Structure and Catalytic Properties of Supported Vanadium Oxides: Support Effects on Oxidative Dehydrogenation Reactions

Abstract

The effects of support (Al2O3, SiO2, HfO2, TiO2, and ZrO2) on the structure and catalytic behavior of supported vanadia in the oxidative dehydrogenation of propane were examined over a wide range of vanadium surface densities (0.5–15.0 VOx/nm2). X-ray diffraction and Raman and UV-visible spectra showed that vanadia exists as highly dispersed species at surface densities below 7 VOx/nm2on Al2O3, HfO2, TiO2, and ZrO2, but as large V2O5crystallites on SiO2. Surface structures evolve from isolated monovanadates to polyvanadate domains and V2O5crystallites as VOxsurface density increases. Polyvanadates appear at lower surface densities on ZrO2and TiO2than on Al2O3and HfO2. UV-visible edge energies decrease as VOxdomains grow with increasing VOxsurface density on all supports. Initial propene selectivities increase with increasing VOxsurface density, as monovanadate species and exposed support sites, which favor primary combustion pathways, decrease in concentration. Oxidative dehydrogenation rates per V-atom reach a maximum on VOxdomains of intermediate size, which provide a balance between the activity of surface VOxspecies and their accessibility to reactants. Interactions with supports determine the type of VOxstructures present at a given surface density, but turnover rates do not depend on the identity of the support when differences in VOxstructure are taken into account. Oxidative dehydrogenation turnover rates are similar on polyvanadate species and on surface VOxsites on bulk V2O5. The relative rates of oxidative dehydrogenation to form propene and of secondary propene oxidation to COxdo not depend on the identity of the support or on VOxsurface density or structure. Thus, it appears that these two reactions require similar VOxsurface sites and that these sites are present at similar surface densities on polyvanadate domains and small V2O5clusters.