No abstract

Periodically ordered mesoporous titania thin films (MTTF) present a high surface area, controlled porosity in the 2-20 nm pore diameter range and an amorphous or crystalline inorganic framework. These materials are nowadays routinely prepared by combining soft chemistry and supramolecular templating. Photocatalytic transparent coatings and titania-based solar cells are the immediate promising applications. However, a wealth of new prospective uses have emerged on the horizon, such as advanced catalysts, perm-selective membranes, optical materials based on plasmonics and photonics, metamaterials, biomaterials or new magnetic nanocomposites. Current and novel applications rely on the ultimate control of the materials features such as pore size and geometry, surface functionality and wall structure. Even if a certain control of these characteristics has been provided by the methods reported so far, the needs for the next generation of MTTF require a deeper insight in the physical and chemical processes taking place in their preparation and processing. This article presents a critical discussion of these aspects. This discussion is essential to evolve from know-how to sound knowledge, aiming at a rational materials design of these fascinating systems.

Mesoporous titania thin films with accessible porosity and anatase structure were synthesized on conductive glass or silicon substrates. Ti K-edge XANES was used to assess Ti local coordination. Analysis of the pre-edge region permitted accurate quantification of the degree of crystalline nature of the inorganic walls upon thermal treatment. The substrate has a marked effect:  film crystallization takes places at temperatures 100 °C lower in the crystalline Si, with respect to conductive glass. Accordingly, remarkable photocatalytic properties are found in well-crystallized mesoporous titania deposited onto conductive silicon.