Toward an understanding of the formation of vanadia-titania catalysts.

Structures of hydrated vanadia species on the TiO2-anatase surfaces were investigated using the semiempirical molecular orbital method MSINDO. The (101), (001), and (100) surfaces of anatase were considered. They were modeled by appropriate two-dimensional cyclic clusters of TiO2. Monomeric and dimeric hydrated vanadia species on the anatase surfaces were simulated by adsorbing VO4H3 and V2O7H4 molecules, respectively. Different adsorption structures were considered, and their stabilities at 300 and 600 K were tested by constant-temperature Born-Oppenheimer molecular dynamics simulations in the framework of MSINDO. Structural features of the vanadia-titania catalysts found in extended X-ray absorption fine structure, secondary ion mass spectrometry, IR, Raman, and NMR spectroscopy and conductivity experiments can be explained by the present calculations.