SiO2包覆nZVI@Fe3O4类Fenton体系对偶氮染料的降解

钟金魁; 何嘉文; 王新昊; 张尹; 高原虎; 朱彩亚; 周鑫悦; 王思倩

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (8) : 4341-4353.

水污染与控制

SiO₂包覆nZVI@Fe₃O₄类Fenton体系对偶氮染料的降解

钟金魁^1,2, 何嘉文¹, 王新昊¹, 张尹¹, 高原虎¹, 朱彩亚¹, 周鑫悦¹, 王思倩¹

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Degradation of azo dyes in sio₂coated nzvi@Fe₃O₄ Fenton-like system

ZHONG Jin-kui^1,2, HE Jia-wen¹, WANG Xin-hao¹, ZHANG Yin¹, GAO Yuan-hu¹, ZHU Cai-ya¹, ZHOU Xin-yue¹, WANG Si-qian¹

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摘要

通过液相还原法和stőber水解法合成了SiO₂@nZVI@Fe₃O₄复合材料,并采用SEM-EDS、TEM、XRD、FTIR、VSM和XPS对其微观结构和物相组成进行了分析和表征.以SiO₂@nZVI@Fe₃O₄为非均相催化剂与H₂O₂耦合构建类Fenton体系,考察该体系对偶氮类染料的降解性能.结果表明,SiO₂包覆后nZVI@Fe₃O₄复合材料的分散性和抗氧化性得到提高,由其构建的类Fenton反应体系能促进Fe²⁺和HO·的生成.在25℃,pH3,H₂O₂浓度为15mmol/L,材料投加量为0.6g/L的条件下,刚果红、橙黄Ⅱ和酸性黑210的去除率分别为99.68%、98.14%和99.35%.复合材料在循环利用3次后对3种污染物的去除率仍保持在79%以上,表明SiO₂@nZVI@Fe₃O₄材料具有良好的稳定催化性能.活性氧物种淬灭实验和紫外-可见光谱分析表明,SiO₂@nZVI@Fe₃O₄类Fenton体系对偶氮染料的去除机理主要是通过nZVI的还原作用和HO·的氧化作用.

Abstract

SiO₂@nZVI@Fe₃O₄ composites were successfully synthesized by liquid-phase reduction and stőber hydrolysis. The microstructures and physical phase compositions of SiO₂@nZVI@Fe₃O₄ were analyzed by SEM-EDS, TEM, XRD, FTIR, VSM, and XPS. The degradation performance of azo dyes was investigated by using SiO₂@nZVI@Fe₃O₄ as a non-homogeneous catalyst combined with H₂O₂to construct a Fenton-like system. The results showed that the SiO₂ coating improved the dispersion and oxidation resistance of nZVI@Fe₃O₄, and it was able to enhance the generation of Fe²⁺ and HO· in the Fenton-like reaction system. Under the conditions of 25℃, pH 3, H₂O₂ concentration of 15mmol/L, and material dosage of 0.6g/L, the removal efficiency of Congo red, Orange II and Acid Black 210 reached 99.68 %、98.14 % and 99.35 %. The composite material could still remove more than 79% of the three pollutants after recycling for three times, which has good stable catalytic performance. The removal of azo dyes by SiO₂@nZVI@Fe₃O₄ combined with Fenton-like system was mainly through the reduction of nZVI and the oxidation of HO·, as demonstrated by reactive oxygen species quenching experiment and UV-visible spectral analysis.

导出引用

钟金魁, 何嘉文, 王新昊, 张尹, 高原虎, 朱彩亚, 周鑫悦, 王思倩. SiO₂包覆nZVI@Fe₃O₄类Fenton体系对偶氮染料的降解[J]. 中国环境科学. 2025, 45(8): 4341-4353

ZHONG Jin-kui, HE Jia-wen, WANG Xin-hao, ZHANG Yin, GAO Yuan-hu, ZHU Cai-ya, ZHOU Xin-yue, WANG Si-qian. Degradation of azo dyes in sio₂coated nzvi@Fe₃O₄ Fenton-like system[J]. China Environmental Science. 2025, 45(8): 4341-4353

