Mesoporous Silicates with Spherical Morphology Modified with Vanadium Highly Active in Oxidation of Cyclohexene with H2O2

Abstract

Vanadium-containing mesoporous molecular sieves have been prepared by hydrothermal treatment at 373 K. These materials showed spherical morphology with a narrow particle size distribution between 2 and 4 lm. The techniques used for their physicochemical characterization were: XRD, AAS, N2 physisorption, SEM, TEM and DR–UV–Vis spectroscopy. All the materials presented high specific surface area ([900 m2/g), characteristic of MCM-41 materials. A well-defined mesoporous structure was observed by TEM measures although there was no onedimensionalordering of pores characteristic of such materials. Additionally, secondary mesoporosity domainswere determined in the BJH size distribution. The sample synthesized with the highest content of V presented marked differences in their structural characteristics, which were attributed to the blockage of channels by the presence of nano-clusters and/or VxOy nano-oxides. From the DR–UV–Vis analysis, a successful incorporation of V ions to silica structure in tetrahedral coordination with oxygen of the network could be inferred. The catalytic activity of these materials was evaluated in the test reaction of cyclohexene oxidation using H2O2 as oxidizing agent, showing a high conversion of about 93% respect to the maximum, resulting dominant the radicalary mechanism over the direct oxidation mechanism. Apparently, the isolated V ions incorporated into the silica structure would be responsible for the high catalytic activity of these materials.