In situ X-ray absorption spectroscopic studies of TiO₂ photocatalytic active sites for degradation of trace CHCl₃ in drinking water

Toxic disinfection byproducts such as trihalo­methanes (e.g. CHCl₃) are often found after chlorination of drinking water. It has been found that photocatalytic degradation of trace CHCl₃ in drinking water generally lacks an expected relationship with the crystalline phase, band-gap energy or the particle sizes of the TiO₂-based photocatalysts used such as nano TiO₂ on SBA-15 (Santa Barbara amorphous-15), TiO₂ clusters (TiO₂–SiO₂) and atomic dispersed Ti [Ti-MCM-41 (Mobil Composition of Matter)]. To engineer capable TiO₂ photocatalysts, a better understanding of their photoactive sites is of great importance and interest. Using in situ X-ray absorption near-edge structure (XANES) spectroscopy, the A₁ (4969 eV), A₂ (4971 eV) and A₃ (4972 eV) sites in TiO₂ can be distinguished as four-, five- and six- coordinated Ti species, respectively. Notably, the A₂ Ti sites that are the main photocatalytic species of TiO₂ are shown to be accountable for about 95% of the photocatalytic degradation of trace CHCl₃ in drinking water (7.2 p.p.m. CHCl₃ gTiO₂⁻¹ h⁻¹). This work reveals that the A₂ Ti species of a TiO₂-based photocatalyst are mainly responsible for the photocatalytic reactivity, especially in photocatalytic degradation of CHCl₃ in drinking water.