CoFe2O4@MoS2活化PMS降解环丙沙星的产物及毒性分析

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摘要利用实验室制备的CoFe₂O₄@MoS₂活化过一硫酸氢盐(PMS)降解水中的环丙沙星(CIP),SEM及XRD的表征结果证明了CoFe₂O₄@MoS₂的成功制备.降解结果表明,CoFe₂O₄@MoS₂/PMS体系中CIP的去除率在120min达到74.38%,高于单独的CoFe₂O₄@MoS₂以及PMS体系之和,证实了CoFe₂O₄@MoS₂对PMS的活化能力.淬灭实验结果表明CoFe₂O₄@MoS₂/PMS体系中的主要的氧化活性物种为^·OH、SO4^·-以及¹O₂,且SO₄^·-和¹O₂对CIP的降解起主要作用.通过密度泛函理论并结合HPLC分析,得到8种可能的中间产物并提出了CIP可能的两种降解路径.T.E.S.T程序对降解产物的环境风险的评价预测结果显示,和母体相比,大部分产物的急性毒性降低、致突变性减弱、生物累积性和发育毒性降低,生态毒性明显降低.此外,4次循环后CoFe₂O₄@MoS₂/PMS体系对CIP的去除率仍能达到60.04%,且XRD结果显示反应前后催化剂的晶体结构变化不明显,说明了催化剂的高效稳定性.

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	王杰
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关键词 ： CoFe₂O₄@MoS₂, 活化过一硫酸氢盐(PMS), 环丙沙星, 降解产物, 毒性分析

Abstract：CoFe₂O₄@MoS₂ was prepared by the hydrothermal method and used to activate permonosulfate (PMS) for the degradation of ciprofloxacin (CIP) in water. The successful preparation of CoFe₂O₄@MoS₂ was confirmed by the characterization results obtained from SEM and XRD. Degradation results showed that the removal rate of CIP in the CoFe₂O₄@MoS₂/PMS system can reached 74.38% in 120minutes, which is higher than the sum of the individual CoFe₂O₄@MoS₂ and PMS systems, verifying the activation ability of CoFe₂O₄@MoS₂ on PMS. The quenching experiment results indicated that the main oxidative active species in the system are ^·OH、SO₄^·- and ¹O₂, with SO₄^·- and ¹O₂ playing a major role in the degradation of CIP. Based on density functional theory combined with HPLC analysis, eight possible products were obtained and two possible degradation pathways of CIP were proposed. The environmental risks of the degradation products were evaluated and predicted using the TEST program, and it was shown that, compared with the parent compound, most products exhibited reduced acute toxicity, weakened mutagenicity, decreased bioaccumulation and developmental toxicity, and significantly lower ecotoxicity. Additionally, the CIP removal rate of the CoFe₂O₄@MoS₂/PMS system can still reached 60.04% after four cycles, and the XRD results demonstrated that the crystal structure of the catalyst did not undergo significant changes before and after the reaction, indicating the high efficiency and stability of the catalyst.

Key words： CoFe₂O₄@MoS₂ PMS ciprofloxacin degradation products toxic analyst

收稿日期: 2024-10-23

PACS:

X703

基金资助:安徽省高校自然科学研究项目(KJ2021A0383)

作者简介: 王杰(2000-),男,安徽铜陵人,安徽工业大学硕士研究生,主要研究方向为高级氧化技术处理水中有机污染物.wangjie000210@163.com.

引用本文:

王杰, 马梦杰, 谢鹏飞, 章慧娟. CoFe₂O₄@MoS₂活化PMS降解环丙沙星的产物及毒性分析[J]. 中国环境科学, 2025, 45(5): 2865-2874. WANG Jie, MA Meng-jie, XIE Peng-fei, ZHANG Hui-juan. Degradation products and toxicity analysis of ciprofloxacin by activation of peroxymonosulfate using CoFe₂O₄@MoS₂. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(5): 2865-2874.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2025/V45/I5/2865

