增强非均相光催化自芬顿体系中的Fe(III)/Fe(II)循环用于有机污染物降解

doi:10.1016/S1872-2067(26)65034-6

催化学报 ›› 2026, Vol. 91: 376-385.DOI: 10.1016/S1872-2067(26)65034-6

增强非均相光催化自芬顿体系中的Fe(III)/Fe(II)循环用于有机污染物降解

季蓉^a^,^b, 易靖然^a, 孙新宇^a, 董玉明^a^,^*(), 潘成思^a, 赵辉^a, 朱永法^c

^a 江南大学化学与材料工程学院, 光响应分子与材料国际联合研究中心, 江苏无锡 214122
^b 南京理工大学新能源学院, 江苏南京 210094
^c 清华大学化学系, 北京 100084

收稿日期:2025-12-23 接受日期:2026-02-22 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: dongym@jiangnan.edu.cn (董玉明).
基金资助:
国家自然科学基金(22136002);国家自然科学基金(22172064);国家自然科学基金(22572073);中央高校基本科研业务费专项资金(JUSRP202404010);江苏省基础研究计划(BK20220023)

Enhanced Fe(III)/Fe(II) cycle in heterogeneous photocatalysis-self-Fenton system for organic pollutants degradation

Rong Ji^a^,^b, Jingran Yi^a, Xinyu Sun^a, Yuming Dong^a^,^*(), Chengsi Pan^a, Hui Zhao^a, Yongfa Zhu^c

^a International Joint Research Center for Photo-responsive Molecules and Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China
^b School of New Energy, Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China
^c Department of Chemistry, Tsinghua University, Beijing 100084, China

Received:2025-12-23 Accepted:2026-02-22 Online:2026-12-18 Published:2026-10-13
Supported by:
National Natural Science Foundation of China(22136002);National Natural Science Foundation of China(22172064);National Natural Science Foundation of China(22572073);Research Funds for the Central Universities(JUSRP202404010);Basic Research Program of Jiangsu(BK20220023)

摘要/Abstract

摘要：

芬顿反应基于过氧化氢(H₂O₂)与亚铁离子(Fe(II))产生的强氧化性羟基自由基(^•OH), 在废水处理领域展现出巨大潜力. 然而, 传统芬顿技术面临诸多挑战: Fe(II)在反应中易被迅速氧化为Fe(III)且再生缓慢, 导致反应效率下降; 需要持续外加H₂O₂, 增加成本与安全风险; 反应后产生大量含铁污泥, 易造成二次污染. 非均相光催化自芬顿体系将光催化原位合成H₂O₂与芬顿反应耦合, 为解决上述问题提供了新思路. 然而, 该体系的关键瓶颈在于Fe(III)/Fe(II)循环速率缓慢, 严重限制了H₂O₂向^•OH的高效转化和污染物的持续矿化. 因此, 开发能够同时实现高效H₂O₂原位合成与快速Fe(III)还原的新型光催化材料, 对于提升非均相光催化自芬顿体系的实用性具有重要意义.
本文创新性地设计并合成了一种新型铁基共轭聚合物光催化剂(Fe-Py-Tp-BDTO), 成功构建了高效的非均相光催化自芬顿体系. 该催化剂采用给体(D)-π-受体(A)型分子结构: 以具有强给电子能力的平面共轭芘单元(Py)为电子给体, 噻吩(Tp)为π桥促进电子离域, 二苯并噻吩-S,S-二氧化物(BDTO)为电子受体. 这种D-π-A结构不仅有利于光生电荷的快速分离与迁移, 而且BDTO单元通过2电子氧还原反应(2e^- ORR)高效原位合成H₂O₂, 噻吩桥则作为独立的电子传输中心促进^•OOH中间体的生成. 更重要的是, Fe活性位点通过Fe-O键锚定在电子受体BDTO的富电子区域, 形成的Fe-O簇不仅稳定了Fe位点, 还使其周围富集高密度电子, 从而极大加速了Fe(III)向Fe(II)的还原, 实现了原位生成H₂O₂的快速活化. 实验结果表明, 优化后的Fe-Py-Tp-BDTO催化剂在模拟太阳光下对4-氯苯酚的降解表现卓越: 反应速率常数高达0.14 min^-1, 30 min内去除率接近100%, 总有机碳去除率达到79.1%, 显著优于目前报道的大多数光芬顿催化剂. 其H₂O₂向^•OH的转化率高达75.8%, 是传统芬顿反应的3.5倍. 该体系在pH=3-7的宽范围内均保持高效活性, 对双酚A、四环素等多种有机污染物也表现出优异的广谱降解能力, 且经20次循环实验后活性无明显衰减, 展现出优异的稳定性. D-π-A结构促进了光生电子从Py单元经Tp桥向BDTO的快速迁移; 富集在BDTO上的电子一方面将吸附的O₂通过2e^-路径还原为H₂O₂, 另一方面, 富集在Fe-O活性位点, 快速将Fe(III)还原为Fe(II); 原位生成的H₂O₂随即在Fe(II)位点被活化, 高效产生大量^•OH, 实现对污染物的深度矿化. 这种空间分离式设计, 从根本上解决了传统芬顿反应中Fe(III)再生难、H₂O₂利用率低的问题.
综上, 本研究通过精准的分子工程设计, 成功构建了集高效H₂O₂原位合成与快速Fe(III)/Fe(II)循环于一体的铁基共轭聚合物光催化自芬顿体系, 为突破传统芬顿技术的瓶颈提供了新思路. 该工作不仅为高效水处理技术的开发提供了理论依据和可行的材料方案, 也展示了共轭聚合物在环境催化领域的广阔应用前景. 未来, 结合原位动态表征技术与理论计算, 进一步阐明活性中心的动态演变规律, 优化分子结构以提升太阳光利用率和稳定性, 并探索其在真实水体环境中的应用性能, 将推动该技术向实用化方向迈进.

