Supercritical preparation of a highly active S-doped TiO2 photocatalyst for methylene blue mineralization.

Sulfur-modification of the TiO2 was achieved by treating the TiO2 precursor (xerogel) under supercritical conditions in CS2/ethanol fluid. Nuclear magnetic resonance, X-ray photoelectron spectroscopy and Fourier transform infrared spectra demonstrated that the TiO2 was modified by the S-species incorporated into the TiO2 network by forming S-Ti-O bonds rather than by the adsorbed CS2. During liquid-phase photocatalytic degradation of methylene blue (MB) under visible light irradiation (> 420 nm), the as-prepared S-doped TiO2 exhibited much higher activity than the undoped TiO2 obtained via either supercritical treatment or direct calcinations and even the N-doped TiO2 obtained via supercritical treatment. The promoting effects of both the supercritical treatment and S-modification on the photocatalytic activity were discussed by considering the high surface, large porous channels, well crystallized anatase phase, excellent thermal stability, and strong absorbance for visible lights, corresponding to the high quantum efficiency. The maximum activity was obtained at 1.8% S/Ti molar ratio, nearly 8 times higher than that of the commercially available P25 TiO2.