Long-Range Electronically Polarized Fe-N Catalysts Redirect Polymerization-Driven Phenolic Pollutant Removal Toward Sustainable Carbon Sequestration.

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 coordination at the atomic iron centers (Fe-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-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.