Atomic
Structure and Special Reactivity Toward Methanol
Oxidation of Vanadia Nanoclusters on TiO<sub>2</sub>(110)
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Abstract
We have grown highly controlled VO<sub><i>x</i></sub> nanoclusters on rutile TiO<sub>2</sub>(110).
The combination of
photoemission and photoelectron diffraction techniques based on synchrotron
radiation with DFT calculations has allowed identifying these nanostructures
as exotic V<sub>4</sub>O<sub>6</sub> 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 V<sub>4</sub>O<sub>6</sub> nanoclusters can selectively convert
methanol to formaldehyde at an unprecedented low temperature (300
K)