Novel catalyst-free activation of chlorine by visible light for micropollutant abatement

This study systematically investigated the direct activation of chlorine by visible light emitting diode (Vis-LED). Vis-LED could effectively activate chlorine to degrade micropollutants with degradation efficiency and pseudo-first-order degradation rate constant range of 64.3–100 % and 0.0340–0.195 min−1, respectively. Quenching experiments and modeling results suggested that reactive chlorine species (RCS, including ClO•, Cl2•-, and Cl•) and hydroxyl radical (•OH) were involved in the degradation of atenolol (ATL). The contribution ratio of ClO•, free available chlorine, Cl•, Cl2•-, and •OH to ATL degradation were 58.7 %, 17.4 %, 15.6 %, 1.8 %, and 5.9 %, respectively, in Vis-LED448/chlorine process. Moreover, the innate quantum yields of HClO and ClO- decreased from 0.229 and 0.0206 to 0.0489 and 0.0109 mol·Einstein−1, respectively, as the wavelength increased from 448 to 513 nm, leading to a decrease in ATL degradation, which was consistent with the model results. Experimental and modeling results have confirmed that ATL degradation decreased when pH increased from 4.0 to 9.0. Cl- had little effect on the degradation of ATL, while HA and HCO3- affected ATL degradation by scavenging reactive species and/or shielding effect. The concentration of disinfection by-products decreased with the increase of wavelength and pH. In summary, Vis-LED/chlorine is an efficient water treatment process even without a catalyst. [Display omitted] •Visible light can effectively activate chlorine to degrade organic micropollutants in water.•The innate quantum yield of chlorine decreased with the increase of visible light wavelength and pH.•ClO• was the major contributor to ATL degradation in the pH range of 4.0-9.0.•The increase of pH enhanced the contribution of ClO•.