A general sol-gel process has been developed to form a coating of resorcinol-formaldehyde (RF) resin on inorganic nanostructures of various compositions and morphologies. The RF shell can be conveniently converted into carbon through high temperature carbonization under an inert atmosphere.

Mesoporous nanocrystal clusters of anatase TiO 2 with large surface area and enhanced photocatalytic activity have been successfully synthesized. The synthesis involves the self-assembly of hydrophobic TiO 2 nanocrystals into submicron clusters, coating of these clusters with a silica layer, thermal treatment to remove organic ligands and improve the crystallinity of the clusters, and finally removing silica to expose the mesoporous catalysts. With the help of the silica coating, the clusters not only maintain their small grain size but also keep their mesoporous structure after calcination at high temperatures (with BET surface area as high as 277 m 2 /g). The etching of SiO 2 also results in the clusters having high dispersity in water. We have been able to identify the optimal calcination temperature to produce TiO 2 nanocrystal clusters that possess both high crystallinity and large surface area, and therefore show excellent catalytic efficiency in the decomposition of organic molecules under illumination by UV light. Convenient doping with nitrogen converts these nanocrystal clusters into active photocatalysts in both visible light and natural sunlight. The strategy of forming well-defined mesoporous clusters using nanocrystals promises a versatile and useful method for designing photocatalysts with enhanced activity and stability.

The spectroscopic and photocatalytic properties of a series of Au@TiO(2) core-shell nanostructures are characterized. The crystallinity of the TiO(2) shells was varied by changing the etching and calcination conditions. Measurements of the photoluminescence, transient absorption, and H(2) production rate permit us to look for correlations between the spectroscopic and catalytic behaviors. We found that there is a strong effect of crystallinity on the H(2) production rate and also the stretched exponential lifetime of the photoluminescence created by short-wavelength (266 and 300 nm) photoexcitation. As the TiO(2) crystallinity is increased, the photoluminescence lifetime increases from 22 to 140 ps in a 1 ns detection window, while the H(2) production rate increases by a factor of ~4. There is no discernible effect of crystallinity on the photoluminescence dynamics excited at 350 or 430 nm, or on the electronic dynamics measured by femtosecond transient absorption after excitation at 300 nm. We hypothesize that high-energy photons create reactive and emissive charge-separated states in parallel, and that both species are subject to similar electron-hole recombination processes that depend on sample crystallinity. Based on our observations, it can be concluded that the photoluminescence dynamics may be used to evaluate the potential performance of this class of photocatalysts.

In this work, we carried out both theoretical calculation and experimental studies to reveal the contribution of hollow geometry to the light utilization efficiency of the TiO2 photocatalysts in diluted aqueous solution. It is found that the single or multi-shelled hollow structures do not induce significant multiple reflections within the shells as widely believed in previous reports, and therefore the geometric factor has minimal contribution to the improvement of the light utilization efficiency of the photocatalyst. To design TiO2 photocatalysts with higher activity, it is more appropriate to focus on the improvement of the crystallinity, diffusion, surface area, and dispersity of the catalysts, rather than their geometric shapes.