title: The absence of a gap state and enhancement of the Mars-van Krevelen reaction on oxygen defective Cu/CeO2 surfaces.
abstract: We report a detailed first-principles analysis of the electronic structures of oxygen defective CeO2 and Cu/CeO2 surfaces aimed at elucidating the disappearance of the gap state of defective CeO2 when a Cu atom is added at the surface. The top of the valence band of Cu/CeO2 originates from the O 2p states around this Cu atom. We show that this redistribution of electronic states at the defective Cu/CeO2 surface enhances the reactivity of the surface O atoms. Indeed, dynamical simulations show an acceleration of catalytic NO oxidation occurring via the Mars-van Krevelen mechanism mediated by these highly reactive oxygens.
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan. nobusada@ims.ac.jp and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
authors.forename: Kenichi
authors.initials: K
authors.lastname: Koizumi
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan. nobusada@ims.ac.jp and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
authors.forename: Katsuyuki
authors.initials: K
authors.lastname: Nobusada
authors.affiliation: Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, University of Strasbourg and CNRS, 23 rue du Loess, F-67034 Strasbourg, France.
authors.forename: Mauro
authors.initials: M
authors.lastname: Boero