[1] 陈雅真,胡同珂,牛继亮,等.F-F@FeS@5C-400催化剂的制备及其活化过硫酸盐降解环丙沙星的性能与机理研究[J].环境科学学报, 2024,44(5):57–68. Chen Y Z, Hu T K, Niu J L, et al. Preparation of F-F@FeS@5C-400 catalyst and its performance and mechanism of activated persulfate degradation of ciprofloxacin[J]. Acta Scientiae Circumstantiae, 2024, 44(5):57-68.
[2] Zhu J F, Wang H W, Duan A B, et al. Mechanistic insight into the degradation of ciprofloxacin in water by hydroxyl radicals[J]. Journal of Hazardous Materials, 2023,446:130676.
[3] Chu Y H, Chen X, Li S N, et al. Novel insights into revealing the intrinsic degradation mechanism of ciprofloxacin by Chlorella sorokiniana: Removal efficiency, pathways and metabolism[J]. Chemical Engineering Journal, 2024,500:157015.
[4] Peng X M, Yang Z H, Hu F P, et al. Mechanistic investigation of rapid catalytic degradation of tetracycline using CoFe₂O₄@MoS₂ by activation of peroxymonosulfate[J]. Separation and Purification Technology, 2022,287:120525.
[5] 余小玉,郭家华,孙建良.工业废铁屑活化过硫酸盐降解水中环丙沙星的研究[J].环境污染与防治, 2020,42(8):999-1004. Yu X Y, Guo J H, Sun J L. Study on the degradation of ciprofloxacin in water by activated persulfate with industrial waste iron[J]. Environmental Pollution& Control, 2020,42(8):999-1004.
[6] Feng Y, Wu D L, Deng Y, et al. Sulfate radical-mediated degradation of sulfadiazine by CuFeO₂ rhombohedral crystal-catalyzed peroxymonosulfate: synergistic effects and mechanisms[J]. Environmental Science& Technology, 2016,50:3119–3127.
[7] Huang G X, Wang C Y, Yang C W, et al. Degradation of bisphenol a by peroxymonosulfate catalytically activated with Mn_1.8Fe_1.2O₄ nanospheres: synergism between Mn and Fe[J]. Environmental Science& Technology, 2017,51(21):12611–12618.
[8] Hu P D, Su H R, Chen Z Y, et al. Selective degradation of organic pollutants using an efficient metal-free catalyst derived from carbonized polypyrrole via peroxymonosulfate activation[J]. Environmental Science& Technology, 2017,51:11288–11296.
[9] Zeng T, Li S Q, Hua J N, et al. Synergistically enhancing Fenton-like degradation of organics by in situ transformation from Fe₃O₄ microspheres to mesoporous Fe, N-dual doped carbon[J]. Science of the Total Environment, 2018,645:550–559.
[10] Ao X W, Liu W J, Sun W J, et al. Mechanisms and toxicity evaluation of the degradation of sulfamethoxazole by MPUV/PMS process[J]. Chemosphere, 2018,212:365–375.
[11] Zhang Y X, Liu H L, Dai X H, et al. The release of organic matter, nitrogen, phosphorus and heavy metals from erythromycin fermentation residue under heat-activated persulfate oxidation conditioning[J]. Science of the Total Environment, 2020,724:138349.
[12] Cai C, Zhang H, Zhong X, et al. Ultrasound enhanced heterogeneous activation of peroxymonosulfate by a bimetallic Fe-Co/SBA-15 catalyst for the degradation of Orange II in water[J]. Journal of Hazardous Materials, 2015,283:70–79.
[13] 权衡,牛琳,时迪,等.负载纳米零价铁的铁碳材料制备及其降解抗生素性能研究[J].环境科学研究, 2022,35(12):2732-2747. Quan H, Niu L, Shi D, et al. Preparation of iron-carbon materials loaded with nano zero-valent iron and their performance of degrading antibiotics[J]. Research of Environmental Sciences[J]. 2022,35(12): 2732-2747.
[14] 苏冰琴,温宇涛,林昱廷,等.活性碳纤维-过硫酸盐体系处理焦化废水生化出水的实验研究[J].环境科学学报, 2022,42(7):182-195. Su B Q, Wen N T, Lin Y T, et al. Advanced treatment of bio-treated coking wastewater with peroxymonosulfate activated by activated carbon fiber system[J]. Acta Scientiae Circumstantia
[14]. 2022,42(7): 182-195.
