Block Copolymer Templating Syntheses of Mesoporous Metal Oxides with Large Ordering Lengths and Semicrystalline Framework

A simple and general procedure has been developed for the syntheses of ordered large-pore (up to 14 nm) mesoporous metal oxides, including TiO2, ZrO2, Nb2O5, Ta2O5, Al2O3, SiO2, SnO2, WO3, HfO2, and mixed oxides SiAlOy, Al2TiOy, ZrTiOy, SiTiOy, ZrW2Oy. Amphiphilic poly(alkylene oxide) block copolymers were used as structure-directing agents in nonaqueous solutions for organizing the network-forming metal oxide species. Inorganic salts, rather than alkoxides or organic metal complexes, were used as soluble and hydrolyzable precursors to the polymerized metal oxide framework. These thermally stable mesoporous oxides have robust inorganic frameworks and thick channel walls, within which high densities of nanocrystallites can be nucleated. These novel mesoporous metal oxides are believed to be formed through a mechanism that combines block copolymer self-assembly with alkylene oxide complexation of the inorganic metal species.