Enhanced electron transfer and multiple reactive species formation via a reductive heterojunction...

Addressing technical challenges in the advanced treatment of disinfection by-products (DBPs) is essential for ensuring the safety of drinking water. In this study, a novel treatment process was developed by coupling CFB photocatalysis with sulfite photoactivation (abbreviated as CFBP-SA process), wherein CFB refers to a previously reported reductive heterojunction photocatalyst, CoFe-layered double oxide/oxygen-vacancy-rich BiOBr. For trichloroacetamide (TCAcAm), one of the typical emerging DBPs, the CFBP-SA process achieved nearly complete removal within 60 min under simulated solar light with 0.6 g/L CFB and 2 mM sulfite. The corresponding reaction rate approached 0.062 min^-1, and the dechlorination rate reached 40%. As proved by electron paramagnetic resonance (EPR) and photoelectrochemical measurements, the enhanced process performance can be attributed to the improved electron utilization and the formation of multiple reactive species during the process. Quenching experiments and kinetic modeling demonstrated that e⁻ and H• are the primary contributors to the dechlorinative removal of TCAcAm under varying reaction conditions. Density functional theory (DFT) calculations in combination with product identification revealed that the major reaction pathways involve reductive dechlorination, sulfonation/desulfonation and deamination. Furthermore, the ecotoxicity evaluation based on quantitative structure-activity relationship predictions and zebrafish larvae behavioral assays reflected a significant detoxification of TCAcAm treated via the CFBP-SA process.