Long‐Range Electronic‐Regulation‐Modulated Peracetic Acid Nonradical Activation for Water Decontamination via Selective High‐Valent Cobalt–Oxo Species Formation

Rapid generation of high‐valent cobalt–oxo species, Co(IV)═O, is crucial for selectively oxidizing electron‐rich pollutants but is limited by high energy barriers of Co(II)‐oxidant‐complexes and low Co 3d‐orbital electron density. Herein, a strategy is proposed to construct MXene‐based heterojunction catalyst (Ti 3 C 2 O V /Co) featuring strategically designed “oxygen‐vacancy–metal (O V –metal) bridge” defect at the interface in a peracetic acid (PAA) system. These intrinsic defects beyond the first coordination shell optimize the electron distribution of the Co 3d‐orbital through long‐range electronic regulation (LRER), promoting Bader charge transfer, enhancing the PAA adsorption energy. This regulation facilitates key intermediate (CH 3 C(O)*OH─*O) formation, lowers the deprotonation energy barrier of *O via intramolecular proton migration, and ultimately boosts selective Co(IV)═O generation. Ti 3 C 2 O V /Co/PAA system demonstrates exceptional catalytic performance, achieving a pollutant degradation kinetic constant of 0.16 µ m min −1 mg −1 , surpassing most reported heterogeneous catalyst/PAA systems. Competitive kinetics analysis reveals that Ti 3 C 2 O V /Co/PAA system achieves Co(IV)═O‐dominant pollutant oxidation (91.54% contribution) with a steady‐state concentration of 2.91 × 10 −10 m . This highly selective oxidation process converts pollutants into low‐toxic products via oxygen transfer reactions. Life cycle assessment and long‐term tests confirm the system's potential for continuous industrial‐scale wastewater treatment. This study presents an efficient PAA activation strategy via LRER‐driven high‐valent metal‐oxo oxidation for water purification.