The properties of mesoporous materials hinge on control of their composition, pore dimensions, wall thickness, and the size and shape of the crystallite building units. We create ordered mesoporous materials in which all of these parameters are independently controlled. Different sizes (from 4.5 to 8 nm) and shapes (spheres and rods) of ligand-stripped nanocrystals are assembled using the same structure-directing block copolymers, which contain a tethering domain designed to adsorb to their naked surfaces. Material compositions range from metal oxides (Sn-doped In(2)O(3) or ITO, CeO(2), TiO(2)) to metal fluorides (Yb,Er-doped NaYF(4)) and metals (FePt). The incorporation of new types of nanocrystals into mesoporous architectures can lead to enhanced performance. For example, TiO(2) nanorod-based materials withstand >1000 electrochemical cycles without significant degradation.

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SiO 2 /TiO 2 xerogel ultrathin protective coatings, with tunable refractive index between 1.45 and 2.20, have been prepared by dip-coating sol-gel solutions of TiCl 4 and tetraethyl orthosilicate with various molar compositions. In situ thermal ellipsometry analysis is used to follow the modifications of optical properties of these binary oxide systems upon thermal treatment up to 820 °C. Involved phenomena, such as dehydration, condensation, viscous sintering, crystallization, and diffusive sintering have been clearly identified and studied with respect to the Ti/Si atomic proportion and the treatment conditions. Due to the influence of the crystal size on the semiconducting properties of titania nanoparticles, its crystallization kinetic has been specifically investigated. We show that the crystallization of TiO 2 is globally taking place between 300 and 600 °C depending on the silica to titania ratio and on the heating rate. Films containing more than 40% of silica remain amorphous at 820 °C. Poor silica contents tend to be associated to lower crystallization temperature (T c ) and larger crystal sizes. The size of the smallest detected anatase nanoparticles was close to 4 nm, while those of the largest were limited by the film thickness around 35 nm. Interestingly, we observed that, while faster heating rates induce high T c for pure TiO 2 , the inverse tendency is observed for binary oxide films, which is explained by the diminution of the atomic diffusion due to the progressive condensation of the silica network. Electronic microscopy investigations revealed that smoother surface topologies and more homogeneously structured films are obtained in the presence of silica.