Surface reactivity of non-hydrolytic silicophosphate xerogels: a simple method to create Bronsted or Lewis acid sites on porous supports
|Year of publication
|Article in Periodical
|Magazine / Source
|New Journal of Chemistry
|MU Faculty or unit
|Non-hydrolytic; sol-gel; silicon acetate; silicophosphate; xerogel; heterogeneous; catalysis; Lewis acid; Bronsted acid
|Non-hydrolytic sol-gel reactions of silicon acetates with trimethylsilyl (TMS) esters of phosphoric and phosphonic acids produce cross-linked matrices containing homogeneous dispersions of silicate and phosphoryl groups connected together by networks of Si-O-P(QO) linkages. The condensation degrees reach 80 to 90%. Residual organic groups (10 to 20%) were reacted with a variety of compounds (H2O, Me3SiOSiMe3, POCl3, SiCl4, AlMe3, Al(NMe2)(3), and AlCl3) in order to enrich the surface of these porous matrices with Bronsted (RP-OH) and Lewis (tetracoordinated Al) acid functional groups. The differences in the reactivity of RSi-OAc and RP-OSiMe3 groups were utilized for the selective modification at the silicon and phosphorus atoms. The reaction procedures were optimized and significantly porous silicophosphate materials with a high content of either hydroxyl groups or four-coordinated aluminium species were obtained. The activity and selectivity of prepared samples as catalysts for the dimerization of a-methylstyrene were tested. Excellent activities and moderate to very high selectivities were achieved suggesting the potential use of silicophosphate xerogels in heterogeneous catalysis.