[15] Zhang S S, Li J, Ni Z B, et al. Core-shell structured cobalt–nickel bimetallic sulfide with dual redox cycles to activate peroxymonosulfate for glyphosate removal[J]. Chemical Engineering Journal, 2023,453:139972.
[16] Liu Y, Zhao Y, Wang J L, et al. Fenton/Fenton-like processes with insitu production of hydrogen peroxide/hydroxyl radical for degradation of emerging contaminants: Advances and prospects[J]. Journal of Hazardous Materials, 2021,404:124191.
[17] Xiao S, Zhang L N, Lian Zhou, et al. The long-term effect of Fe₃O₄ in activating persulfate to degrade refractory organic contaminants for groundwater remediation[J]. Chemical Engineering Journal, 2024,482: 148801.
[18] Pan S L, Guo S R, Lu X, et al. Boosting peroxymonosulfate activation by a novel bifunctional core-shell nanoreactor MnFe₂O₄@HZO for nitrilotris-methylenephosphonic acid removal[J]. Applied Catalysis B: Environmental, 2023,330:122508.
[19] Labchir N, Amaterz E, Hannour A, et al. Highly efficient nanostructured CoFe₂O₄ thin film electrodes for electrochemical degradation of rhodamine B[J]. Water Environment Research, 2020, 92:759-765.
[20] Lai B, Li J, Xu M J, et al. Enhancement of the degradation of atrazine through CoFe₂O₄ activated peroxymonosulfate (PMS) process: Kinetic, degradation intermediates, and toxicity evaluation[J]. Chemical Engineering Journal, 2018,348:1012–1024.
[21] Jia B Y, Liu D D, Chen D Q, et al. Efficient degradation of Rhodamine B in water by CoFe₂O₄/H₂O₂ and CoFe₂O₄/PMS systems: A comparative study[J]. Chemosphere, 2022,307:135935.
[22] Cai C, Liu Y F, Xu R, et al. Bicarbonate enhanced heterogeneous activation of peroxymonosulfate by copper ferrite nanoparticles for the efficient degradation of refractory organic contaminants in water[J]. Chemosphere, 2023,312:137285.
[23] Du M M, Yi Q Y, Ji J H, et al. Sustainable activation of peroxymonosulfate by the Mo (IV) in MoS₂ for the remediation of aromatic organic pollutants[J]. Chinese Chemical Letters, 2020,31: 2803-2808.
[24] Wang J K, Feng S, Yu M G, et al. MoS₂/CoFe₂O₄ heterojunction for boosting photogenerated carrier separation and the dominant role in enhancing[J]. Chemical Engineering Journal, 2022,433:134467.
[25] Dai H L, Peng X M, Yang Z H, et al. Mechanistic investigation of rapid catalytic degradation of tetracycline using CoFe₂O₄@MoS₂ by activation of peroxymonosulfate[J]. Separation and Purification Technology, 2022,287:120525.
[26] 贺泳迪,宋金瓯,武斌,等.应用毒性评价软件工具和Toxtree软件预测硝基烃及其衍生物的毒性[J].中国药理学与毒理学杂志, 2022, 36(7):509-520. He Y D, Song J O, G B, et al. Prediction of toxicity of nitro-organic compounds by toxicity estimation software tool and toxtree software[J]. Chinese Journal of Pharmacology and Toxicology, 2022,36(7):509-520.
[27] 黄鹏程,许泽平,郭雨欣,等.紫外/二氯异氰尿酸盐体系对水中抗病毒药物降解路径及降解产物毒性分析[J].环境化学, 2024,43(6): 2058-2068. Huang P C, Xu Z P, Guo Y X, et al. Analysis of degradation pathways and toxicity of degradation productsof antiviral drugs in water by UV/Dichloroisocyanurate process[J]. Environmental Chemistry, 2024, 43(6):2058-2068.
[28] Shao Y S, Deng J, Gao N Y, et al. CoFe₂O₄ magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water[J]. Journal of Hazardous Materials, 2013,262:836-844.
[29] Liu C L, Jia Y F, Ma H X, et al. Au nanoparticles enhanced Z-scheme Au-CoFe₂O₄/MoS₂ visible light photocatalyst with magnetic retrievability[J]. Applied Surface Science, 2019,463:854-862.
[30] Liu L L, Mi H S, Zhang M, et al. Efficient moxifloxacin degradation by CoFe₂O₄ magnetic nanoparticles activated peroxymonosulfate: Kinetics, pathways and mechanisms[J]. Chemical Engineering Journal, 2021,407:127201.
