Keggin-type H4PVMo11O40-based catalysts for the isobutane selective oxidation

Cesium heteropolysalts Cs₃PMo₁₂O₄₀ and HCs₃PVMo₁₁O₄₀ were synthesized by modifying the preparation conditions in order to get materials with a much higher surface area than the original Keggin-type heteropolyacids (H₃PMo₁₂O₄₀ and H₄PVMo₁₁O₄₀). These solids were used as carriers for the dispersion of H₄PVMo₁₁O₄₀ heteropolyacid by the incipient wetness impregnation technique. The textural and structural properties of supports and catalysts were examined by scanning electron microscopy, N₂ adsorption-desorption isotherms and Raman spectroscopy. The supported catalysts were studied before and after red/ox pretreatments by X-ray photoelectron spectroscopy, which showed that both the surface composition and oxidized to reduced species ratio depend on the used carrier. The catalytic performances of these novel supported catalysts in the selective oxidation of isobutane to methacrylic acid and methacrolein were studied. The best catalytic properties were obtained when H₄PVMo₁₁O₄₀ was supported on HCs₃PVMo₁₁O₄₀. The isobutane conversion and yield of the desired oxygenates increased along the unsupported H₄PVMo₁₁O₄₀ < H₄PVMo₁₁O₄₀/Cs₃PMo₁₂O₄₀ < H₄PVMo₁₁O₄₀/HCs₃PVMo₁₁O₄₀ series.