Optically Transparent Colloidal Dispersion of Titania Nanoparticles Storable for Longer than One Year Prepared by Sol/Gel Progressive Hydrolysis/Condensation

The molecular catalyst sensitized system (MCSS), where an excited molecular catalyst adsorbed on a semiconductor such as TiO2 injects electrons to the conduction band of the semiconductor leading to hydrogen evolution/CO2 reduction coupled with an oxidation of water on the molecular catalyst, has been one of the most probable candidates in the approach to artificial photosynthesis. For a full utilization of visible light, however, a serious light scattering of the aqueous suspension of TiO2 in the visible region, which is generally experienced, should be avoided. Here, we report a preparation of optically transparent colloidal dispersion of TiO2 by the sol/gel reaction of TiCl4 through progressive hydrolysis/condensation under the basic condition without any calcination processes. The TiO2 nanoparticles (TiO2(NPs)) obtained were characterized as an amorphous particle (∼10-15 nm) having a microcrystal domain of anatase within several nm by XRD, Raman spectroscopies, XRF, XAFS, TG/DTA, and HRTEM, respectively. The energy-resolved distribution of carrier electron traps in TiO2(NPs) as a fingerprint of TiO2 was characterized through reversed double-beam photo-acoustic spectroscopy to have a close similarity to that of TiO2(ST-01) as well as the observation of carrier traps by transient absorption spectroscopy. Though the powder TiO2(NP) itself was not dispersed well in aqueous solution, the wet TiO2(NPs) as prepared before being dried up provided a completely transparent aqueous dispersion under the acidic condition (1 M HCl). Addition of methanol enabled the colloidal dispersion (TiO2(NPs, MeOH/H2O, 0.1 M HCl)) to keep the optical transparency for longer than 1 year (550 days), which is the first example of TiO2 dispersion storable for such a long period. TiO2(NPs, MeOH/H2O) exhibited a moderate photocatalytic reactivity of H2 evolution with a quantum yield of ∼2.6% upon 365 nm light irradiation. An optically transparent thin film of TiO2(NPs, MeOH/H2O) was also successfully prepared on a glass plate to exhibit an enhanced hydrophilicity upon UV light irradiation.