First-Principles Study of CO Adsorption and Oxidation on Ru-Doped CeO2(111) Surface

被引：104
作者：
Chen, Hsin-Tsung [1 ]
机构：
[1] Chung Yuan Christian Univ, Dept Chem, Chungli 32023, Taiwan
来源：
JOURNAL OF PHYSICAL CHEMISTRY C | 2012年 / 116卷 / 10期
关键词：
GENERALIZED GRADIENT APPROXIMATION; TRANSFORM INFRARED-SPECTROSCOPY; LOW-INDEX SURFACES; CERIUM OXIDE; ELECTRONIC-STRUCTURE; CEO2; SURFACES; REDUCTION-MECHANISMS; MESOPOROUS CERIA; ROOM-TEMPERATURE; CARBON-MONOXIDE;
D O I：
10.1021/jp210864m
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 interaction and mechanism for CO oxidation on a Ru-modified CeO2 surface have been investigated by using periodic density functional theory calculations corrected with the on-site Coulomb interaction via a Hubbard term (DFT + U). Our calculations showed that (i) the Ru dopant facilitates oxygen vacancy formation, while the Ru adatoms may suppress oxygen vacancy formation. (ii) Physisorbed CO, physisorbed CO2, and chemisorbed CO (carbonite, CO2-) species are observed on the Ru-doped CeO2(111) surface; in contrast, only physisorbed CO is found on the clean CeO2(111) surface. The vibrational frequency calculations are carried to characterize these species. (iii) Incorporating Ru ions into the ceria lattice as substitutional point defects can instead sustain a full catalytic cycle for CO oxidation and catalyst regeneration. The Ru dopant promotes CO oxidation without any activation energy leading to O vacancy formation and CO2 desorption. Molecular O-2 adsorbs at the O vacancy forming O adspecies that then drive CO oxidation and recover the stoichiometric Ru-doped CeO2 surface. The Bader charge analysis is carried to characterize the oxidation state of Ru ions along the catalytic cycle.
引用
收藏
页码：6239 / 6246
页数：8
相关论文
共 53 条
[41]   ACCURATE AND SIMPLE ANALYTIC REPRESENTATION OF THE ELECTRON-GAS CORRELATION-ENERGY [J].
PERDEW, JP ;
WANG, Y .
PHYSICAL REVIEW B, 1992, 45 (23) :13244-13249
[42]   ATOMS, MOLECULES, SOLIDS, AND SURFACES - APPLICATIONS OF THE GENERALIZED GRADIENT APPROXIMATION FOR EXCHANGE AND CORRELATION [J].
PERDEW, JP ;
CHEVARY, JA ;
VOSKO, SH ;
JACKSON, KA ;
PEDERSON, MR ;
SINGH, DJ ;
FIOLHAIS, C .
PHYSICAL REVIEW B, 1992, 46 (11) :6671-6687
[43]  
Perdew JP, 1997, PHYS REV LETT, V78, P1396, DOI 10.1103/PhysRevLett.77.3865
[44]   Preferential CO oxidation in hydrogen (PROX) on ceria-supported catalysts, part I:: Oxidation state and surface species on Pt/CeO2 under reaction conditions [J].
Pozdnyakova, O ;
Teschner, D ;
Wootsch, A ;
Kröhnert, J ;
Steinhauer, B ;
Sauer, H ;
Toth, L ;
Jentoft, FC ;
Knop-Gericke, A ;
Paál, Z ;
Schlögl, R .
JOURNAL OF CATALYSIS, 2006, 237 (01) :1-16
[45]   Catalysis by doped oxides:: CO oxidation by AuxCe1-xO2 [J].
Shapovalov, Vladimir ;
Metiu, Horia .
JOURNAL OF CATALYSIS, 2007, 245 (01) :205-214
[46]   Ce1-xRuxO2-δ (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst [J].
Singh, Preetam ;
Hegde, M. S. .
CHEMISTRY OF MATERIALS, 2009, 21 (14) :3337-3345
[47]   Electronic, bonding, and optical properties of CeO2 and Ce2O3 from first principles -: art. no. 115108 [J].
Skorodumova, NV ;
Ahuja, R ;
Simak, SI ;
Abrikosov, IA ;
Johansson, B ;
Lundqvist, BI .
PHYSICAL REVIEW B, 2001, 64 (11)
[48]  
Trovarelli Alessandro., 2002, CATALYSIS CERIA RELA
[49]   Unusual physical and chemical properties of cu in Ce1-xCuxO2 oxides [J].
Wang, XQ ;
Rodriguez, JA ;
Hanson, JC ;
Gamarra, D ;
Martínez-Arias, A ;
Fernández-García, M .
JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (42) :19595-19603
[50]   Physisorbed, Chemisorbed, and Oxidized CO on Highly Active Cu-CeO2(111) [J].
Yang, Zongxian ;
He, Bingling ;
Lu, Zhansheng ;
Hermansson, Kersti .
JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (10) :4486-4494
123456