One electron oxidation-induced degradation of brominated flame retardants in electroactive membrane filtration system: Vital role of dichlorine radical-mediated process.

Reactive chlorine species (RCS) are inevitably generated in electrochemical oxidation process for treating high-salinity industrial wastewater, thereby resulting in the competition with coexisting hydroxyl radicals (•OH) for oxidizing recalcitrant organic compounds. Due to the low redox potentials compared to •OH, the role of RCS has been often overlooked. In this work, we developed an electroactive membrane filtration (EMF) system that had a high removal efficiency (99.1 ± 0.5 %) for tetrabromobisphenol S (TBBPS) at low energy consumption (1.45 kWh m). Electron spin resonance spectroscopy and molecular probing tests indicated the predominance of Cl, of which steady-state concentration (2.2 ×10 M) was extremely higher than those of ClO• (6.7 ×10 M), •OH (0.95 ×10 M), and Cl• (2.39 ×10 M). The density functional theory (DFT) and intermediate product analysis highlighted that Cl radicals had a higher electrophilic attack efficacy than •OH radicals for inducing changes in the electron density of the carbon atoms around phenolic hydroxyl groups, thus leading to the generation of transition state intermediates and accelerating the degradation of TBBPS. Our work demonstrates the vital role of Cl radicals for pollutant degradation, highlighting the potential of this technology for cost-effective removal of recalcitrant organic compounds from water and wastewater.