氯酚类污染物在Fe<sub>3</sub>O<sub>4</sub>-nZVI类Fenton体系中的降解

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摘要用共沉淀法和液相还原法制得Fe₃O₄负载nZVI复合材料（Fe₃O₄-nZVI），以Fe₃O₄-nZVI为非均相催化剂与H₂O₂耦合构建类Fenton体系，将其用于降解废水中的氯酚（CPs），如，对氯苯酚（4-CP）、2，4-二氯苯酚（2，4-DCP）及2，4，6-三氯苯酚（2，4，6-TCP）.SEM、EDS、XPS、XRD和VSM表征结果表明，Fe₃O₄-nZVI是可通过磁回收循环利用的纳米级复合材料，且可促进Fe²⁺和Fe³⁺循环并增加HO·的产量.动力学拟合参数表明，Fe₃O₄-nZVI类Fenton体系对3种CPs的降解过程均符合拟一级动力学方程（R²>0.9）.在25℃，Fe₃O₄和nZVI物质的量比1：1，溶液初始pH=3，H₂O₂浓度15mmol/L，CPs初始浓度40mg/L，Fe₃O₄-nZVI投加量0.6g/L的优化条件下，Fe₃O₄-nZVI类Fenton体系对4-CP、2，4-DCP和2，4，6-TCP的降解率分别为96.28%、98.77%和98.03%.3种CPs的降解速率顺序为k_4-CP>k_2，4-DCP>k_{2，4，6-TCP}，表明随着苯环上氯取代基的增加，CPs的降解速率随之减小.淬灭实验和质谱结果表明HO·氧化和取代脱氯是CPs降解的主要方式.

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关键词 ： Fe₃O₄-nZVI, 类Fenton, 氯酚, 降解机理

Abstract：The ferriferrous oxide supported nano zero-valent iron (Fe₃O₄-nZVI) was prepared by co-precipitation and liquid phase reduction method, and used as heterogeneous catalysts with H₂O₂ of Fenton-like systems to degrade chlorophenols (CPs) in wastewater, such as p-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). The characterisation results of SEM, EDS, XPS, XRD and VSM showed that Fe₃O₄-nZVI was a nanoscale magnetic composite that could be recycled by magnetic recovery and could promote the circulation of Fe²⁺ and Fe³⁺ and increase the yield of HO·. The fitting parameters of kinetics showed that the degradation process of three kinds of CPs in Fe₃O₄-nZVI Fenton-like system fitted the pseudo-first-order kinetics model (R²>0.9). Under the optimization conditions, which were reaction temperature 25℃, Fe₃O₄:nZVI=1:1 (mol:mol), pH=3, H₂O₂ 15mmol/L, CPs 40mg/L, and Fe₃O₄-nZVI 0.6g/L, the degradation rates of 4-CP, 2,4-DCP and 2,4,6-TCP by Fe₃O₄-nZVI Fenton-like systems were 96.28%, 98.77% and 98.03%, respectively. The degradation rates of three kinds of CPs were in the order of k_4-CP>k_2,4-DCP>k_2,4,6-TCP. The degradation rates of CPs decreased with the increase of chlorine atoms on the benzene ring. The quenching experiments and mass spectrometry results indicated that HO· oxidation and substitution dechlorination played a critical role on degrading CPs.

Key words： Fe₃O₄-nZVI Fenton-like chlorophenols degradation mechanism

收稿日期: 2023-03-15

PACS:

X703.1

基金资助:国家自然科学基金资助项目（22166022）；甘肃省科技计划项目（20JR2RA002）；兰州交通大学创新创业项目（CXXL20230087）

通讯作者: 钟金魁,教授,zhongjk@mail.lzjtu.cn E-mail: zhongjk@mail.lzjtu.cn

作者简介: 钟金魁(1968-),男,甘肃古浪人,教授,主要从事水处理技术和土壤污染修复.发表论文44篇.zhongjk@mail.lzjtu.cn.

引用本文:

钟金魁, 李闻青, 谢亚瑞, 李静, 委嘉禾. 氯酚类污染物在Fe₃O₄-nZVI类Fenton体系中的降解[J]. 中国环境科学, 2023, 43(11): 5746-5756. ZHONG Jin-kui, LI Wen-qing, XIE Ya-rui, LI Jing, WEI Jia-he. Degradation of chlorophenolic pollutants in Fe₃O₄-nZVI Fenton-like system. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(11): 5746-5756.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2023/V43/I11/5746

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