中图分类号： X53

参考文献

[1] 宗刚,高存.金属氧化物光催化剂降解偶氮染料废水的研究进展[J].应用化工, 2023,52(3):874-879. Zong G, Gao Z. Progress in the degradation of azo dye wastewater by metal oxide photocatalysts [J]. Applied Chemical Industry, 2023,52(3): 874-879.
[2] 袁思杰,张芮铭.染料废水处理技术研究进展[J].染料与染色, 2022,59(4):55-62. Yuan S J, Zhang R M. Research progress of dye wastewater treatment technology [J]. Dyestuffs and Coloration, 2022,59(4):55-62.
[3] Rawat D, Sharma R S, Karmakar S, et al. Ecotoxic potential of a presumably non-toxic azo dye [J]. Ecotoxicology and Environmental Safety, 2018,148:528-537.
[4] Barbora K. Chemical degradation of azo dyes using different reducing agents: A review [J]. Journal of Water Process Engineering, 2024,61: 105350.
[5] 武哲,曲树光,冯练享,等.海藻酸钠/微晶纤维素复合水凝胶对水中甲基橙和亚甲基蓝的吸附性能与机理[J].化工进展, 2023,43(8): 1-15. Wu Z, Qu S G, Feng L X, et al. Adsorption performance and mechanism of sodium alginate/microcrystalline cellulose composite hydrogel for aqueous methyl orange and methylene blue [J]. Chemical Industry and Engineering Progress, 2023,43(8):1-15.
[6] Garba Z N, Lawan I, Zhou W M, et al. Microcrystalline cellulose (MCC) based materials as emerging adsorbents for the removal of dyes and heavy metals-A review [J]. Science of the Total Environment, 2020,717:135070.
[7] 程雪荣,张洛红,王瑜,等.PVP改性吸附剂处理印染及重金属废水研究进展[J].化学工程师, 2022,36(3):55-58. Cheng X R, Zhang L H, Wang Y, et al. Research progress of PVP modified adsorbent in the treatment of dyeing and heavy metal wastewater [J]. Chemical Engineer, 2022,36(3):55-58.
[8] 刘华晨,李博宇,程玉拓.MOF衍生氮掺杂碳及其膜材料去除染料性能试验[J].净水技术, 2024,43(S2):76-82. Liu H C, Li B Y, Cheng Y T. Experiment on dye removal of MOF-derived nitrogen doped carbon and mixed matrix membrane [J]. Water Purification Technology, 2024,43(S2):76-82.
[9] 程爱华,张佳宝.高级还原技术处理偶氮染料废水的研究[J].现代化工, 2019,39(4):112-115. Cheng A H, Zhang J B. Research on treatment of azo dye wastewater by advanced reduction process [J]. Modern Chemical Industry, 2019, 39(4):112-115.
[10] Shahriar S, Mesbah A W, Somayeh G, et al. A new azine-based ferrocenophane for azo dyes degradation in dark-ambient conditions [J]. Surfaces and Interfaces, 2024,51:104551.
[11] Wang W M, Li X Z, Du X, et al. A feasible approach for azo dye degradation using natural magnetite in heterogeneous fenton oxidation [J]. Water Cycle, 2022,3:100-105.
[12] 王诗语.杂化型g-C₃N₄基光催化剂的制备及其降解偶氮染料性能研究[D].大庆:东北石油大学, 2024. Wang S Y. Study on preparation of hybrid g-C₃N₄-based photocatalyst and degradation performance of azo dyes [D]. Daqing: Northeast Petroleum University, 2024.
[13] 赵联芳,丁奎元,于雪晴.海藻酸钠-活性炭固定化藻菌球的制备及其对碱性橙Ⅱ的降解[J].中国环境科学, 2024,44(2):781-792. Zhao L F, Ding K Y, Yu X Q. Preparation of sodium alginate-activated carbon immobilized algal-bacteria and its effect on basic orange degradation Ⅱ [J]. China Environmental Science, 2024,44(2):781- 792.
[14] 李亚婷,付欢,肖贵谦,等.红树林混合菌群协同降解偶氮染料活性黑5脱色性能研究[J].生物资源, 2023,45(5):431-439. Li Y T, Fu H, Xiao G Q, et al. Synergistic decolorization of azo dye reactive black 5 by mangrove mixed microbial community [J]. Biotic Resources, 2023,45(5):431-439.
