Activity and selectivity of propane oxidative dehydrogenation over VO3/CeO(2()111) catalysts: A density functional theory study

作者：Huang, Chang; Wang, Zhi-Qiang; Gong, Xue-Qing^*

来源：Chinese Journal of Catalysis, 2018, 39(9): 1520-1526.

DOI：10.1016/S1872-2067(18)63072-4

• Oxidative dehydrogenation
• Propane to propylene
• C-H bond cleavage
• Ceria-supported vanadia
• Density functional theory calculations

The oxidative dehydrogenation (ODH) of propane on monomeric VO3 supported by CeO2(111) (VO3/CeO2(111)) is studied by periodic density functional theory calculations. Detailed energetic, structural, and electronic properties of these reactions are determined. The calculated activation energies of the breaking of the first and second C-H bonds of propane on the VO3/CeO2(111) catalyst are compared, and it is found that both the unique structural and electronic effects of the VO3/CeO2(111) catalyst contribute to the relatively easy rupture of the first C-H bond of the propane molecule during the ODH reaction. In particular, the so-called new empty localized states that are mainly constituted of O 2p orbitals of the ceria-supported VO3 species are determined to be crucial for assisting the cleavage of the first C-H bond of the propane molecule. Following this they become occupied and the remaining C-H bonds become increasingly difficult to break owing to the increasing repulsion between the localized 4f electrons at the Ce cations, resulting in the adsorption of more H and other moieties. This work illustrates that CeO2-supported monomeric vanadium oxides can exhibit unique activity and selectivity for the catalytic ODH of alkanes to alkenes.

• 出版日期2018-9
• 单位华东理工大学