Mesoporous silica coated silica-titania spherical particles: from impregnation to core-shell formation

摘要

The coating of solid surfaces with inorganic materials is a promising approach not only to impart various functionalities but also to modify physicochemical properties that are affected by the geometry/structure of the coating. In this study, a silica-hexadecyltrimethylammonium (silica-CTA) hybrid layer was deposited on monodispersed spherical particles composed of titania and octadecylamine (titania-ODA) by a sol-gel reaction of tetraethoxysilane in aqueous CTA/ammonia/methanol solution. The formation of the coating was confirmed by SEM and TEM observations. The coating thickness varied from a few nm to 100 nm depending on the Si/Ti ratio. We found that Si/Ti = 0.68 resulted in the formation of microporous silica-titania particles with the pore size of 0.7 nm as revealed by nitrogen adsorption/desorption measurements. Because the titania-ODA particles can be converted to mesoporous titania particles after removing ODA by acid/base treatment, the silica species can be impregnated into the titania particles and replace ODA under basic conditions. By increasing the Si/Ti molar ratio up to 1.4, silica-titania particles with non-porous structures were obtained. An amorphous to anatase transition occurred at around 800 degrees C, indicating the complete impregnation of silica inside the titania particles. Further increases of the Si/Ti molar ratio (to 3.4 and 6.8) led to the formation of the silica-CTA shell on the core particles, and the shell was converted to mesoporous silica layers with a pore size of 2 nm after calcination at 550 degrees C for 5 h. Non-linear control of the pore size/structure is presented for the first time; this will be useful for the precise design of diverse hybrid materials for optical, catalytic and biomedical applications.