Computational Study of Structure and Reactivity of Oligomeric Vanadia Clusters Supported on Anatase and Rutile TiO₂ Surfaces

We use density functional theory to examine structure–activity relationships of small vanadia clusters supported on anatase TiO 2 (001) and rutile TiO 2 (110) surfaces. A thermodynamic analysis indicates that the vanadia monomer cluster can be stabilized on the anatase TiO 2 (001) surface in a catalytically relevant oxygen environment. On the other hand, vanadia clusters tend to aggregate into dimers on the rutile TiO 2 (110) surface because this surface binds the monomer less strongly as compared to anatase. Hydrogen adsorption is found to be exothermic on the vanadia monomer adsorbed on both supports, enhanced by a charge transfer between the adsorbate and the substrate. There is no such charge transfer on vanadia dimers and tetramers, where the hydrogen adsorption energies are similar to that on the single crystal V 2 O 5 (001) surface. The improved catalytic performance of the anatase support can be attributed to the ability of this surface to stabilize the catalytically active vanadia monomer clusters.