Hierarchically Porous Titania Thin Film Prepared by Controlled Phase Separation and Surfactant Templating

Poly(propylene glycol) (PPG) of moderately high molecular weight (M-n = 3500 Da) exhibits amphibious behavior in aqueous solution in that it is hydrophilic at low temperature but hydrophobic at high temperature. This property is utilized to generate porous titania thin films with a hierarchical structure consisting of macroporous voids/cracks in films with mesoporous walls. The smaller mesopores result from the self-assembly of the Pluronic block copolymer P123 to form micellar templates in well-ordered arrays with hexagonal symmetry. The larger pores are generated from the phase separation of PPG during aging of the films. The PPG acts to a limited degree as a swelling agent for the P123 micelles, but because the films are aged at a low temperature where PPG is hydrophilic, much of the PPG remains in the polar titania phase. Upon heating, the PPG phase separates to form randomly dispersed, large pores throughout the film while retaining the ordered mesoporous P123-templated structure in the matrix of the material. TEM and SEM imaging confirm that calcined titania thin films have interconnected hierarchical porous structures consisting of ordered mesopores 4-12 nm in diameter and macroporous voids >100 nm in size. The density and size of the voids increase as more PPG is added to the films.