title: Atomic structure and special reactivity toward methanol oxidation of vanadia nanoclusters on TiO2(110).
abstract: We have grown highly controlled VOx nanoclusters on rutile TiO2(110). The combination of photoemission and photoelectron diffraction techniques based on synchrotron radiation with DFT calculations has allowed identifying these nanostructures as exotic V4O6 nanoclusters, which hold vanadyl groups, even if vanadium oxidation state is formally +3. Our theoretical investigation also indicates that on the surface of titania, vanadia mononuclear species, with oxidation states ranging from +2 to +4, can be strongly stabilized by aggregation into tetramers that are characterized by a charge transfer to the titania substrate and a consequent decrease of the electron density in the vanadium 3d levels. We then performed temperature programmed desorption experiments using methanol as probe molecule to understand the impact of these unusual electronic and structural properties on the chemical reactivity, obtaining that the V4O6 nanoclusters can selectively convert methanol to formaldehyde at an unprecedented low temperature (300 K).
authors.affiliation: Department of Chemical Sciences, University of Padua , I-35131 Padova, Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: Artiglia
authors.forename: Stefano
authors.initials: S
authors.lastname: Agnoli
authors.forename: Andrea
authors.initials: A
authors.lastname: Vittadini
authors.forename: Alberto
authors.initials: A
authors.lastname: Verdini
authors.forename: Albano
authors.initials: A
authors.lastname: Cossaro
authors.forename: Luca
authors.initials: L
authors.lastname: Floreano
authors.forename: Gaetano
authors.initials: G
authors.lastname: Granozzi