CoOh-O-MnOh edge-sharing engineering in Co-Mn inverse spinel oxides for PMS activation: Electronic reconfiguration-driven nonradical oxidation via synergistic CoⅣ=O and 1O2

Precisely controlling atomic occupancy in edge-sharing sites remains challenging and limits the application of spinel oxides in advanced oxidation processes (AOPs). Herein, a series of inverse spinel oxides featuring edge-sharing Co Oh -O-Mn Oh (Oh means octahedral) configurations were designed to leverage inter-octahedral electronic redistribution and spin-state modulation, thereby enhancing catalytic performance for peroxymonosulfate (PMS) activation and pollutant degradation. The energy redistribution induced by this structure enhances the O-p/Mn-d orbital hybridization, accelerates the electron transfer kinetics between Co and Mn, and promotes the generation of high-valent cobalt-oxo (Co IV =O) species and singlet oxygen ( 1 O 2 ), thereby increasing the degradation efficiency of organic pollutants. The optimized Co-Mn inverse spinel achieved complete BPA removal within 15 min, exhibiting 11.4-fold enhancement in PMS activation efficiency than unmodified cobalt oxide, and with < 6.5 % average efficiency deviation at 100 mM ionic concentration. This study offers a strategy for the precise design of edge-sharing reactive sites in inverse spinel oxides and their application in AOPs.