Reaction path analysis of propene selective oxidation over V2O5 and V2O5/TiO2

► First ab initio modeling of propene oxidation over a V2O5 monolayer on TiO2. ► Reaction network not limited to allylic oxidation only. ► Reaction mechanism includes detailed description of catalyst reduction. ► V2O5 is overall more active; V2O5/TiO2 is more selective in acrolein formation. ► Disproportionation of V4+ on V2O5/TiO2 hinders product desorption.