Long‐Range Electronically Polarized Fe‐N5 Catalysts Redirect Polymerization‐Driven Phenolic Pollutant Removal Toward Sustainable Carbon Sequestration

Abstract A sustainable strategy for simultaneous pollutant removal and carbon sequestration is offered by the peroxymonosulfate (PMS)‐mediated electron transfer mechanism. However, it remains challenging to achieve catalysts with durable and high activity. A novel catalyst design strategy leveraging boron doping that induces long‐range electronic polarization to precisely modulate PMS complexation dynamics on single‐atom catalysts (SACs) is proposed in this study. It is demonstrated that B‐doping induces asymmetric Fe‐N 5 coordination at the atomic iron centers (Fe SA ‐BNC) while creating electron‐enriched carbon auxiliary sites. The electron distribution is synergistically optimized by this dual‐site configuration through lowering the d‐band center and establishing a polarized charge transfer pathway. Complexes with enhanced oxidation potential are generated by the engineered Fe SA ‐BNC/PMS, redirecting bisphenol A degradation from conventional radical‐mediated mineralization to an interfacial polymerization pathway via outer‐sphere electron transfer. Remarkably, >3 times higher total organic carbon (TOC) removal activity compared to state‐of‐the‐art catalysts and 4 orders of magnitude higher reactivity than conventional carbon nitride (CN) catalyst are exhibited by the optimized catalyst. Excellent operational stability (>1700 h continuous operation) with >120 L actual wastewater treatment capacity is demonstrated by practical implementation in a continuous‐flow microreactor. This work advances electronic modulation strategies for sustainable water purification technologies.