Stability and morphology of cerium oxide surfaces in an oxidizing environment: A first-principles investigation
- 8 September 2009
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 131 (10), 104701
- https://doi.org/10.1063/1.3191784
Abstract
We present density functional theory investigations of the bulk properties of cerium oxides ( Ce O 2 and Ce 2 O 3 ) and the three low index surfaces of Ce O 2 , namely, (100), (110), and (111). For the surfaces, we consider various terminations including surface defects. Using the approach of “ab initio atomistic thermodynamics,” we find that the most stable surface structure considered is the stoichiometric (111) surface under “oxygen-rich” conditions, while for a more reducing environment, the same (111) surface, but with subsurface oxygen vacancies, is found to be the most stable one, and for a highly reducing environment, the (111) Ce-terminated surface becomes energetically favored. Interestingly, this latter surface exhibits a significant reconstruction in that it becomes oxygen terminated and the upper layers resemble the Ce 2 O 3 ( 0001 ) surface. This structure could represent a precursor to the phase transition of Ce O 2 to Ce 2 O 3 .Keywords
This publication has 76 references indexed in Scilit:
- Density-Functional Calculations of the Structure of Near-Surface Oxygen Vacancies and Electron Localization onPhysical Review Letters, 2009
- Modeling doped and defective oxides in catalysis with density functional theory methods: Room for improvementsThe Journal of Chemical Physics, 2008
- Theoretical study of CeO2 and Ce2O3 using a screened hybrid density functionalThe Journal of Chemical Physics, 2006
- Probing theTransition in Bulk Ce under Pressure: A Direct Investigation by Resonant Inelastic X-Ray ScatteringPhysical Review Letters, 2006
- Density-functional calculation of CeO2 surfaces and prediction of effects of oxygen partial pressure and temperature on stabilitiesThe Journal of Chemical Physics, 2005
- Surface properties offrom first principlesPhysical Review B, 2004
- Catalysis and corrosion: the theoretical surface-science contextSurface Science, 2002
- Toward reliable density functional methods without adjustable parameters: The PBE0 modelThe Journal of Chemical Physics, 1999
- Catalytic Properties of Ceria and CeO2-Containing MaterialsCatalysis Reviews, 1996
- Surface Segregation of Metal Ions in Cerium DioxideThe Journal of Physical Chemistry, 1994