基于改性Fe<sup>0</sup>的非均相电Fenton-过硫酸盐体系降解抗生素

doi:10.19965/j.cnki.iwt.2025-0418

摘要/Abstract

摘要：

水体中抗生素污染日益严重，对生态环境和人类健康构成潜在威胁。利用预磁化耦合硫化改性零价铁（pre-S/Fe⁰）作为催化剂，MoS₂负载双功能电极（MC）为阴极，过硫酸盐（PS）为电解质构建了一种高效的非均相电Fenton体系（PS/pre-S/Fe⁰-EF@MC），考察该体系对抗生素磺胺二甲基嘧啶（SMT）的降解效能。结果表明，当PS浓度为10 mmol/L，电解电流为25 mA，pre-S/Fe⁰投加量为28 mg/L，初始pH为4时，反应5 min后SMT的降解率即可达到99.7%，对SMT的降解速率常数达到0.728 min^-1，是以Na₂SO₄为电解质传统电Fenton体系的2.3倍，显著降低了催化剂用量和成本。自由基捕获实验和EPR分析表明，体系中·OH是降解SMT的主要活性物质，贡献率达到90.6%。此外，PS在阴极被活化产生的SO₄ ^·-也提升了对SMT的降解效率。研究为水体中抗生素污染的有效治理提供了新的思路和技术方案。

关键词: 改性零价铁, 双功能阴极, 非均相电Fenton工艺, 过硫酸盐活化, 磺胺二甲基嘧啶降解

Abstract:

The increasing presence of antibiotic contamination in water bodies poses a potential threat to both the ecosystem and human health. An efficient heterogeneous electro-Fenton system (pre-S/Fe⁰-EF@MC) was constructed, employing pre-magnetized and sulfidized modified zero-valent iron (pre-S/Fe⁰) as the catalyst, MoS₂-loaded bifunctional cathode (MC) as the cathode, and persulfate (PS) as the electrolyte. This study investigated the degradation efficiency of the system towards the antibiotic sulfamethazine(SMT). When the PS dosage was 10 mmol/L, the current was 25 mA, the dosage of pre-S/Fe⁰was 28 mg/L, and the initial pH was 4, the removal rate of SMT reached 99.7% in 5 minutes. Under optimal conditions, the degradation rate constant of SMT by this system reached 0.728 min^-1, which was 2.3 times higher than that of the traditional Na₂SO₄ system, and the amount of catalyst and cost was significantly reduced. Radical quenching experiments and EPR spectra analysis showed that ·OH was the primary active substances for SMT degradation, accounting for 90.6%. In addition, SO₄ ^·- generated by the activation of PS at the cathode further enhanced the degradation efficiency of SMT. This study provides new insights and technical solutions for the effective treatment of antibiotic contamination in water.

Key words: modified zero-valent iron, bifunctional cathode, heterogeneous electro-Fenton, persulfate activation, sulfamethazine degradation

中图分类号:

X703

田雨丝, 吉晋兰, 周明华. 基于改性Fe⁰的非均相电Fenton-过硫酸盐体系降解抗生素[J]. 工业水处理, 2025, 45(11): 53-61.

Yusi TIAN, Jinlan JI, Minghua ZHOU. Degradation of antibiotics by the heterogeneous electro- Fenton-persulfate system with modified zero-valent iron[J]. Industrial Water Treatment, 2025, 45(11): 53-61.

https://www.iwt.cn/CN/Y2025/V45/I11/53

图/表 13

图1 @M（a）、@MC（b）的SEM-EDS和@MC的拉曼谱图（c）

Fig.1 SEM-EDS of @M（a），@MC（b） and Raman spectrum of @MC（c）

图2 PS浓度对SMT降解率（a）和降解速率常数（b）的影响

Fig.2 Effects of PS concentrations on the degradation rate（a） and degradation rate constant（b） of SMT

图3 电解电流对SMT降解率（a）和降解速率常数（b）的影响

Fig.3 Effects of current on the degradation rate（a） and degradation rate constant（b） of SMT

图4 pre-S/Fe⁰投加量对SMT降解率（a）和降解速率常数（b）的影响

Fig.4 Effects of pre-S/Fe⁰ dosage on the degradation rate（a） and degradation rate constant（b） of SMT

图5 初始pH对SMT降解率（a）和降解速率常数（b）的影响

Fig.5 Effects of initial pH on the degradation rate（a） and degradation rate constant（b） of SMT

图6 不同体系下SMT的降解曲线（a）及拟一级反应动力学拟合曲线（b）

Fig.6 Degradation curves（a）and pseudo-first-order reaction kinetic fitting curves（b） of SMT at different systems

表1 不同工艺降解SMT的速率常数

Table 1 The degradation rate constants of SMT by different processes

工艺	PS/pre-S/Fe⁰-EF@MC	pre-S/Fe⁰-EF@MC	PS/电氧化@MC	PS/pre-S/Fe⁰@MC	PS/pre-S/Fe⁰	单独PS
k/min^-1	0.728	0.320	0.243	0.097	0.021	0.004
r ²	0.992	0.975	0.998	0.965	0.977	0.989

