| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 61448 | Journal of Catalysis | 2012 | 13 Pages |
The selective oxidation of propane on the vanadyl and bridging oxygen sites of the fully oxidized (0 0 1) V2O5 surface and of an epitaxial vanadia monolayer supported on (0 0 1) TiO2 anatase is analysed using periodic density functional theory (DFT). Both the oxidative dehydrogenation leading to propene and the formation of oxygenated products, namely n-propanol, i-propanol, propanal and acetone, are investigated. Selective oxidation proceeds via a Mars–van Krevelen redox mechanism, and its elementary steps on the vanadia surface are identified. Propane chemisorption preferentially occurs through a secondary CH bond activation via a direct hydrogen abstraction by a lattice oxygen. Supporting a vanadia monolayer on titania strongly enhances the CH bond activation as compared to unsupported V2O5, yielding a lower activation energy and a more exothermic propane chemisorption. In accordance with experimental observations, the calculations show that the titania support not only modifies the activity of the vanadia monolayer but it also affects the selectivity of the catalyst, favouring the formation of propene compared to the formation of i-propanol and acetone. The vanadyl oxygen is overall the most active site on V2O5 and V2O5/TiO2, while the bridging oxygen is more selective towards propane dehydrogenation.
Graphical abstractCompared to the unsupported (0 0 1) V2O5 surface, a V2O5 monolayer supported on (0 0 1) TiO2 anatase exhibits a higher selectivity for the oxidative dehydrogenation of propane to propene.Figure optionsDownload full-size imageDownload high-quality image (191 K)Download as PowerPoint slideHighlights► First ab initio modelling of propane oxidation over a V2O5 monolayer on TiO2. ► Reaction network not limited only to propane dehydrogenation. ► Increased activity and selectivity of V2O5/TiO2 in propane dehydrogenation. ► VO is overall most active; VOV is selective towards propane dehydrogenation. ► Formation of V4+ sites is more favourable than formation of V3+ sites.
