Iron Redox Cycling in Persulfate Activation: Strategic Enhancements, Mechanistic Insights, and Environmental Applications—A Review

Iron-based catalysts for peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation represent a cornerstone of advanced oxidation processes (AOPs) in environmental remediation, prized for their cost-effectiveness, environmental compatibility, and high catalytic potential. These catalysts, including zero-valent iron, iron oxides, and iron-organic frameworks, activate PMS/PDS through heterogeneous and homogeneous pathways to generate reactive species such as sulfate radicals (SO₄•^-) and hydroxyl radicals (•OH). However, their large-scale implementation is constrained by inefficient iron cycling, characterized by sluggish Fe³⁺/Fe²⁺ conversion and significant iron precipitation, leading to catalyst passivation and oxidant wastage. This comprehensive review systematically dissects innovative strategies to augment iron cycling efficiency, encompassing advanced material design through elemental doping, heterostructure construction, and defect engineering; system optimization via reductant incorporation, bimetallic synergy, and pH modulation; and external field assistance using light, electricity, or ultrasound. We present a mechanistic deep-dive into these approaches, emphasizing facilitated electron transfer, suppression of iron precipitation, and precise regulation of radical versus non-radical pathways. The performance in degrading persistent organic pollutants-including antibiotics, per- and polyfluoroalkyl substances (PFASs), and pesticides-in complex environmental matrices is critically evaluated. We further discuss practical challenges related to scalability, long-term stability, and secondary environmental risks. Finally, forward-looking directions are proposed, focusing on rational catalyst design, integration of sustainable processes, and scalable implementation, thereby providing a foundational framework for developing next-generation iron-persulfate catalytic systems.