图7 不同体系对TOC的去除率对比

Fig.7 The comparison of different systems on TOC removal rate

图8 自由基捕获实验结果（a）和EPR谱图（b）

Fig.8 The free radical quenching experiment results（a） and EPR spectra（b）

表2 不同捕获剂条件下SMT的降解速率常数

Table 2 Degradation rate constants of SMT under different quenching agents

捕获剂	TBA	MeOH	空白
k/min^-1	0.068	0.011	0.728
r ²	0.976	0.962	0.992

图9 不同条件下PS浓度变化

Fig.9 PS concentration under various conditions

图10 PS/pre-S/Fe⁰-EF@MC降解SMT机理

Fig.10 Mechanism of SMT degradation in PS/pre-S/Fe⁰-EF@MC system

图11 PS/pre-S/Fe⁰-EF@MC体系降解SMT的可能途径

Fig.11 The possible pathways for SMT degradation in PS/pre-S/Fe⁰-EF@MC system

参考文献 26

[1]	张照荷，陈典，赵微，等. 水环境中药物与个人护理品（PPCPs）的环境水平及降解行为研究进展［J］. 岩矿测试，2023，42（4）：649-666.
	ZHANG Zhaohe， CHEN Dian， ZHAO Wei，et al. Environmental levels and degradation behavior of pharmaceuticals and personal care products（PPCPs） in the water environment［J］. Rock and Mineral Analysis，2023，42（4）：649-666.
[2]	XU Jian， ZHANG Yuan， ZHOU Changbo，et al. Distribution，sources and composition of antibiotics in sediment，overlying water and pore water from Taihu Lake，China［J］. Science of the Total Environment，2014，497：267-273. doi:10.1016/j.scitotenv.2014.07.114
[3]	JING Jiana， UNIVERSITY N，et al. Anode-cathode synergistic filter activating peroxymonosulfate at multiple active sites for highly efficient and economical water purification［J］. Environmental Science & Technology，2025，59（23）：11919-11934. doi:10.1021/acs.est.5c02729
[4]	ZHANG Chen， LAI Cui， ZENG Guangming，et al. Efficacy of carbonaceous nanocomposites for sorbing ionizable antibiotic sulfamethazine from aqueous solution［J］. Water Research，2016，95：103-112. doi:10.1016/j.watres.2016.03.014
[5]	XIONG Weiping， ZENG Zhuotong， LI Xin，et al. Multi-walled carbon nanotube/amino-functionalized MIL-53（Fe） composites：Remarkable adsorptive removal of antibiotics from aqueous solutions［J］. Chemosphere，2018，210：1061-1069. doi:10.1016/j.chemosphere.2018.07.084
[6]	TANG Juntao， WANG Jianlong. Metal organic framework with coordinatively unsaturated sites as efficient Fenton-like catalyst for enhanced degradation of sulfamethazine［J］. Environmental Science & Technology，2018，52（9）：5367-5377. doi:10.1021/acs.est.8b00092
[7]	PAN Yuwei， GUO Hongjin， ZHOU Minghua，et al. EDTA enhanced removal of sulfamethazine by pre-magnetized Fe⁰ without oxidant addition［J］. Chemical Engineering Journal，2019，372：905-916. doi:10.1016/j.cej.2019.04.211
[8]	SONG Yali， TIAN Jiayu， GAO Shanshan，et al. Photodegradation of sulfonamides by g-C₃N₄ under visible light irradiation：Effectiveness，mechanism and pathways［J］. Applied Catalysis B：Environmental，2017，210：88-96. doi:10.1016/j.apcatb.2017.03.059
[9]	YE Shujing， ZENG Guangming， WU Haipeng，et al. Co-occurrence and interactions of pollutants，and their impacts on soil remediation：A review［J］. Critical Reviews in Environmental Science and Technology，2017，47（16）：1528-1553. doi:10.1080/10643389.2017.1386951
[10]	LIN S H， JUANG R S. Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents：A review［J］. Journal of Environmental Management，2009，90（3）：1336-1349. doi:10.1016/j.jenvman.2008.09.003
[11]	SONUNE A， GHATE R. Developments in wastewater treatment methods［J］. Desalination，2004，167：55-63. doi:10.1016/j.desal.2004.06.113
[12]	VAN DER ZEE F P， VILLAVERDE S. Combined anaerobic-aerobic treatment of azo dyes：A short review of bioreactor studies［J］. Water Research，2005，39（8）：1425-1440. doi:10.1016/j.watres.2005.03.007
[13]	KARADAG D， KÖROĞLU O E， OZKAYA B，et al. A review on anaerobic biofilm reactors for the treatment of dairy industry wastewater［J］. Process Biochemistry，2015，50（2）：262-271. doi:10.1016/j.procbio.2014.11.005
