Redox properties of CeO2-MO2 (M=Ti, Zr, Hf, or Th) solid solutions from first principles calculations

被引:92
作者
Andersson, D. A. [1 ]
Simak, S. I.
Skorodumova, N. V.
Abrikosov, I. A.
Johansson, B.
机构
[1] Royal Inst Technol, Dept Mat Sci & Engn, SE-10044 Stockholm, Sweden
[2] Linkoping Univ, Dept Phys Chem & Biol, IFM, SE-58183 Linkoping, Sweden
[3] Uppsala Univ, Dept Phys, Condensed Matter Theory Grp, SE-75121 Uppsala, Sweden
关键词
D O I
10.1063/1.2431775
中图分类号
O59 [应用物理学];
学科分类号
摘要
The authors have used density functional theory calculations to investigate how the redox thermodynamics and kinetics of CeO2 are influenced by forming solid solutions with TiO2, ZrO2, HfO2, and ThO2. Reduction is facilitated by dissolving TiO2 (largest improvement), HfO2, or ZrO2 (least improvement), while ThO2 makes reduction slightly more difficult. The migration barrier is much lower in the neighborhood of a Ti (largest decrease), Hf, or Zr (least decrease), while the binding energy of solute ions and vacancies increases in the same sequence. They rationalize the properties of ceria solid solutions in terms of defect cluster relaxations. (c) 2007 American Institute of Physics.
引用
收藏
页数:3
相关论文
共 25 条
[1]   Modeling of CeO2, Ce2O3, and CeO2-x in the LDA plus U formalism [J].
Andersson, D. A. ;
Simak, S. I. ;
Johansson, B. ;
Abrikosov, I. A. ;
Skorodumova, N. V. .
PHYSICAL REVIEW B, 2007, 75 (03)
[2]   Optimization of ionic conductivity in doped ceria [J].
Andersson, DA ;
Simak, SI ;
Skorodumova, NV ;
Abrikosov, IA ;
Johansson, B .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2006, 103 (10) :3518-3521
[3]   Bulk reduction and oxygen migration in the ceria-based oxides [J].
Balducci, G ;
Islam, MS ;
Kaspar, J ;
Fornasiero, P ;
Graziani, M .
CHEMISTRY OF MATERIALS, 2000, 12 (03) :677-681
[4]   PROJECTOR AUGMENTED-WAVE METHOD [J].
BLOCHL, PE .
PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979
[5]   Electrical and oxygen storage/release properties of nanocrystalline ceria-zirconia solid solutions [J].
Boaro, M ;
Trovarelli, A ;
Hwang, JH ;
Mason, TO .
SOLID STATE IONICS, 2002, 147 (1-2) :85-95
[6]   Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J].
Dudarev, SL ;
Botton, GA ;
Savrasov, SY ;
Humphreys, CJ ;
Sutton, AP .
PHYSICAL REVIEW B, 1998, 57 (03) :1505-1509
[7]   Origin of enhanced reducibility/oxygen storage capacity of Ce1-xTixO2 compared to CeO2 or TiO2 [J].
Dutta, Gargi ;
Waghmare, Umesh V. ;
Baidya, Tinku ;
Hegde, M. S. ;
Priolkar, K. R. ;
Sarode, P. R. .
CHEMISTRY OF MATERIALS, 2006, 18 (14) :3249-3256
[8]   RH-LOADED CEO2-ZRO2 SOLID-SOLUTIONS AS HIGHLY EFFICIENT OXYGEN EXCHANGERS - DEPENDENCE OF THE REDUCTION BEHAVIOR AND THE OXYGEN STORAGE CAPACITY ON THE STRUCTURAL-PROPERTIES [J].
FORNASIERO, P ;
DIMONTE, R ;
RAO, GR ;
KASPAR, J ;
MERIANI, S ;
TROVARELLI, A ;
GRAZIANI, M .
JOURNAL OF CATALYSIS, 1995, 151 (01) :168-177
[9]   Use of CeO2-based oxides in the three-way catalysis [J].
Kaspar, J ;
Fornasiero, P ;
Graziani, M .
CATALYSIS TODAY, 1999, 50 (02) :285-298
[10]   Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J].
Kresse, G ;
Furthmuller, J .
PHYSICAL REVIEW B, 1996, 54 (16) :11169-11186