Synergistic mechanisms and regulatory principles of metal-pollutant complexation-mediated Fenton-like reactions

doi:10.19965/j.cnki.iwt.2025-0198

Abstract

Abstract:

Homogeneous Fenton-like technology, as an efficient water treatment process, has been widely applied in the remediation of complex industrial wastewater. In recent years, the continuous proposal of novel mechanisms within homogeneous Fenton-like systems has provided new opportunities for the deep degradation of pollutants,among which the complexation-mediated interactions between metal ions and pollutants are of particular significance. This paper systematically reviewed the critical roles of metal-pollutant complexes in Fenton-like systems, with a focused analysis of the efficiency-enhancing mechanisms of complexes in three representative reaction systems: Photo-Fenton systems, H₂O₂ activation systems, and peroxymonosulfate(PMS)/peroxydisulfate(PDS) activation systems. This paper revealed that complexes significantly improved pollutant degradation efficiency by modulating metal redox cycling kinetics, lowering redox potentials, and altering radical generation pathways. Furthermore, the influences of metal ion properties(oxidation states, coordination modes) and pollutant structural characteristics(functional groups, steric hindrance) on complexation behavior were clarified. Based on these mechanistic insights, an innovative “coordination-oxidation synergy” regulatory strategy was proposed. This strategy not only provided novel perspectives for designing highly selective heterogeneous catalysts but also established a theoretical foundation for optimizing process parameters in complex wastewater treatment.

Key words: Fenton-like reaction, metal ions, organic pollutants, complexation, advanced oxidation

摘要：

均相类Fenton技术作为一种高效的水处理工艺，在复杂工业废水处理领域获得广泛应用。近年来，均相类Fenton体系中新机制的不断提出为污染物深度降解提供了新契机，其中金属离子与污染物间的络合介导机制尤为值得关注。系统综述了金属-污染物络合体在类Fenton体系中的关键作用，重点解析了光Fenton体系、H₂O₂活化体系及过一硫酸盐（PMS）/过二硫酸盐（PDS）活化3类典型反应系统中络合体的增效作用机制，揭示了络合体可通过调控金属循环动力学、降低氧化还原电位及改变自由基生成路径显著提升污染物降解效能，明确了金属离子特性（价态、配位模式）和污染物结构（官能团、空间位阻）对络合行为的影响。基于上述机理，提出了“配位-氧化协同”调控策略，该策略不仅为设计高选择性非均相催化剂提供了新思路，同时为优化复杂废水处理工艺参数奠定了理论基础。

关键词: 类Fenton反应, 金属离子, 有机污染物, 络合作用, 高级氧化

CLC Number:

X703

Xiaoyu WU, Shurun YANG, Jiali LIU, Jiamei LIU, Zhihui XIE, Peng ZHOU, Heng ZHANG, Jing ZHANG, Zhaokun XIONG, Chuanshu HE, Bo LAI. Synergistic mechanisms and regulatory principles of metal-pollutant complexation-mediated Fenton-like reactions[J]. Industrial Water Treatment, 2026, 46(2): 19-28.

伍晓雨, 杨树润, 刘嘉丽, 刘嘉美, 谢智慧, 周鹏, 张恒, 张静, 熊兆锟, 何传书, 赖波. 金属-污染物络合介导的类Fenton反应协同机制与影响规律[J]. 工业水处理, 2026, 46(2): 19-28.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0198

https://www.iwt.cn/EN/Y2026/V46/I2/19

Figures/Tables 6

Fig.1 Pathway of the generation of free radicals or intermediates modulated by EDTA in Fenton systems

Fig.2 Mechanism of TET by photo-Fenton（a） and the formation of complex in Vis/PS/Fe（Ⅲ） system（b）

Fig.3 Mechanism of enhancing Fe（Ⅱ）activation of H₂O₂ through chelation

Fig.4 Mechanism of enhancing Cu（Ⅱ）activation of peroxydisulfate system through chelation

Table 1 Comparative analysis of complexation efficiency in different Fenton-like systems

类Fenton

体系

污染物降解速率提升1.5~2.5倍^〔51-53〕

H₂O₂

Co²⁺/Cu²⁺-污染物络合激活过硫酸盐

SO₄ ^·-、¹O₂主导

Cu-CN体系污染物降解效率提升2.8倍^〔71〕

高盐/含氰化物电镀废水

Fig.5 Effect of metal ion concentration on the degradation process

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