Fe3O4/FeS2活化H2O2降解典型苯胂酸类污染物

华洁; 王敏; 林舒婷; 江彦亭; 林春香; 吕源财; 刘明华

PDF(2593 KB)

中国环境科学 ›› 2021, Vol. 41 ›› Issue (6) : 2646-2656.

水污染与控制

Fe₃O₄/FeS₂活化H₂O₂降解典型苯胂酸类污染物

华洁, 王敏, 林舒婷, 江彦亭, 林春香, 吕源财, 刘明华

作者信息 +

Fe₃O₄/FeS₂ activated H₂O₂ degradation of typical phenylarsonic acid pollutants

HUA Jie, WANG Min, LIN Shu-ting, JIANG Yan-ting, LIN Chun-xiang, LV Yuan-cai, LIU Ming-hua

Author information +

文章历史 +

摘要

利用水热法成功制备了Fe₃O₄/FeS₂催化剂，并将其用于构建非均相芬顿体系降解典型的苯胂酸类污染物（洛克沙胂，ROX）.XRD、SEM、XPS和磁学测量系统（VSM）等表征结果表明，Fe₃O₄/FeS₂呈明显的颗粒状且具有良好的磁性.降解实验结果显示，在最优条件下（初始pH值为4.5、ROX起始浓度为20mg/L、Fe₃O₄/FeS₂投加量为0.15g/L和H₂O₂浓度为0.034g/L，Fe₃O₄/FeS₂介导的非均相芬顿体系可以超快速降解ROX，1min后的降解效率达到96.74%，明显优于单独的Fe₃O₄或FeS₂体系.此外，Fe₃O₄/FeS₂可以通过磁铁进行快速回收利用，同时也具有良好的重复利用性能，使用3次后，ROX的降解效率仍超过80%.机理分析表明，Fe₃O₄/FeS₂能够快速地催化H₂O₂产生具有强氧化性的羟基自由基（·OH）.在·OH的作-用下，ROX分子结构中C-As、C-N和C-C等化学键发生断裂，发生脱砷、脱硝和开环等反应，进而生成一系列的有机产物（如酚类、醌类、小分子有机酸等）和无机产物（As （V）和NO₃^-）.之后，无机砷能够被吸附在催化剂表面，而有机产物则进一步被矿化.

Abstract

Fe₃O₄/FeS₂ catalyst was successfully prepared by hydrothermal method, and employed to mediate a heterogeneous Fenton system for the remediation of a typical phenylarsonic acid pollutant (roxarsone, ROX). The characterization results of XRD, SEM, XPS and magnetic measurement system (VSM) showed that Fe₃O₄/FeS₂ displayed evident granular particles and good magnetic properties. The results of ROX degradation experiments showed that under optimal conditions (4.5of the initial pH, 20mg/L of ROX initial concentration, 0.15g/L of Fe₃O₄/FeS₂ dosage and 0.034g/L of H₂O₂ concentration), the heterogeneous Fenton system could instantaneously degrade 96.74% of ROX in 1min, which was much better than of the systems mediated by sole Fe₃O₄ or FeS₂. In addition, Fe₃O₄/FeS₂ could be effectively recycled by magnets, and also exhibited good reusability. After 3 runs, the degradation efficiency of ROX was still over 80%. Mechanism analysis revealed that plenty of hydroxyl radicals (·OH) could be generated via the catalytic reaction between Fe₃O₄/FeS₂ and H₂O₂. Subsequently, the ·OH could quickly attacked the C-As, C-N, and C-C bonds in the ROX molecule, resulting in the dearsenication, denitrification and ring opening reactions, as well as the formation of a series of organic products (such as phenols, quinones, small molecular organic acids, etc.) and inorganic products (As(V) and NO₃^-). Finally, the released inorganic arsenic could be adsorbed on the surface of the catalyst, while the organic product was further mineralized.

