Peer-Reviewed Journal Details
Mandatory Fields
Yeriskin, I,Nolan, M;
2009
September
Journal of Chemical Physics
Effect of La doping on CO adsorption at ceria surfaces
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Optional Fields
adsorption carbon compounds defect states density functional theory doping profiles oxidation vacancies (crystal) DENSITY-FUNCTIONAL THEORY AUGMENTED-WAVE METHOD LOW-INDEX SURFACES ELECTRONIC-STRUCTURE STABILIZED ZIRCONIA METAL-OXIDES OXIDATION CEO2 1ST-PRINCIPLES TRANSITION
131
In this paper we use density functional theory corrected for on-site Coulomb interactions (DFT+U) to study the adsorption of CO at La-doped ceria (111) and (110) surfaces. Doping of ceria with La is known to enhance oxidation of CO to CO2 and this study investigates the atomic level details of this reaction. With La3+ doping, an [La3+-O-] defect state with an oxygen hole is formed at both surfaces. The formation energy of an oxygen vacancy is reduced and vacancy formation results in the appearance of Ce3+, instead of hole compensation. On the doped surfaces weak and strong adsorption of CO is found. In the former, the molecule remains intact. In the latter, the final adsorption species depends strongly on the surface and whether oxygen vacancies are present or not. On (111) a CO2-like species forms, while on the (110) surface, mono- or bidentate carbonates are present. La-doping of ceria surfaces shows enhanced reactivity over the undoped surfaces and we discuss the origin of the enhanced reactivity and the nature of the surface species upon CO adsorption.
ARTN 244702
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