[14]	TIAN Yusi， FU Wenyang， WANG Qi，et al. High electron transfer rate and efficiency on Fe0 modified by sulfidation and pre-magnetization for carbamazepine degradation by heterogeneous electro-Fenton in wide pH ranges［J］. Chemical Engineering Journal，2022，427：131694. doi:10.1016/j.cej.2021.131694
[15]	TIAN Yusi， ZHOU Minghua， PAN Yuwei，et al. MoS₂ as highly efficient co-catalyst enhancing the performance of Fe⁰ based electro-Fenton process in degradation of sulfamethazine：Approach and mechanism［J］. Chemical Engineering Journal，2021，403：126361. doi:10.1016/j.cej.2020.126361
[16]	XING Mingyang， XU Wenjing， DONG Chencheng，et al. Metal sulfides as excellent co-catalysts for H₂O₂ decomposition in advanced oxidation processes［J］. Chem，2018，4（6）：1359-1372. doi:10.1016/j.chempr.2018.03.002
[17]	LIU Jun， DONG Chencheng， DENG Yuanxin，et al. Molybdenum sulfide co-catalytic Fenton reaction for rapid and efficient inactivation of Escherichia coli ［J］. Water Research，2018，145：312-320. doi:10.1016/j.watres.2018.08.039
[18]	丁洁然，张宏宇，韩智博，等. Fe₃O₄催化电Fenton偶联活化过硫酸盐降解甲硝唑［J］. 水处理技术，2025，51（4）：53-58.
	DING Jieran， ZHANG Hongyu， HAN Zhibo，et al. Acetylene black-PTFE cathode coupled with persulfate activated by Fe₃O₄ for metronidazole degradation［J］. Technology of Water Treatment，2025，51（4）：53-58.
[19]	张水珍，李墨华，李方，等. 金属有机框架（MOFs）基电催化膜活化过硫酸盐降解磺胺甲唑［J］. 环境化学，2023，42（11）：3779-3788.
	ZHANG Shuizhen， LI Mohua， LI Fang，et al. Degradation of sulfamethoxazole by metal-organic framework（MOFs）-based electrocatalytic membrane activated by peroxymonosulfate［J］. Environmental Chemistry，2023，42（11）：3779-3788.
[20]	ZHANG Lian， ZHANG Yue， GAO Xuyan，et al. Insights on the effects of pH and Fe（Ⅱ） regeneration during the chromate sequestration by sulfidated zero-valent iron［J］. Chemical Engineering Journal，2019，378：122115. doi:10.1016/j.cej.2019.122115
[21]	ZHANG Xinyi， WEI Jian， WANG Chen，et al. Recent advance of Fe-based bimetallic persulfate activation catalysts for antibiotics removal：Performance，mechanism，contribution of the key ROSs and degradation pathways［J］. Chemical Engineering Journal，2024，487：150514. doi:10.1016/j.cej.2024.150514
[22]	CHEN Luchuan， LEI Chaojun， LI Zhongjian，et al. Electrochemical activation of sulfate by BDD anode in basic medium for efficient removal of organic pollutants［J］. Chemosphere，2018，210：516-523. doi:10.1016/j.chemosphere.2018.07.043
[23]	LIANG Chenju， WANG Z S， BRUELL C J. Influence of pH on persulfate oxidation of TCE at ambient temperatures［J］. Chemosphere，2007，66（1）：106-113. doi:10.1016/j.chemosphere.2006.05.026
[24]	MATZEK L W， TIPTON M J， FARMER A T，et al. Understanding electrochemically activated persulfate and its application to ciprofloxacin abatement［J］. Environmental Science & Technology，2018，52（10）：5875-5883. doi:10.1021/acs.est.8b00015
[25]	WACŁAWEK S， ANTOŠ V， HRABÁK P，et al. Remediation of hexachlorocyclohexanes by electrochemically activated persulfates［J］. Environmental Science and Pollution Research International，2016，23（1）：765-773. doi:10.1007/s11356-015-5312-y
[26]	BARHOUMI N， OTURAN N， OLVERA-VARGAS H，et al. Pyrite as a sustainable catalyst in electro-Fenton process for improving oxidation of sulfamethazine：Kinetics，mechanism and toxicity assessment［J］. Water Research，2016，94：52-61. doi:10.1016/j.watres.2016.02.042

选择文件类型/文献管理软件名称

选择包含的内容

基于改性Fe⁰的非均相电Fenton-过硫酸盐体系降解抗生素

Degradation of antibiotics by the heterogeneous electro- Fenton-persulfate system with modified zero-valent iron

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 26

相关文章 1

编辑推荐

Metrics

本文评价

模态框（Modal）标题

选择文件类型/文献管理软件名称

选择包含的内容

基于改性Fe0的非均相电Fenton-过硫酸盐体系降解抗生素

Degradation of antibiotics by the heterogeneous electro- Fenton-persulfate system with modified zero-valent iron

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 26

相关文章 1

编辑推荐

Metrics

本文评价

基于改性Fe⁰的非均相电Fenton-过硫酸盐体系降解抗生素