[15] 冯凡,郭波,曹群,等.改性CNT负载纳米铁阴极的电芬顿法降解左氧氟沙星[J].中国环境科学, 2024:1-10. Feng F, Guo B, Cao Q, et al. Degradation of levofloxacin by electro fenton method with modified CNT supported nano-iron cathode [J]. China Environmental Science, 2024:1-10.
[16] 陈凤霞,马家海.Fe₃O₄@PCDP纳米复合材料的制备及其在类芬顿体系中的应用[J].中国科学院大学学报, 2020,37(5):593-598. Chen F X, Ma J H. Preparation of Fe₃O₄@PCDP nanocomposite and its application in fenton-like system [J]. Journal of University of Chinese Academy of Sciences, 2020,37(5):593-598.
[17] 张永祥,杜伟,李雅君,等.纳米零价铁在水处理中的应用研究综述[J].中国环境科学, 2022,42(11):5163-5178. Zhang Y X, Du W, Li Y J, et al. A review of nano zero valent iron in water treatment [J]. China Environmental Science, 2022,42(11):5163- 5178.
[18] 郭波,李赛,徐婷婷,等.膨胀珍珠岩负载纳米铁降解酸性大红与甲基橙的研究[J].现代化工, 2020,40(8):107-112. Guo B, Li S, Xu T T, et al. Degradation of acid scarlet and methyl orange by nanoscale zero-valent iron supported on expanded perlite [J]. Modern Chemical Industry, 2020,40(8):107-112.
[19] 刘也峰,曾双晴,邓大乐,等.改性酵母载纳米铁对水中甲基橙的吸附性能研究[J].化学与生物工程, 2023,40(6):22-27,39. Liu Y F, Zeng S Q, Deng D L, et al. Adsorption property of modified yeast supported iron nanoparticles against methyl orange in water [J]. Chemistry & Bioengineering, 2023,40(6):22-27,39.
[20] Zhu F, Li L W, Ren W T, et al. Effect of pH, temperature, humic acid and coexisting anions on reduction of Cr(Ⅵ) in the soil leachate by nZVI/Ni bimetal material [J]. Environmental Pollution, 2017,227:444- 450.
[21] 闫秋羽.修饰改性的纳米零价铁吸附降解有机污染物的研究[D].兰州:兰州理工大学, 2021. Yan Q Y. Study on the adsorption and degradation of organic pollutants bymodified nanometer zero-valent iro [D]. Lanzhou: Lanzhou University of Technology, 2021.
[22] Hou D B, Cui X D, Liu M, et al. Degradation of trichloroethylene by biochar supported nano zero-valent iron (BC-nZVI): the role of specific surface area and electrochemical properties [J]. The Science of the total environment, 2023,908:168341.
[23] Cui L, Wang N, Xu F H, et al. Pomelo peel biochar supported nZVI@Bi⁰ as a persulfate activator for the degradation of acetaminophen: enhanced performance and degradation mechanism [J]. Separation and Purification Technology, 2024,350:127966.
[24] 严芳敏,郭明帅,王菲.炭铁材料修复三氯乙烯污染地下水的性能[J].中国环境科学, 2024,44(2):825-831. Yan F M, Guo M S, Wang F. The performance of biochar/nZVI composite in remediating trichloroethylene contaminated groundwater [J]. China Environmental Science, 2024,44(2):825-831.
[25] Sharareh F, Mahmoud R S, Fereshte M, et al. Organophosphorus diazinon pesticide removing from aqueous solution by zero-valent iron supported on biopolymer chitosan: RSM optimization methodology [J]. Journal of Polymers and the Environment, 2020,29(1):1-18.
[26] 陈宗定,孔祥科,许春雪,等.硫化纳米零价铁在地下水修复中的研究进展[J].中国环境科学, 2024,44(7):3682-3697. Chen Z D, Kong X K, Xu C X, et al. Research advances in groundwater remediation by sulfidized nanoscale zerovalent iron [J]. China Environmental Science, 2024,44(7):3682-3697.
[27] 郑博文.四氧化三铁负载纳米零价铁类Fenton法处理废水中的多环芳烃[D].兰州:兰州交通大学, 2022. Zheng B W. Treatment of polycyclic aromatic hydrocarbons in wastewater by ferroferric oxide supported nano zero valent iron fenton-like method [D]. Lanzhou: Lanzhou Jiaotong University, 2022.