[31] Feng C S, Chen C, Zhu Y, et al. Degradation of ofloxacin using peroxymonosulfate activated by nitrogen-rich graphitized carbon microspheres: Structure and performance controllable study[J]. Journal of Environmental Sciences, 2021,99:10-20.
[32] 石紫龙,谢晶.盐酸羟胺强化Fe~(0)/PS体系对柠檬黄的处理[J/OL].环境工程, 2024:1-11[2025-04-24].http://kns.cnki.net/kcms/detail/11.2097.X.20240819.1900.002.html. Shi Z L, Xie J. Enhanced lemon yellow removed by Fe⁰/PS system with hydroxylamine[J/OL]. Environmental Engineering, 2024:1-11[2025-04-24].http://kns.cnki.net/kcms/detail/11.2097.X.20240819.1900.002.html.
[33] Chen S N, Deng J, Ye C, et al. Degradation of p-arsanilic acid by pre-magnetized Fe⁰/persulfate system: Kinetics, mechanism, degradation pathways and DBPs formation during subsequent chlorination[J]. Chemical Engineering Journal, 2021,410:128435.
[34] Qi F, Wang Q, Zeng Z Q, et al. Insight into the roles of microenvironment and active site on the mechanism regulation in metal-free persulfate activation process coupling with an electric field[J]. Journal of Hazardous Materials, 2022,439:129673.
[35] Dai H L, Peng X M, Yang Z H, et al. Mechanistic investigation of rapid catalytic degradation of tetracycline using CoFe₂O₄@MoS₂ by activation of peroxymonosulfate[J]. Separation and Purification Technology, 2022,287:120525.
[36] Wang T, Zhang T T, Ta M M, et al. Peroxymonosulfate oxidation of carbamazepine by Iron-Biochar via nonradical pathways: Singlet oxygen, electron transfer, and Fe (IV)[J]. Separation and Purification Technology, 2024,328:125134.
[37] Benhaliliba M, Ben Ahmed A, Kaleli M, et al. Structural, optical, nonlinear optical, HUMO-LUMO properties and electrical characterization of Poly (3-hexylthiophene)(P3HT)[J]. Optical Materials, 2022,132:112782.
[38] Alaşalvar C, öztürk N, Abdel-Aziz A, et al. Molecular structure, Hirshfeld surface analysis, spectroscopic (FT-IR, Laser-Raman, UVvis. and NMR), HOMO-LUMO and NBO investigations on N-(12- amino-9,10-dihydro-9,10-ethanoanthracen-11-yl)-4-methylbenzene sulfonamide[J]. Journal of Molecular Structure, 2018,1171:696-705.
[39] Yi X H, Ji H D, Wang C C, et al. Photocatalysis-activated SR-AOP over PDINH/MIL-88A (Fe) composites for boosted chloroquine phosphate degradation: Performance, mechanism, pathway and DFT calculations[J]. Applied Catalysis B: Environmental, 2021,293:120229.
[40] He B, Song L X, Zhao Z X, et al. CuFe₂O₄/CuO magnetic nanocomposite activates PMS to remove ciprofloxacin: Ecotoxicity and DFT calculation[J]. Chemical Engineering Journal, 2022,446:137183.
[41] Liu C, Mao S, Shi M X, et al. Peroxymonosulfate activation through 2D/2D Z-scheme CoAl-LDH/BiOBr photocatalyst under visible light for ciprofloxacin degradation[J]. Journal of Hazardous Materials, 2021,420:126613.
[42] Fan X D, Lin Q T, Zheng J L, et al. Peroxydisulfate activation by nano zero-valent iron graphitized carbon materials for ciprofloxacin removal: Effects and mechanism[J]. Journal of Hazardous Materials, 2022,437:129392.
[43] Shang J W, Zhang T N, Li X C, et al. Mn₃O₄-ZnMn₂O₄/SnO₂ nanocomposite activated peroxymonosulfate for efficient degradation of ciprofloxacin in water[J]. Separation and Purification Technology, 2023,311:123342.
[44] Guo H, Li Z, Zhang Y, et al. Degradation of chloramphenicol by pulsed discharge plasma with heterogeneous Fenton process using Fe₃O₄ nanocomposites[J]. Separation and Purification Technology, 2020,253:117540.