Overcoming metals redox rate limitations in spinel oxide-driven Fenton-like reactions via synergistic heteroatom doping and carbon anchoring for efficient micropollutant removal.

The transition metals redox rate limitations of spinel oxides during Fenton-like reactions hinder its efficient and sustainable treatment of actual wastewater. Herein, we propose to optimize the electronic structure of Co-Mn spinel oxide (CM) via sulfur doping and carbon matrix anchoring synergistically, enhancing the radicals-nonradicals Fenton-like processes for efficient water decontamination. Activating peroxymonosulfate (PMS) with optimised spinel oxide (CMSAC) achieved near-complete removal of ofloxacin (10 mg/L) within 6 min, showing 8.4 times higher efficiency than CM group. Significantly higher yields of SO· and high-valent metal species in CMSAC/PMS system provided exceptional resistance to co-existing anions, enabling efficient removal of various emerging contaminants in high salinity leachate. Specifically, sulfur coordination and carbon anchoring-induced oxygen vacancy synergistically improved the electronic structure and electron transfer efficiency of CMSAC, thus forming highly reactive Co sites and significantly reducing the energy barrier for Co(IV)=O generation. The reductive sulfur species facilitated the conversion of Co(III) to Co(II), thereby maintaining the stability of the catalytic activity of CMSAC. This work developed a synergistic optimization strategy to overcome the metals redox rate limitations of spinel oxides in Fenton-like reactions, providing deep mechanistic insights for designing Fenton-like catalysts suitable for practical applications.