Dispersed Vanadium in Three-Dimensional Dendritic Mesoporous Silica Nanospheres: Active and Stable Catalysts for the Oxidative Dehydrogenation of Propane in the Presence of CO 2 .

The uniform monodispersed vanadium-doped three-dimensional dendritic mesoporous silica nanospheres (nV-MSNSs) were successfully synthesized in a heterogeneous oil-water biphase stratification reaction system and characterized by several state-of-the-art methods. The synthesized nV-MSNSs were applied to the oxidative dehydrogenation of the propane (ODHP) reaction with the presence of CO2 and exhibited excellent catalytic performances. The results show that the vanadium loading (1.3-8.0 wt %) evidently influences the textural properties, oxidation state, and polymerization degree of vanadium species of nV-MSNSs. The specific surface area (SBET ), pore diameter (Dp ), and pore volume (Vp ) of nV-MSNSs decrease with the loading of vanadium species. The excessively high vanadium loading leads to the slight connection of nanospheres, but does not affect the assembly and growth of the three-dimensional (3D) dendritic channels. The percentage of highly dispersed vanadium VV species gradually increases and attains the maximum value for 5.2V-MSNSs with the loading of vanadium and then decreases with further vanadium addition. The higher-polymerized VOx species gradually generates above 5.2 wt % vanadium content for nV-MSNSs. The lower-polymerized VOx species appear to be more active than the higher-polymerized VOx species. Markedly, the 5.2V-MSNSs exhibit the highest catalytic activity with the initial propane conversion of 58% for the ODHP. The excellent catalytic performance can be maintained after eight reaction-regeneration cycles. The silica mesoporous frameworks can be well preserved in the reaction-regeneration cycles; meanwhile, the highly dispersed vanadium oxide also can be fully recovered after in situ regeneration. Hence, nV-MSNS catalysts exhibit outstanding activity and stability, and it would have a promising application in the DH of alkanes.