导出引用

华洁, 王敏, 林舒婷, 江彦亭, 林春香, 吕源财, 刘明华. Fe₃O₄/FeS₂活化H₂O₂降解典型苯胂酸类污染物[J]. 中国环境科学. 2021, 41(6): 2646-2656

HUA Jie, WANG Min, LIN Shu-ting, JIANG Yan-ting, LIN Chun-xiang, LV Yuan-cai, LIU Ming-hua. Fe₃O₄/FeS₂ activated H₂O₂ degradation of typical phenylarsonic acid pollutants[J]. China Environmental Science. 2021, 41(6): 2646-2656

中图分类号： X703.5

参考文献

[1] 孟计忠.洛克沙胂的光化学降解及其强化的研究[D]. 合肥:合肥工业大学, 2019. Meng J Z. Study on photochemical degradation and Enhancement of Roxarsone[D]. HeFei:HeFei University of Technology, 2019.
[2] Carpenter L E. The effect of 3-nitro-4-hydroxy phenyl arsonic acid on the growth of swine[J]. Archives of Biochemistry & Biophysics, 1951,32(1):181-186.
[3] Chen N, Wan Y, Ai Z, et al. Fast transformation of roxarsone into toxic arsenic species with ferrous iron and tetrapolyphosphate[J]. Environmental Chemistry Letters, 2019,17(2):1077-1084.
[4] Garbarino J R, Bednar A J, Rutherford D W, et al. Environmental fate of roxarsone in poultry litter. I. Degradation of roxarsone during composting[J]. Environmental Science & Technology, 2003,37(8):1509-1514.
[5] Li P Y, Wu Y Z, Wang Y L, et al. Soil Behaviour of the veterinary drugs lincomycin, monensin, and roxarsone and their toxicity on environmental organisms[J]. Molecules, 2019,24(24):4465.
[6] Abdo K M, Elwell M R, Montgomery C A, et al. Toxic responses in F344rats and B6C3F1mice given roxarsone in their diets for up to 13weeks[J]. Toxicology Letters, 1989,45(1):55-66.
[7] Chen S, Deng J, Ye C, et al. Simultaneous removal of p ara-arsanilic acid and the released inorganic arsenic species by CuFe₂O₄ activated peroxymonosulfate process[J]. Science of the Total Environment, 2020,742.DOI:10.1016/j.scitotenv.2020.140587.
[8] Zheng S, Jiang W, Cai Y, et al. Adsorption and photocatalytic degradation of aromatic organoarsenic compounds in TiO₂ suspension[J]. Catalysis Today, 2014,224:83-88.DOI:10.1016/j.cattod.2013. 09.040.
[9] Zhao Z, Pan S, Ye Y, et al. FeS₂/H₂O₂ mediated water decontamination from p-arsanilic acid via coupling oxidation, adsorption and coagulation:Performance and mechanism[J]. Chemical Engineering Journal, 2020,381.DOI:10.1016/j.cej.2019.122667.
[10] Xie X, Zhao W, Hu Y, et al. Permanganate oxidation and ferric ion precipitation (KMnO₄-Fe(III)) process for treating phenylarsenic compounds[J]. Chemical Engineering Journal, 2019,357:600-610. DOI:10.1016/j.cej.2018.09.194.
[11] Fenton H. Oxidation of tartaric acid in presence of iron[J]. Journal of the Chemical Society Transactions, 1894,65:899-910.DOI:10.1039/CT8946500899.
[12] 杨远秀,姚创,刘晖,等.磁性Fe^n+@GO非均相Fenton催化氧化亚甲基蓝[J]. 中国环境科学, 2018,38(5):121-128. Yang Y X, Yao C, Liu H, et al. Catalytic oxidation of methylene blue by magnetic Fe^n+@GO heterogeneous Fenton[J]. China Environmental Sciences, 2018,38(5):121-128.
[13] Simond O, Schaller V, Comninellis C. Theoretical model for the anodic oxidation of organics on metal oxide electrodes[J]. 1997,42(13/14):2009-2012.
[14] 周玉莲,于永波,黄湾,等.氧化石墨烯电催化高效降解有机染料RBk5[J]. 中国环境科学, 2019,39(11):4653-4659. Zhou Y L, Yu Y B, Huang W, et al. Electrocatalytic degradation of organic dye RBK5by graphene oxide[J]. China Environmental Sciences, 2019,39(11):4653-4659.
[15] Snyder S A, Wert E C, Rexing D J, et al. Ozone Oxidation of Endocrine Disruptors and Pharmaceuticals in Surface Water and Wastewater[J]. Ozone Science & Engineering, 2006,28(6):445-460.
