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硫化纳米零价铁活化过二硫酸盐降解废水中四环素OA北大核心CSTPCD

Degradation of Tetracycline in Wastewater by Persulfate Activated by Sulfidated Nanometer Zero-valent Iron

中文摘要英文摘要

硫化零价铁(S-nZVI)因其电子传递效率高、选择性好,近年来在水处理领域应用广泛.将S-nZVI与高级氧化技术结合,可发挥材料优异的催化性能,实现对污染物的高效降解.本文以硫脲为硫源制备高活性S-nZVI,构建S-nZVI活化过二硫酸盐(PDS)高级氧化体系实现对四环素(TC)的高效降解.采用扫描电子显微镜(SEM)、X射线衍射(XRD)、比表面积(BET)、X射线光电子能谱仪(XPS)等表征方法分析S-nZVI的组成结构和表面形貌,考察硫铁物质的量的比(S/Fe)、硫化时间、S-nZVI投加量、PDS浓度、溶液初始pH和共存离子对TC降解的影响作用,通过活性物种淬灭实验和电子顺磁共振实验(EPR)探究自由基和非自由基活性物质对TC的降解作用,利用液相色谱-质谱联用(LC-MS)分析TC降解的可能路径.结果表明:纳米零价铁(nZVI)经硫化改性后,比表面积增大,Fe和S均匀地分布在材料表面;S/Fe对TC降解的影响作用较小,TC降解率与S-nZVI投加量和PDS浓度呈正相关,但随着硫化时间增加呈现降低趋势;S-nZVI/PDS体系在较宽pH范围(pH=5~9)内均具有较优的TC降解效果;反应溶液中存在不同阴离子时,TC降解率受到不同程度抑制作用,其中HCO3抑制作用最为显著;当S/Fe为0.028、硫化时间为2 h、S-nZVI投加量为1 g/L、PDS浓度为2 mmol/L,不调节初始溶液pH时,反应120 min后TC降解率可达94.6%;S-nZVI/PDS体系的活性物种除常见自由基(SO4·-和HO·)外,还包括非自由基活性物质Fe(Ⅳ),但Fe(Ⅳ)对TC的降解作用较小;TC降解主要通过特定官能团裂解和开环反应进行,最终氧化降解成CO2和H2O.

Sulfidated zero-valent iron(S-nZVI)has been extensively utilized in wastewater treatment in recent years due to its superior electron transfer efficiency and selectivity.Integrating S-nZVI with advanced oxidation technology enhances the catalytic performance of the material,leading to efficient pollutant degradation.This study employs thiourea as the sulfur source to prepare highly active S-nZVI and constructs an S-nZVI-activated per-disulfide PDS oxidation system to achieve efficient tetracycline degradation.The composition and surface morphology of S-nZVI is characterized using scanning electron microscopy(SEM),X-ray diffraction(XRD),specific surface area(BET),and X-ray photoelec-tron spectroscopy(XPS).The effects of the molar ratio(S/Fe),vulcanization time,S-nZVI dosage,PDS concentration,initial pH of the solution,and coexisting ions on tetracycline(TC)degradation are examined.Active species quenching experiments and electron paramagnetic resonance(EPR)experiments explore TC degradation by both free radical and non-radical active species,while liquid chromatography-mass spectrometry(LC-MS)analyzes the potential pathways of tetracycline degradation.Test results indicated that vulcanization modification increases the specific surface area of nano-zero-valent iron(nZVI),and iron(Fe)and sulfur(S)are uniformly distributed on the surface of the material.The impact of S/Fe on TC degradation is minimal,and the degradation rate correlates positively with the dosage of S-nZVI and PDS concentration but shows a decreasing trend with prolonged vulcanization time.The S-nZVI/PDS system exhibits an enhanced TC degradation effect across a wide pH range(pH=5~9).The presence of different anions in the reaction solution variably inhibits the degradation rate of TC,with HCO3-having the most sig-nificant effect.At a S/Fe ratio of 0.028,a vulcanization time of 2 h,an S-nZVI dosage of 1 g/L,a PDS concentration of 2 mmol/L,and an unad-justed initial pH,the degradation rate of TC reaches 94.6%after 120 min of reaction.In addition to common free radicals(SO4·-and HO·),the active species in the S-nZVI/PDS system include the non-radical active substance Fe(Ⅳ),which has a minor effect on TC degradation.The primary pathways of TC degradation involve specific functional group cleavage and ring-opening reactions,ultimately leading to oxidative de-gradation into CO2 and H2O.

叶秋月;胡正春;王紫宜;胥雯;赵施怡;邓旭盈;郭明浩;郭娜;廖兵

成都理工大学地质灾害防治与地质环境保护国家重点实验室,四川成都 610059||成都理工大学生态环境学院国家环境保护水土污染协同控制与联合修复重点实验室,四川成都 610059||四川聚汇兴源建筑工程设计有限公司,四川成都 610000成都理工大学地质灾害防治与地质环境保护国家重点实验室,四川成都 610059||成都理工大学生态环境学院国家环境保护水土污染协同控制与联合修复重点实验室,四川成都 610059四川建筑职业技术学院四川省城市污泥建材资源化利用工程研究中心,四川德阳 618000成都理工大学地质灾害防治与地质环境保护国家重点实验室,四川成都 610059||成都理工大学生态环境学院国家环境保护水土污染协同控制与联合修复重点实验室,四川成都 610059||四川建筑职业技术学院四川省城市污泥建材资源化利用工程研究中心,四川德阳 618000

环境科学

硫化纳米零价铁过二硫酸盐四环素影响因素降解机理

sulfidated nanoscale zero-valent ironpersulfatetetracyclineinfluencing factorsdegradation mechanism

《工程科学与技术》 2024 (004)

35-45 / 11

国家自然科学基金项目(42007168);成都理工大学2020年度中青年骨干教师发展资助计划项目(10912-JXGG-06836)

10.15961/j.jsuese.202300510

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