Dual‐Promotion of Fenton‐Like Activity via Mn/N Electron‐Rich Configuration and Micro‐Contaminants Co‐Mediated Electron Transfer Process

ABSTRACT Non‐radical mechanisms are widely recognized as an effective strategy for the selective oxidation of organic micro‐contaminants. Herein, this study systematically elucidates a dual‐promotion mechanism that enhances Fenton‐like oxidation efficiency through co‐mediation by the Mn/N electron‐rich configuration and micro‐contaminants co‐mediated electron transfer processes (ETP). The Mn 1 /N 2 ‐BC+PMS system demonstrates superior degradation efficiency and promotes selectivity toward electron‐rich micro‐contaminants. Notably, within this dual‐promoted Fenton‐like oxidation system, a unique dual‐electron supply pathway for peroxymonosulfate (PMS) activation has been identified: in addition to direct electron donation from the Mn 1 ‐N site, electrons can also be transferred from micro‐contaminants via the N‐Mn 2 site to the Mn 1 center through an ETP, serving as an auxiliary electron source that facilitates PMS activation and enables the formation of a closed‐loop electron circulation. The dual‐electron activation pathway not only promotes 1 O 2 generation but also minimizes the migration distance, significantly enhancing its utilization efficiency. The Mn 1 /N 2 ‐BC+PMS system demonstrates outstanding decontamination efficiency, robustness against interfering substances, long‐term operational stability, and excellent environmental adaptability in treating actual wastewater. By integrating the perspectives of catalyst micro‐interface engineering and the electrophilic/nucleophilic characteristics of micro‐contaminants, this work reveals a previously overlooked synergistic interaction between 1 O 2 and ETP, offering new insights into non‐radical mediated oxidation mechanisms for advanced wastewater remediation.