Direct synthesis of polyoxometalates-functionalized mesoporous hybrid silicas

Novel polyoxometalates (POMs)-functionalized mesoporous hybrid silicas (SiW11/MHS) were synthesized for the first time by the co-condensation of tetraethoxysilane (TEOS) with Keggin-type monovacant SiW11 in the presence of block copolymer EO20PO70EO20 (P123). The as-obtained SiW11/MHS samples were characterized by FT-IR, UV/DRS, XRD, ICP-AES, and N2 adsorption-desorption measurements. It is shown that not only a hexagonal packing of channels with homogeneous pore diameter is obtained, but also Keggin units remain perfectly in the hybrid materials, and Si species insert into the vacancies of lacunary SiW11 during the synthesis to form SiW11Si2 structure, which condenses with the framework of mesoporous silica thus grafting POM molecules onto the pore wall of mesoporous silica by covalent linkage. This linkage results in a firmer immobilization of POMs on the mesoporous material. The water-leaching percent of POMs in the hybrid material is much less than those in the impregnated samples. Therefore, the synthesis strategy for the hybrid material is significant for acquiring supported POM catalysts of high efficiency and practicability.