculations that account for the on-site Coulomb interaction via a Hubbard term (DFT+U). We address the adsorption of CO on the (111) and (110) surfaces, and its oxidation via participation of lattice oxygen leading to vacancy formation and CO2 desorption. CO physisorbs on the (111) ceria surface (E-bind < 0.2 eV), while it chemisorbs on the more open (110) surface (E-bind > 2 eV) yielding carbonate formation and surface reduction. The DFT+U energy of CO adsorption and oxidation is studied as a function of the parameter U. This analysis demonstrates that the values of U presently used in the literature (U > 4 eV) tend to overestimate the binding energy of CO to ceria surfaces. In contrast, the energy for the complete CO oxidation reaction is effectively independent of U and in good agreement with the available experimental data. The discussion of these results in the context of temperature programmed desorption and microcalorimetry measurements allow us to suggest that lower values of U can be more appropriate for modeling redox reactions on ceria surfaces with the DFT+U method.
引用
收藏
页码:8643 / 8648
页数:6
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