Pure and Applied Chemistry

Abstract: The influence of halide ions on the photocatalytic process on titanium dioxide has been investigated carefully. Chloride and bromide ions, acting as hole scavengers, generate active radical species (e.g., ·Cl and ·Br) that participate in reactions with the organic compounds and the transient intermediates. Chloride and bromide ions have shown to deeply inhibit the degradation rate of chloroform and tetrachloromethane and to modify both the qualitative and quantitative distribution of their intermediates formed during the degradation process. In the presence of bromide, CBrCl3 is detected as intermediate during CCl4 degradation, while in the presence of chloride, formation of CCl4 is observed in the CHCl3 degradation. Fluoride ions, differently from the other halides, cannot be oxidized by the valence hole and may be used as a diagnostic tool in mechanistic studies. The influence of fluoride on phenol has been investigated, and, by choosing appropriate experimental conditions, it was possible to evaluate the role of the different active species in the photocatalytic process.