Tungstophosphoric acid supported over zirconia in mesoporous channels of MCM-41 as catalyst in veratrole acetylation

Abstract

Tungstophosphoric acid (TPA) over zirconia dispersed uniformly in mesoporous silica (MS) channels of MCM-41 and MCM-48 were synthesized and tested for their catalytic activity in veratrole acetylation. Catalysts with different TPA loadings (5–50 wt.%) on 22.4 wt.%ZrO 2/MCM-41 and 15 wt.%TPA on different zirconia loadings (10–70 wt.%)/MCM-41 were prepared and calcined at 1123 K. The physico-chemical characterization of the supported catalysts was done by powder X-ray diffraction (XRD), surface area measurement (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed-infrared (FT-IR) spectroscopy, UV–vis diffuse reflectance spectra, Temperature programmed desorption (TPD) of ammonia, FT-IR pyridine adsorption and 31P cross polarization-magic angle spinning (CP-MAS) NMR spectroscopy. The mesoporous silica supports play an important role in stabilizing catalytically active TPA along with tetragonal phase of zirconia. Among the catalysts, 15 wt.%TPA/22.4 wt.%ZrO 2/MCM-41 calcined at 1123 K was found to have highest acidity and at least four times more active than neat 15 wt.%TPA/ZrO 2 in veratrole acetylation to acetoveratrone by acetic anhydride. Reaction conditions were evaluated with 15 wt.%TPA/22.4 wt.%ZrO 2/MCM-41 calcined at 1123 K to get higher conversion of acetic anhydride to acetoveratrone. The reaction was found to be heterogeneously catalyzed and no contribution from homogeneous (leached) TPA into the medium under the reaction conditions.