Stimuli-Responsive Ti-Organic Gels and Aerogels Derived from Ti-Oxo Clusters: Hierarchical Porosity and Photocatalytic Activity

Herein, we report titanium-organic gels (TOGs) as new Ti-oxo-based materials that exhibit stimuli-responsive sol-gel transformations and hierarchical porosity upon the removal of solvent molecules. Heating a solution of Ti-oxo clusters and pyromellitic acid as a tetratopic ligand produces TOGs that readily become sols by applying physical stimuli such as shaking or vortexing under ambient conditions. Porous titanium-organic aerogels (TOAs) were obtained by the CO₂ supercritical point drying (CPD) of the TOGs, and their porous structures were characterized by N₂ adsorption and desorption isotherm measurements. These TOAs, based on the Ti-oxo clusters, possess hierarchical micro-, meso-, and macropores. Furthermore, accompanying the prominent photochromic phenomena, reduction of Ti⁴⁺ to Ti³⁺ was observed upon UV irradiation. The TOAs were successfully applied in the adsorption and photocatalytic degradation of several dye molecules. This research introduces a versatile method for preparing stimuli-responsive and porous Ti-oxo-based photocatalysts.