[16] 马富军,李新洋,宗博洋,等.电-多相臭氧催化技术处理金刚烷胺制药废水[J]. 中国环境科学, 2018,38(10):115-121. Ma F J, Li X Y, Zong B Y, et al. Treatment of Amantadine Pharmaceutical Wastewater by Electro-heterogeneous Ozone Catalytic Technology[J]. China Environmental Science, 2018,38(10):115-121.
[17] Mishra V S, Mahajani V V, Joshi J B. Wet Air Oxidation[J]. Industrial Engineering Chemistry Research, 1995,34(1):2-48.
[18] 张宣娇,孙羽,刘明,等.CeO₂形貌结构对催化湿式空气氧化苯酚性能的影响[J]. 中国环境科学, 2020,40(10):157-161. Zhang X J, Sun Y, Liu M, et al. The effect of CeO₂ morphology and structure on catalytic wet air oxidation of phenol[J]. China Environmental Science. 2020,40(10):157-161.
[19] Babuponnusami A, Muthukumar K. A review on Fenton and improvements to the Fenton process for wastewater treatment[J]. Journal of Environmental Chemical Engineering, 2014,2(1):557-572.
[20] Tian C, Zhao J, Zhang J, et al. Enhanced removal of roxarsone by Fe₃O₄@3D graphene nanocomposites:synergistic adsorption and mechanism[J]. Environmental Science Nano, 2017,4(11):2134-2143.
[21] Xie X, Hu Y, Cheng H. Rapid degradation of p-arsanilic acid with simultaneous arsenic removal from aqueous solution using Fenton process[J]. Water Research, 2016,89:59-67.
[22] Lv Y, Huang S, Huang G, et al. Remediation of organic arsenic contaminants with heterogeneous Fenton process mediated by SiO₂-coated nano zero-valent iron[J]. EnvironmentaL Science and Pollution Research, 2020,27(11):12017-12029.
[23] Satishkumar G, Landau M V, Buzaglo T, et al. Fe/SiO₂heterogeneous Fenton catalyst for continuous catalytic wet peroxide oxidation prepared in situ by grafting of iron released from LaFeO₃[J]. Applied Catalysis B:Environmental, 2013,138:276-284.DOI:10.1016/j.apcatb.2013.02.040.
[24] Zhang Y, Zhang K, Dai C, et al. An enhanced Fenton reaction catalyzed by natural heterogeneous pyrite for nitrobenzene degradation in an aqueous solution[J]. Chemical Engineering Journal, 2014, 244:438-445.DOI:10.1016/j.cej.2014.01.088.
[25] Wan Z, Wang J. Degradation of sulfamethazine using Fe₃O₄-Mn₃O₄/reduced graphene oxide hybrid as Fenton-like catalyst[J]. Journal of Hazardous Materials, 2017,324(B):653-664.
[26] Li J, Li X, Han J, et al. Mesoporous bimetallic Fe/Co as highly active heterogeneous Fenton catalyst for the degradation of tetracycline hydrochlorides[J]. Scientific Reports, 2019,9(1).DOI:10.1038/s41598-019-52013-y.
[27] Liu J, Du Y, Sun W, et al. Preparation of new adsorbent-supported Fe/Ni particles for the removal of crystal violet and methylene blue by a heterogeneous Fenton-like reaction[J]. Rsc Advances, 2019,9(39):22513-22522.
[28] Wu D, Feng Y, Ma L. Oxidation of Azo Dyes by H₂O₂ in Presence of Natural Pyrite[J]. Water air and soil pollution, 2013,224(2):1-11.
[29] Chen H, Zhang Z, Yang Z, et al. Heterogeneous Fenton-like catalytic degradation of 2,4-dichlorophenoxyacetic acid in water with FeS[J]. Chemical Engineering Journal, 2015,273:481-489.DOI:10.1016/j.cej.2015.03.079.
[30] Guo C, Tong X, Guo X Y. Solvothermal synthesis of FeS₂ nanoparticles for photoelectrochemical hydrogen generation in neutral water[J]. Materials Letters, 2015,161:220-223.DOI:10.1016/j.matlet. 2015.08.112.
[31] Stucki J W. The Quantitative Assay of Minerals for Fe²⁺ and Fe³⁺ Using 1,10-Phenanthroline:II. A Photochemical Method1[J]. Soil Science Society of America Journal, 1981,45(3):633-637.
