Unveiling Roles of Nonradical Electron‐Donation Pathway in Peroxymonosulfate Activation for Boosted Interfacial Radical Generation

In conventional studies, radicals and nonradicals were often considered independent mechanisms for organic pollutant oxidation, with their potential interaction between radicals and nonradicals largely overlooked in Fenton-like reactions. Herein, Cu-Co3O4 catalysts (x wt% Cu-Co3O4/OVs) featuring bifunctional bonding centers were fabricated, which enabled simultaneous co-capture of electron-rich contaminants and peroxymonosulfate (PMS) at their interfaces. The optimized 0.75 wt% Cu-Co3O4/OVs demonstrated exceptional efficiencies in degrading diverse micropollutants through synergistic oxidation pathways involving radicals and nonradical electron transfer process (ETP). Significantly, we found the unique dual electron migration pathways for PMS activation during synergistic oxidation process: besides the electron donation from Co centers, electron could be migrated via ETP from micropollutants to Co sites via heteroatomic Cu, serving as additional electron source for assisting PMS activation. In addition, synergistic oxidation pathways not only enhanced the generation of reactive species but also improved their utilization efficiency by shortening the migration distance of radicals. Such system exhibited remarkable long-term stability (up to 16 h) in wastewater treatment, with its environmental applicability further validated through life cycle assessment and bio-experiments. This work uncovered a previously unrecognized synergistic interaction between radical and nonradical pathways, offering new insights into the interfacial radical-mediated oxidation behavior for advanced wastewater remediation.