Discriminative Peroxymonosulfate Activation on Iron Carbides for Redox‐Neutral Singlet Oxygen Generation

Abstract In conventional redox cycle‐based Fenton‐like processes, the imbalanced rates between the reductive activation of peroxymonosulfate (PMS) and the subsequent catalyst recovery by PMS oxidation often leads to the catalyst deactivation, posing a major challenge to achieving long‐term stability. Herein, we report a discriminative, redox‐neutral PMS activation pathway enabled by a core–shell Fe 3 C@C catalyst, which eliminates performance loss caused by such redox imbalance. Covalent Fe─C bonds within Fe 3 C@C suppress complete electron transfer for PMS oxidation or reduction, preventing the radical‐forming pathways. Instead, PMS is activated through electronic induction, discriminatively cleaving the peroxyl O─O bond to generate singlet oxygen ( 1 O 2 ) as the sole reactive oxygen species (ROS) without significant changes in the Fe valence state, thereby greatly enhancing catalyst durability. Beyond PMS activation, the highly conductive Fe 3 C@C network serves as an efficient electron relay, promoting pollutant degradation with 1 O 2 by facilitating electron‐exchange between PMS and pollutant. By integrating redox‐neutral PMS activation with electron‐connection driven pollutant oxidation, Fe 3 C@C achieves both high reactivity and exceptional long‐term stability, overcoming the traditional trade‐off between activity and durability. This work introduces a new paradigm in Fenton‐like catalysis, demonstrating how covalent coordination engineering can unlock selective, nonradical pathways for sustainable and robust water treatment.