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

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• 作者：Konstantinos Alexopoulos ; Marie-Franç ; oise Reyniers ; ^{MarieFrancoise.Reyniers@ugent.be} ; Guy B. Marin
• 关键词：DFT ; V2O5/TiO2 catalyst ; Monolayer vanadia ; Oxygen sites ; CH bond activation ; Propane dehydrogenation
• 刊名：Journal of Catalysis
• 出版年：2012
• 期刊代码：97_00219517
• 类别：ce
• 出版时间：May, 2012
• 卷：289
• 期：Complete
• 页码：127-139
• 文件大小：3548 K

摘要

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.