Textile wastewater was typically characterized by high concentrations of chloride ions, with Acid Red 14 (AR14) representing a significant pollutant. Nevertheless, research into the degradation of AR14 by electrochemical advanced oxidation processes (EAOPs) had largely overlooked the influence of chloride ions. In this regard, the EC-Clorine-MMO/Ti system was designed, and the degradation mechanism of AR14 was subjected to meticulous investigation. The adopted anode was composed of Ti/IrO2-Ta2O5 (mixed metal oxide, MMO). It demonstrated superior efficiency in degrading AR14 within a sodium chloride (NaCl) electrolyte, registering an apparent kinetic constant rate approximately 16.76 times greater than that observed within a sodium perchlorate (NaClO4) electrolyte. The optimal chloride ion concentration was identified as 0.04 mol/L. Besides, alkaline conditions were not conducive to the degradation of AR14. It was noteworthy that the electrochemical byproducts chlorite (ClO2−), chlorate (ClO3−), perchlorate (ClO4−), and trihalomethane (THMs) were not produced in the solution treated by the EC-Clorine-MMO/Ti system. Electron paramagnetic resonance (EPR) spectroscopy, probe, and quenching experiments identified that hydroxyl radicals (•OH), superoxide radicals (O2•−), and dichloride radicals/chlorine monoxide radicals (Cl2•−/ ClO•) were the major reactive species. Of these, •OH played a pivotal role in AR14 degradation. Additionally, the three principal degradation pathways of AR14 were deduced by LC-MS analysis, UV–vis spectra, density-functional theory (DFT) calculations, and excitation-emission matrix (EEM) fluorescence spectroscopy. Furthermore, the generation mechanism of reactive species and the proposed mechanism of AR14 degradation by the EC-Clorine-MMO/Ti system were presented. The study made a significant contribution to the understanding of the electrochemical reactions occurring in textile wastewater and provided valuable insights into the rational control of electrolytic conditions for the treatment of saline wastewater.
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