[28] 谢欣卓,钟金魁,李静,等.Fe₃O₄-nZVI类Fenton法降解水中磺胺甲恶唑[J].中国环境科学, 2022,42(7):3103-3111. Xie X Z, Zhong J K, Li J, et al. Degradation of sulfamethoxazole in water by fenton-like method using Fe₃O₄-nZVI [J]. China Environmental Science, 2022,42(7):3103-3111.
[29] 李品华.SiO₂包覆磁性Fe₃O₄纳米粒子负载催化剂的制备及其在有机合成中的应用[D].合肥:中国科学技术大学, 2019. Li P H. Preparation of SiO₂@Fe₃O₄ magnetic nanoparticles supported catalysts and their applications in organic synthesis [D]. Hefei: University of Science and Technology of China, 2019.
[30] Hasanin T H A, Fouly E A, Soliman E M. Microwave assisted facile green synthesis of silica coated magnetite nanoparticles for fast removal of methylene blue dye from environmental water samples [J]. International Journal of Environmental Analytical Chemistry, 2024, 104(9):1974-1993.
[31] 李勇超.功能化核壳型纳米铁的制备及修复地下水中六价铬的研究[D].天津:南开大学, 2012. Li C Y. Synthesis and characterization of functionalized core-shell Fe nanoparticles and application for Cr(Ⅵ) removal in groundwater [D]. Tianjin: Nankai University, 2012.
[32] Tan L, Lu S Y, Fang Z Q, et al. Enhanced reductive debromination and subsequent oxidative ring-opening of decabromodiphenyl ether by integrated catalyst of nZVI supported on magnetic Fe₃O₄ nanoparticles [J]. Applied Catalysis B: Environmental, 2017,200:200-210.
[33] 万俊杰.SiO₂包覆纳米铁的制备及用于难降解有机物2,4-DCP降解研究[D].广州:华南理工大学, 2014. Wan J J. Preparation of SiO₂-coated iron nanoparticles and degradation of 2,4-DCP of refractory organics [D]. Guangzhou: South China University of Technology, 2014.
[34] 王新昊.SiO₂@nZVI@Fe₃O₄类Fenton技术降解废水中的偶氮染料[D].兰州:兰州交通大学, 2023. Wang X H. Degradation of azo dyes in wastewater by SiO₂@nZVI@Fe₃O₄ fenton-like technology [D]. Lanzhou: Lanzhou Jiaotong University, 2023.
[35] 刘沁文,丁爱中,梁信,等.桉树生物炭负载绿色合成纳米零价铁去除水中Cr(Ⅵ) [J].环境科学, 2022,43(12):5657-5666. Liu Q W, Ding A Z, Liang X, et al. Removal of Cr(Ⅵ) from water using green synthesis nanoscale zero-valent iron supported on eucalyptus biochar [J]. Environmental Science, 2022,43(12):5657- 5666.
[36] 郑锦丽,葛红光,马书婷,等.核壳型磁性纳米复合材料Fe₃O₄@SiO₂@mTiO₂@Pt的制备及催化性能[J].功能材料, 2022, 53(1):1064-1071,1076. Zheng J L, Ge H G, Ma S T, et al. Preparation and catalytic properties of core-shell magnetic nanocomposites Fe₃O₄@SiO₂@mTiO₂@Pt [J]. Journal of Functional Materials, 2022,53(1):1064-1071,1076.
[37] 宗晓宁,罗清,张安龙,等.Fe基类Fenton催化剂非均相处理造纸废水[J].中国造纸, 2024,43(3):135-141. Zong X N, Luo Q, Zhang A L, et al. Fe-derived fenton-like catalyst for non-homogeneous treatment of papermaking wastewater [J]. China Pulp & Paper, 2024,43(3):135-141.
[38] Zhang X, He Y H, Gao G F, et al. Novel core-shell structural nZVI@Fe2P for sulfadiazine (SDZ) degradation: accelerated Fe(III)/Fe(II) dynamic cycling, boosted Fenton performance and stability [J]. Separation and Purification Technology, 2024,347: 127705.
[39] 钟金魁,李闻青,谢亚瑞,等.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 J K, Li W Q, Xie Y R, et al. Degradation of chlorophenolic pollutants in Fe₃O₄-nZVI fenton-like system [J]. China Environmental Science, 2023,43(11):5746-5756.