关键词: Fe-Py-Tp-BDTO, 非均相光催化自芬顿, Fe(III)/Fe(II)循环, 污染物降解, 光催化剂

Abstract:

Heterogeneous photocatalysis-self-Fenton systems have emerged as a promising method for wastewater treatment. However, their reaction efficiency is often severely limited by the sluggish regeneration of ferrous (Fe(II)). In this work, we report a novel iron(Fe)-based conjugated polymer capable of simultaneously achieving 2-electron photocatalytic oxygen activation and Fe(III) reduction, thereby enabling efficient degradation of organic pollutants. The underlying mechanism of the accelerated Fe(III)/Fe(II) cycle and enhanced degradation performance within this system is also elucidated. The polymer is constructed using a planar conjugated pyrene (Py) unit as the electron donor, which facilitates electron transfer for the reduction of Fe(III) to Fe(II) during H₂O₂ activation. Thiophene (Tp) and dibenzo[b,d]thiophene-s,s-dioxide (BDTO) are incorporated as the π-spacer and electron acceptor, respectively. The optimized Fe-Py-Tp-BDTO catalyst demonstrated outstanding performance, with an apparent rate constant of 0.14 min^-1 for 4-chlorophenol degradation and a mineralization rate of 79.1%, which significantly surpasses those of current photocatalysts. Quenching experiments confirmed that hydroxyl radicals and holes are the predominant reactive species responsible for pollutant removal. This work successfully establishes a heterogeneous photocatalysis-self-Fenton system with a highly efficient Fe(III)/Fe(II) cycle, thereby broadening the practical application scope of conventional Fenton technology.

Key words: Fe-Py-Tp-BDTO, Heterogeneous photocatalysis-self-Fenton, Fe(III)/Fe(II) cycle, Pollutant degradation, Photocatalyst

季蓉, 易靖然, 孙新宇, 董玉明, 潘成思, 赵辉, 朱永法. 增强非均相光催化自芬顿体系中的Fe(III)/Fe(II)循环用于有机污染物降解[J]. 催化学报, 2026, 91: 376-385.

Rong Ji, Jingran Yi, Xinyu Sun, Yuming Dong, Chengsi Pan, Hui Zhao, Yongfa Zhu. Enhanced Fe(III)/Fe(II) cycle in heterogeneous photocatalysis-self-Fenton system for organic pollutants degradation[J]. Chinese Journal of Catalysis, 2026, 91: 376-385.

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Fig. 1. (a) The structure of Fe-Py-Tp-BDTO. (b) FT-IR spectra of Fe-Py-Tp-BDTO and Py-Tp-BDTO. (c) The XPS spectra of Fe 2p of Fe-Py-Tp-BDTO. (d) O 1s XPS spectra of Py-Tp-BDTO and Fe-Py-Tp-BDTO. (e) The quasi in-situ EPR spectra of Py-Tp-BDTO and Fe-Py-Tp-BDTO.

Fig. 2. (a) Time profiles of H2O2 production for all samples in 4-chlorophenol solution. (b) Degradation ability for 4-chlorophenol over different systems. (c) k-value and TOC removal rate for different systems. (d) Heterogeneous photocatalysis-self-Fenton (PSF) degradation curves at different pH. (e) Wide applicability for various organic pollutants over photocatalysis-self-Fenton system: removal rate within 30 min over Fe-Py-Tp-BDTO. (f) Heterogeneous photocatalysis-self-Fenton cycle performance (Condition: catalyst=0.6 g L-1, 4-chlorophenol=10 mg L-1, 300 W Xe lamp, AM1.5. Concentration of organic pollutants: 10 mg L-1, BPA: bisphenol A, CIP: ciprofloxacin; NOR: norfloxacin; PHE: phenol; TC: tetracycline).

Fig. 3. (a) Free radical capture degradation curve over Fe-Py-Tp-BDTO. (b) EPR spectra of DMPO-•OH for all systems. (c) •OH yield profile of systems. (d) •OH transformation rate over photocatalysis-self-Fenton system and Fenton technology (Condition: catalyst=0.6 g L-1, 4-chlorophenol=10 mg L-1, 300 W Xe lamp, AM 1.5G).

Fig. 4. Steady-state PL spectra (a) and transient photocurrent response (b) of Py-Tp-BDTO and Fe-Py-Tp-BDTO. (c) Surface potential of Py-Tp-BDTO and Fe-Py-Tp-BDTO. fs-TA spectra (d) and pseudocolor plots (e) of Fe-Py-Tp-BDTO (All the samples are tested under 400 nm laser pulse excitation in H2O). (f) Raman spectra of Fe-Py-Tp-BDTO.

Fig. 5. In-situ DRIFT spectra recorded during photocatalytic H2O2 evolution of Py-Tp-BDTO (a) and Fe-Py-Tp-BDTO (b). ESR spectra of Py-Tp-BDTO (c) and Fe-Py-Tp-BDTO (d)+H2O2. (e) Eads of O2 on active sites of Py-Tp-BDTO and Fe-Py-Tp-BDTO. (f) The free-energy diagrams of Fe-Py-Tp-BDTO (Condition: catalyst=0.6 g L-1, 300 W Xe lamp, AM 1.5G).

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增强非均相光催化自芬顿体系中的Fe(III)/Fe(II)循环用于有机污染物降解

Enhanced Fe(III)/Fe(II) cycle in heterogeneous photocatalysis-self-Fenton system for organic pollutants degradation

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