Manipulation of the phase structure of vinyl-functionalized phenylene bridging periodic mesoporous organosilica

A series of vinyl-functionalized periodic mesoporous organosilicas (PMOs) were prepared by co-condensation of 1,4-bis (triethoxysilyl) benzene (BTEB) and triethoxyvinylsilane (TEVS) using the triblock copolymer Pluronic P123 as a template under acid conditions. It is found that the mesophases of resultant PMOs can be controlled via altering the fraction of organosilanes in the synthesis mixture and catalyst HCl concentration. With increasing fraction of TEVS, mesophase of the PMOs materials changed from p6mm to Ia3d, and then becomes a disordered material. For PMOs with 15 molar percentage of TEVS, the increase of HCl concentration can induce a transformation of mesophases from hexagonal p6mm to cubic Ia3d, whereas, a mixture of p6mm/disordered structure forms at lower acid concentration for the PMOs containing 5 % TEVS. The mechanisms of mesophase transformation were discussed based on the adsorption of TEVS into the micelles, influence of acid concentration on the hydrolysis and condensation rate, and the relative reactivities of the organosilane precursors.