Oxidation state of vanadium introduced in dealuminated beta zeolite by impregnation with VIVOSO4 solution: influence of preparation parameters

Vanadium was introduced in dealuminated beta zeolite by impregnation with a VIVOSO4 aqueous solution at 353 K in air or argon (to prevent oxidation of VIV), leading to VSibeta and VSibeta-Ar zeolites, respectively. The samples were characterized by spectroscopy, XRD, and N2-physisorption. The oxidation state and environment of V in Sibeta zeolite depend on the preparation parameters (i.e., on the way the solid is recovered after impregnation and on the drying temperature). In solids recovered by centrifugation, washed with distilled water, and then dried overnight at 298 K in argon, vanadium is found as extra-lattice octahedral VIV ions as evidenced by EPR. In contrast, in solids not washed but directly dried overnight at 353 K in air or argon, vanadium is found in both cases as lattice tetrahedral VV ions. These ions are incorporated into vacant T sites associated with SiOH, SiO-, oxygen vacancies (OVs) or nonbridging oxygen (NBOs) defects as shown by diffuse reflectance UV-visible, 51V MAS NMR, FT-IR, and photoluminescence. The oxidation to VV ions is suggested to be due to an electron transfer from VO2+ to trigonal identical with Si+ defect sites followed by reaction of the resulting VO2+ ions with particular defects of vacant T sites. These processes occur already upon drying of V-impregnated Sibeta at 353 K. 51V MAS NMR allows detection of one kind of lattice tetrahedral V ions in VSibeta and two kinds in VSibeta-Ar. The formation of different kinds of tetrahedral V species is related to the presence in vacant T sites of Sibeta zeolite of different types of defect sites such as trigonal identical with Si+ defect or SiOH and SiO- groups.