Important role of surface fluoride in nitrogen-doped TiO2 nanoparticles with visible light photocatalytic activity.

Nitrogen-doped TiO2 nanoparticles have been synthesized using sol-gel methods and subsequently fluorinated at room temperature by aging in acidic solutions of NaF. The nanoparticles were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis, and IR diffuse reflectance spectroscopy. After aging at room temperature in NaF solutions, the Ti-OH groups on the surface of the TiO2 nanoparticles were replaced by Ti-F bonds, which resulted in a decrease of the point of zero charge from pH 5.4 to 2.8. Most importantly, the nitrogen dopants were retained after the fluorination process, and the amorphous nanoparticles were partially converted into the anatase phase. Annealing the photocatalysts resulted in a decrease of both the nitrogen and fluoride atomic concentration. Diffuse reflectance spectra show an increase in absorbance above 400 nm after annealing the F,N-doped TiO2, which suggests the formation of color centers. The photoactivity of the F,N-doped and N-doped TiO2 catalysts were evaluated by monitoring by the decolorization of methylene blue with visible light. Mass spectrometric analysis revealed that methylene blue undergoes successive demethylation, and more importantly, the rate of decolorization depends on the fluoride concentration. These results show the importance of a two-step synthesis method to independently control the nitrogen and fluoride concentration.