Peroxymonosulfate-Based Electrochemical Advanced Oxidation: Complication by Oxygen Reduction Reaction

Peroxymonosulfate (PMS)-based electrochemical advanced oxidation processes (EAOPs) have received widespread attention in recent years, but the precise nature of PMS activation and its impact on the overall process performance remain poorly understood. This study presents the first demonstration of the critical role played by the oxygen reduction reaction in the effective utilization of PMS and the subsequent enhancement of overall pollutant remediation. We observed the concurrent generation of H₂O₂ via oxygen reduction during the cathodic PMS activation by a model nitrogen-doped carbon nanotube catalyst. A complex interplay between H₂O₂ generation and PMS activation, as well as a locally increased pH near the electrode due to the oxygen reduction reaction, resulted in a SO₄^•–/^•OH-mixed oxidation environment that facilitated pollutant degradation. The findings of this study highlight a unique dependency between PMS-driven and H₂O₂-driven EAOPs and a new perspective on a previously unexplored route for further enhancing PMS-based treatment processes.