The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites

V-silicalite catalysts (VS-1 and VS-2) prepared by hydrothermal synthesis have been studied by ESR, XAFS (XANES and EXAFS) and photoluminescence spectroscopy. The in situ characterization of these V-silicalites shows that vanadium is present within the zeolitic framework as a highly dispersed tetrahedrally coordinated V-oxides, VO₄ unit, having a short V=O bond length. Photoluminescence spectroscopy in static and dynamic mode, as well as XAFS studies allow to detect in the V-silicalites different V species than that present in V-HMS or V/SiO₂, in terms of V=O bond length, vibrational energy, bond angle and lifetime of the excited triplet state. It is suggested that the combined contribution of the neighboring Si-OH group attached to the VO₄ unit and the zeolitic rigid framework structure of V-silicalites cause a more significant and pronounced effect on the chemical properties of the VO₄ unit than the flexible structure of V-HMS or V/SiO₂. Moreover, the dynamic quenching of the phosphorescence by the addition of reactant molecules such as NO or propane indicates that the V species in the excited triplet state can be expected to be the active sites for the photocatalytic reactions.