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<p>Periodate (PI)-based oxidation has emerged as a promising alternative to conventional advanced oxidation processes in water treatment. Among various catalytic systems, manganese-periodate (Mn/PI) systems have attracted increasing attention due to their environmental compatibility, cost-effectiveness, and distinctive reactivity. However, existing studies predominantly interpret Mn/PI chemistry from an “activation” perspective, while a unified understanding of its intrinsic redox nature remains lacking. Herein, we propose that Mn/PI systems should be redefined as redox-coupled catalytic networks, in which manganese species and iodine species undergo mutual redox interactions, driving pollutant transformation through multiple intertwined pathways. This review systematically elucidates the fundamental physicochemical properties of PI and traces the evolution of Mn/PI systems, supported by bibliometric analysis to reveal emerging research trends. Manganese-based catalysts are categorized into six classes according to manganese speciation and structural configuration, and their performance in degrading representative emerging contaminants is critically evaluated. Mechanistically, Mn/PI systems are interpreted through four interconnected pathways: reactive manganese species, reactive iodine species, reactive oxygen species, and electron transfer. Special emphasis is placed on the pivotal role of electron transfer and high-valent manganese intermediates in governing selective oxidation and limited mineralization. Furthermore, emerging evidence suggests that such redox-driven pathways may induce transformation-oriented processes, including coupling or oligomerization of electron-rich contaminants, thereby underscoring the need to reassess Mn/PI systems from both pathway complexity and application-scenario perspectives. Beyond pollutant degradation, the transformation, cycling, and environmental fate of iodine species are comprehensively analyzed, highlighting potential risks associated with iodinated by-products and secondary pollution. Finally, key challenges related to mechanistic ambiguity, mineralization efficiency, material durability, and large-scale applicability are identified. Future research directions are proposed to shift the focus from simple contaminant removal toward redox regulation, iodine risk management, and scenario-oriented application. This review aims to establish a conceptual framework for understanding Mn/PI redox coupling and to provide theoretical guidance for the rational design and sustainable implementation of Mn/PI systems.</p>

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Redox-coupled manganese-periodate systems: mechanistic insights, iodine fate, and environmental implications

  • 期刊论文

  • 发表日期：

    2026年7月9日

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  • Ziyi Dong,
  • Jian Lu,
  • Chenyan Hu,
  • Zhengyu Dong,
  • Tianyang Zhang,
  • Chuqiao Wang,
  • Xiaoming Peng,
  • Bin Xu

摘要

Periodate (PI)-based oxidation has emerged as a promising alternative to conventional advanced oxidation processes in water treatment. Among various catalytic systems, manganese-periodate (Mn/PI) systems have attracted increasing attention due to their environmental compatibility, cost-effectiveness, and distinctive reactivity. However, existing studies predominantly interpret Mn/PI chemistry from an “activation” perspective, while a unified understanding of its intrinsic redox nature remains lacking. Herein, we propose that Mn/PI systems should be redefined as redox-coupled catalytic networks, in which manganese species and iodine species undergo mutual redox interactions, driving pollutant transformation through multiple intertwined pathways. This review systematically elucidates the fundamental physicochemical properties of PI and traces the evolution of Mn/PI systems, supported by bibliometric analysis to reveal emerging research trends. Manganese-based catalysts are categorized into six classes according to manganese speciation and structural configuration, and their performance in degrading representative emerging contaminants is critically evaluated. Mechanistically, Mn/PI systems are interpreted through four interconnected pathways: reactive manganese species, reactive iodine species, reactive oxygen species, and electron transfer. Special emphasis is placed on the pivotal role of electron transfer and high-valent manganese intermediates in governing selective oxidation and limited mineralization. Furthermore, emerging evidence suggests that such redox-driven pathways may induce transformation-oriented processes, including coupling or oligomerization of electron-rich contaminants, thereby underscoring the need to reassess Mn/PI systems from both pathway complexity and application-scenario perspectives. Beyond pollutant degradation, the transformation, cycling, and environmental fate of iodine species are comprehensively analyzed, highlighting potential risks associated with iodinated by-products and secondary pollution. Finally, key challenges related to mechanistic ambiguity, mineralization efficiency, material durability, and large-scale applicability are identified. Future research directions are proposed to shift the focus from simple contaminant removal toward redox regulation, iodine risk management, and scenario-oriented application. This review aims to establish a conceptual framework for understanding Mn/PI redox coupling and to provide theoretical guidance for the rational design and sustainable implementation of Mn/PI systems.