Tuning Texture and Morphology of Mesoporous TiO₂ by Non-Hydrolytic Sol-Gel Syntheses

The development of powerful synthetic methodologies is paramount in the design of advanced nanostructured materials. Owing to its remarkable properties and low cost, nanostructured TiO₂ is widely investigated for applications such as photocatalysis, energy conversion or energy storage. In this article we report the synthesis of mesoporous TiO₂ by three different non-hydrolytic sol-gel routes, and we investigate the influence of the synthetic route and of the presence and nature of the solvent on the structure, texture and morphology of the materials. The first route is the well-known ether route, based on the reaction of TiCl₄ with ⁱPr₂O. The second and third routes, which have not been previously described for the synthesis of mesoporous TiO₂, involve the reaction of Ti(OⁱPr)₄ with stoichiometric amounts of acetophenone and benzoic anhydride, respectively. All materials are characterized by XRD, N₂ physisorption and SEM. By playing with the non-hydrolytic route used and the reaction conditions (presence of a solvent, nature of the solvent, calcination), it is possible to tune the morphology and texture of the TiO₂. Depending on the reaction conditions, a large variety of mesoporous TiO₂ nanostructures could be obtained, resulting from the spontaneous aggregation of TiO₂ nanoparticles, either rounded nanoparticles, platelets or nanorods. These nanoparticle networks exhibited a specific surface area up to 250 m² g^-1 before calcination, or up to 110 m² g^-1 after calcination.