Novel Visible Light-Driven Photocatalytic Chlorine Activation Process for Carbamazepine Degradation in Drinking Water

Photolysis of free chlorine (HOCl/ClO^-) is an advanced oxidation process (AOP) to produce hydroxyl (HO^•) and other radicals for refractory micropollutant degradation. However, HOCl/ClO^- is only conducive to activation and production of radicals by ultraviolet (UV) light. For the first time, we show the use of visible light (>400 nm) to produce HO^• and ClO^•, through use of graphitic carbon nitride (g-C₃N₄) and photogenerated h_vb⁺, e_cb^-, and O₂^•- in the presence of HOCl/ClO^-, which was termed visible light g-C₃N₄-enabled chlorine AOP (VgC-AOP). The VgC-AOP increased the pseudo first-order degradation rate constant of a model micropollutant, carbamazepine, by 16 and 7 times higher than that without g-C₃N₄ and HOCl/ClO^-, respectively, and remained active over multiple use cycles. Effects of water quality [pH, alkalinity, Cu(II), and natural organic matter (NOM)] and the operational conditions (g-C₃N₄ and HOCl/ClO^- concentrations, irradiation wavelength, and dose) were investigated. Of particular significance is its superior performance in the presence of NOM, which absorbs less light at visible light wavelengths and scavenges less surface-bonded reactive species, compared against UV/TiO₂ or UV/chlorine AOPs. The VgC-AOP is practically relevant, feasible, and easily implementable and it expands the potential types of light sources (e.g., LEDs and solar light).