[40] Wang C K, Liu C H. Decontamination of alachlor herbicide wastewater by a continuous dosing mode ultrasound/Fe²⁺/H₂O₂ process [J]. Journal of Environmental Sciences, 2014,26(6):1332- 1339.
[41] 孙秋楠,张荣斌,邓曼君,等.高炉水渣负载硫化纳米零价铁对水中土霉素的去除[J].环境科学, 2021,42(2):867-873. Sun Q N, Zhang R B, Deng M J, et al. Removal of oxytetracycline from water using blast furnace slag loaded sulfide nanoscale zero-valent iron [J]. Environmental Science, 2021,42(2):867-873.
[42] Yang Y Q, Xu Y L, Zhong D J, et al. Zr⁴⁺-modified chitosan coated nZVI enhance the removal of Cr(VI) by adsorption-reduction interaction [J]. Journal of Environmental Chemical Engineering, 2024, 12(5):113315.
[43] Li J R, Su J J, Yang Q, et al. Hydrothermal synthesis of Zr-doped chitosan carbon-shell protected magnetic composites (Zr-Fe₃O₄@C) for stable removal of Cr(VI) from water: enhanced adsorption and pH adaptability [J]. Materials Chemistry and Physics, 2023,306:128057.
[44] Rosari S, Ardiansyah T. Degradation of methylene blue and congo-red dyes using fenton, photo-fenton, sono-fenton, and sonophoto-fenton methods in the presence of iron(II,III) oxide/zinc oxide/graphene (Fe₃O₄/ZnO/graphene) composites [J]. Separation and Purification Technology, 2019,210:563-573.
[45] Daud N K, Hameed B H. Decolorization of acid red 1by fenton-like process using rice husk ash-based catalyst [J]. Journal of Hazardous Materials, 2009,176(1):938-944.
[46] 闫娜.理性改造提高CotA漆酶对刚果红的脱色活性及脱色机理分析[D].无锡:江南大学, 2022. Yan N. Improving the decolorization activity of CotA-laccase to congo red by rational modificationand its decolorization mechanism analysis [D]. Wuxi: Jiangnan University, 2022.
[47] Dutta S, Rajnarayan S, Harjyoti K, et al. Rapid reductive degradation of azo and anthraquinone dyes by nanoscale zero-valent iron [J]. Environmental Technology & Innovation, 2016,5:176-187.
[48] Chen H H, Motuzas J, Martens W, et al. Surface and catalytic properties of stable Me(Ba, Ca and Mg)SrCoO for the degradation of orange II dye under dark conditions [J]. Applied Surface Science, 2018,450:292-300.
[49] Qurat U A, Usman R, Zheng C, et al. Activation of Fe₃O₄/bentonite through anchoring of highly dispersed and photo-reduced Cu ions for higher pH fenton-like degradation and effective adsorption of congo red dye [J]. Journal of Industrial and Engineering Chemistry, 2024, 134:327-342.
[50] Chen Y F, Yan X M, Lin H F, et al. Enhanced fenton-like degradation of rhodamine B and congo red by benzene and K⁺ co-doped carbon nitride with in situ-generated H₂O₂ [J]. Journal of the Taiwan Institute of Chemical Engineers, 2022,131:104179.
[51] 袁广恩.原位生物电催化过氧化氢氧化降解偶氮染料的性能研究[D].大连:大连理工大学, 2015. Yuan G E. Performance study of in situ bioelectrocatalytic oxidative degradation of azo dyes by hydrogen peroxide oxidation [D]. Dalian: Dalian University of Technology, 2015.
[52] Chatkrita R, Duangkamon V, Panida P, et al. Mechanistic study of iodoacetamide degradation by functionalized SiO₂-coated nZVI: The role of surface functional groups on adsorption, dehalogenation and hydrolysis [J]. Journal of Water Process Engineering, 2024,63:105485.