Engineering Electronic Structure of Metal‐Based Catalysts Toward Selective Peroxymonosulfate Activation for Water Purification

ABSTRACT Peroxymonosulfate (PMS) activation by metal‐based catalysts has attracted increasing attention as an effective approach for advanced oxidation processes (AOPs). However, the practical implementation remains limited by inefficient reaction activity, uncontrolled reactive species generation selectivity and unsatisfied long‐term stability. Recent studies have demonstrated that electronic structure regulation of metal‐based catalysts has emerged as a central strategy to address these challenges by regulating PMS adsorption behavior, interfacial electron transfer, and activation pathways. Hence, this review provides a systematic overview of recent advances in PMS activation from an electronic‐structure‐centered perspective, covering key modulation strategies including coordination environment regulation, metal doping, defect engineering and electron‐buffering metal‐support interactions. Particular emphasis is placed on elucidating how electronic structure descriptors, such as charge distribution, orbital hybridization, spin state, and d‐band center position, govern the PMS adsorption and reaction kinetics, charge transfer and recycle, selective generation of radical and non‐radical reactive species. Finally, current challenges related to green synthesis, mechanistic understanding, dynamic electronic evolution, and practical application are highlighted. This review aims to provide a mechanistic clarity and design principles to guide metal‐based catalyst construction for more controllable and efficient PMS‐based water treatment processes.