Coverage-Dependent Behaviors of Vanadium Oxides for Chemical Looping Oxidative Dehydrogenation.

Chemical looping provides an energy- and cost-effective route for alkane utilization. However, there is considerable CO2 co-production caused by kinetically mismatched O2- bulk diffusion and surface reaction in current chemical looping oxidative dehydrogenation systems, rendering a decreased olefin productivity. Sub-monolayer or monolayer vanadia nanostructures are successfully constructed to suppress CO2 production in oxidative dehydrogenation of propane by evading the interference of O2- bulk diffusion (monolayer versus multi-layers). The highly dispersed vanadia nanostructures on titanium dioxide support showed over 90 % propylene selectivity at 500 °C, exhibiting turnover frequency of 1.9×10-2  s-1 , which is over 20 times greater than that of conventional crystalline V2 O5 . Combining in situ spectroscopic characterizations and DFT calculations, we reveal the loading-reaction barrier relationship through the vanadia/titanium interfacial interaction.