A Polymer-Oriented Self-Assembly Strategy toward Mesoporous Metal Oxides with Ultrahigh Surface Areas

Mesoporous metal oxides (MMOs) have attracted comprehensive attention in many fields, including energy storage, catalysis, and separation. Current synthesis of MMOs mainly involve use of surfactants as templates to generate mesopores and organic reagents as solvents to hinder hydrolysis and condensation of inorganic precursors, which is adverse to adjusting the interactions between surfactants and inorganic precursors. The resulting products have uncontrollable pore structure, crystallinity, and relatively lower surface areas. Here, a facile and general polymer-oriented self-assembly strategy to synthesize a series of MMOs (e.g., TiO₂, ZrO₂, NbO₅, Al₂O₃, Ta₂O₅, HfO₂, and SnO₂) by using cationic polymers as porogens and metal alkoxides as metal oxide precursors in a robust aqueous synthesis system are reported. Nitrogen adsorption analysis and transmission electron microscopy confirm that the obtained MMOs have ultrahigh specific surface areas and large pore volumes (i.e., 733 m² g^-1 and 0.485 cm³ g^-1 for mesoporous TiO₂). Moreover, the structural parameters (surface area, pore size, and pore volume) and crystallinity can be readily controlled by tuning the interactions between cationic polymers and precursors. The as-synthesized crystalline mesoporous TiO₂ exhibits promising performance in photocatalytic water splitting of hydrogen production and a high hydrogen production rate of 3.68 mol h^-1 g^-1.