[32] Li D, Zhu X, Zhong Y, et al. Abiotic transformation of hexabromocyclododecane by sulfidated nanoscale zerovalent iron:Kinetics, mechanism and influencing factors[J]. Water Research, 2017,121:140.DOI:10.1016/j.watres.2017.05.019.
[33] Zeng L Y, Gong J Y, Dan J F, et al. Novel visible light enhanced Pyrite-Fenton system toward ultrarapid oxidation of p-nitrophenol:Catalytic activity, characterization and mechanism[J]. Chemosphere, 2019,228:232-240.DOI:10.1016/j.chemosphere.2019.04.103.
[34] 曾令玉.黄铁矿(FeS₂)异相Fenton反应催化氧化对硝基酚的研究[D]. 武汉:华中科技大学, 2019. Zeng L Y. Study on catalytic Oxidation of P-nitrophenol in heterogeneous Fenton reaction of FeS₂.[D]. WuHan:HuaZhong University of Science and Technology, 2019.
[35] Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2008,254(8):2441-2449.
[36] 吕源财.纳米零价铁钯/微生物联合体系降解2,2',4,4'-四溴联苯醚的研究[D]. 广州:华南理工大学, 2016. Lv Y C. Degradation of 2,2',4,4' -tetrabromobiphenyl ether by nanometer zero-valent ferro-palladium/microorganism system[D]. GuangZhou:South China University of Technology, 2016.
[37] Hou L, Zhang Q H, Jéromr F, et al. Shape-controlled nanostructured magnetite-type materials as highly efficient Fenton catalysts[J]. Applied Catalysis B Environmental, 2014,144:739-749.DOI:10.1016/j.apcatb.2013.07.072.
[38] 杨智临.铁基材料产羟基自由基特征与除砷机制[D]. 北京:中国地质大学, 2020. Yang Z L. Hydroxyl radical production and arsenic removal mechanism of iron based materials[D]. BeiJing:China University of Geosciences, 2020.
[39] Zhang Y, Zhou Z, Wen F, et al. A flower-like MoS₂ decorated MgFe₂O₄ nanocomposite:Mimicking peroxidase and colorimetric detection of H₂O₂ and glucose[J]. Sensors and Actuators B-Chemical, 2018,275:155-162.DOI:10.1016/j.snb.2018.08.051.
[40] 陈亚明.Fe⁰及其硫化改性制备FeS_x/Fe⁰去除水中Cr(Ⅵ)的研究[D]. 济南:山东大学, 2016. Chen Y M. Fe⁰ and sulfide modified synthesis FeSx/Fe⁰ removing Cr (Ⅵ) research[D]. JiNan:Shandong University, 2016.
[41] Bae S, Kim D, Lee W. Degradation of diclofenac by pyrite catalyzed Fenton oxidation[J]. Applied Catalysis B Environmental, 2013, 134-135(9):93-102.
[42] 李春娟.芬顿法和类芬顿法对水中污染物的去除研究[D]. 哈尔滨:哈尔滨工业大学, 2009. Li C J. Research on the Removal of pollutants in water by Fenton method and Fenton-like Method[D]. HaErBin:Harbin Institute of Technology, 2009.
[43] GB3838-2002地表水环境质量标准[S].
[44] Min X, Li Y, Ke Y, et al. Fe-FeS₂adsorbent prepared with iron powder and pyrite by facile ball milling and its application for arsenic removal[J]. Water Science and Technology, 2017,76(1):192-200.
[45] Che H, Bae S, Lee W. Degradation of trichloroethylene by Fenton reaction in pyrite suspension[J]. Journal of Hazardous Materials, 2011,185(2):1355-1361.
[46] 朱国鹏.Fe₃O₄@MoS₂量子点光辅助芬顿技术处理四环素废水的研究[D]. 长春:吉林大学, 2020. Zhu G P. Study on treatment of tetracycline Wastewater by Fe₃O₄@MoS₂ Quantum dot Light Assisted Fenton Technology[D]. ChangChun:Jilin University, 2020.
[47] 刘杰.纳米Fe₃O₄及其复合材料催化过氧化物去除水中氯酚的研究[D]. 哈尔滨:哈尔滨工业大学, 2014. Liu J. Catalytic removal of chlorophenol from water by nanometer Fe₃O₄ and its composites[D]. HaErBin:Harbin Institute of Technology, 2014.
[48] Wu D, Chen Y, Zhang Y, et al. Ferric iron enhanced chloramphenicol oxidation in pyrite (FeS₂) induced Fenton-like reactions[J]. Separation and Purification Technology, 2015,154:60-67.DOI:10. 1016/j.seppur.2015.09.016.
[49] 周洋.基于黄铁矿的非均相类-Fenton反应高效降解邻苯二甲酸二乙酯的机制研究[D]. 芜湖:安徽师范大学, 2019. Zhou Y. Degradation of diethyl phthalate by Heterogeneous Fenton reaction based on pyrite[D]. WuHu:AnHui Normal University, 2019.