Multi‐Cation Doped MnO₂ Induced Dual Nonradical Peroxymonosulfate Activation Pathways for Efficient Degradation of Organics

Abstract

Abstract Regulating electron transfer between peroxymonosulfate (PMS) and catalysts is a promising strategy to enhance the activity of the catalytic system. This work demonstrates a multi‐cation co‐doping strategy (Fe,Ni,Cu) to engineer the electronic configuration of δ‐MnO 2 , creating a novel nanocatalyst that synergistically couples electron transfer (PMS‐ETP) with singlet oxygen ( 1 O 2 ) generation for efficient pollutant degradation. The optimized catalyst exhibits excellent PMS activation efficiency, achieving a removal rate of >90.6% for diverse refractory contaminants within 10 min while maintaining satisfactory durability and structural stability during catalytic tests. Advanced synchrotron‐based X‐ray diffraction (SXRD) and density functional theory (DFT) verify that Fe,Ni,Cu co‐doping optimized the d‐band center of Mn and provides the electron‐absorbing sites. The in situ Raman spectroscopy, electrochemical analysis, and quenching tests confirm that the modified electronic structure facilitates bidirectional electron transfer between PMS and the catalyst, enabling broad‐spectrum purification capabilities across complex water matrices. This work provides atomic‐level insights into the multi‐metallic modulation of redox‐active catalysts and new ideas for designing energy‐efficient oxidation systems toward sustainable water remediation.