Fe3O4磁性纳米颗粒催化电化学降解土霉素的研究

doi:10.13208/j.electrochem.210714

摘要/Abstract

摘要：

本研究以Fe₃O₄作为催化剂,活化过氧化二硫酸盐电化学氧化体系,改善土霉素（OTC）的降解为主要内容。通过场发射扫描电子显微镜（SEM）、 X射线衍射（XRD）表征,证明水热法成功制备了150 nm左右的Fe₃O₄磁性纳米颗粒。通过对比实验证明,同时加入Fe₃O₄与施加电流时表现出优秀的OTC降解能力,经证明在过硫酸盐（PDS）浓度为4.0 mmol·L^-1,溶液初始pH值为7,电流密度j为30 mA·cm^-2, Fe₃O₄磁性纳米颗粒用量为0.1 g·L^-1,初始OTC浓度为70 mg·L^-1的条件时,60 min内OTC降解率可达88.75%,一级动力学模拟曲线的速率常数可以达到0.06069。此外, Fe₃O₄连续循环5次后,依然具有良好的稳定性。Fe₃O₄与电流的存在分别可以促进SO₄^·-和^·OH的生成。经自由基猝灭实验证明, SO₄^·-和^·OH均负责抗生素降解。

关键词: 电化学氧化, 土霉素降解, Fe₃O₄磁性纳米颗粒, 稳定性

Abstract:

The purpose of this study is to optimize the electrochemical degradation of oxytetracycline (OTC) in water using a low cost and simple preparation method. In this paper, the Fe₃O₄ magnetic nanoparticles were used as catalysts to activate the electrochemical oxidation system of peroxydisulfates (PDS) which acted as electrolytes to provide active free radicals in order to improve the degradation of OTC under the condition of applying current. As one of the tetracycline antibiotics (TCs), OTC is one of the most used antibiotics in the world, therefore, it is necessary to study the effective degradation of OTC. By means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and other characterization methods, it was proved that the Fe₃O₄ magnetic nanoparticles at about 150 nm were successfully prepared by a simple hydrothermal method. Firstly, it is suggested that the application of electric current and the presence of Fe₃O₄ magnetic nanoparticles are necessary for the effective degradation of OTC. Secondly, the optimal reaction experiment confirmed an excellent OTC degradation ability by combination of Fe₃O₄ magnetic nanoparticles and current. The optimal reaction conditions were as follows: the concentration of PDS was 4.0 mmol·L^-1, the initial pH value of the solution was 7, and the current density j was 30 mA·cm^-2. When the dosage of Fe₃O₄ magnetic nanoparticles was 0.1 g·L^-1 and the initial OTC concentration was 70 mg·L^-1, the degradation rate of OTC could reach 88.75% within 60 min and the rate constant of the first-order kinetics simulation curve could reach 0.06069. In addition, the variation of UV-vis characteristic peak of OTC during the degradation process revealed that the change of OTC concentration was not due to simple physical adsorption, but through the complete degradation of active free radicals. In addition, after the continuous circulation of Fe₃O₄ magnetic nanoparticles for 5 times, the degradation rate of OTC could still reach more than 68%, proving that Fe₃O₄ magnetic nanoparticles have good catalytic stability. The presence of Fe₃O₄ magnetic nanoparticles and the application of electric current could promote the formations of SO₄^·- and ^·OH, respectively. The radical quenching experiments showed that both SO₄^·- and ^·OH were active free radicals degraded by antibiotics. This work uses a low-cost catalyst to enhance an electrochemical degradation of OTC. The experimental operation is simple, the degradation rate is fast, and the energy consumption is low. It is promising to practical applications.

Key words: electrochemical oxidation, oxytetracycline degradation, Fe₃O₄ magnetic nanoparticles, stability

应方, 许珊珊, 许燕冰, 梁苗苗, 李剑锋. Fe₃O₄磁性纳米颗粒催化电化学降解土霉素的研究[J]. 电化学（中英文）, 2022, 28(4): 2107141.

Fang Ying, Shan-Shan Xu, Yan-Bing Xu, Miao-Miao Liang, Jian-Feng Li. Electrochemical Degradation of Oxytetracycline Catalyzed by Fe₃O₄ Magnetic Nanoparticles[J]. Journal of Electrochemistry, 2022, 28(4): 2107141.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210714

https://electrochem.xmu.edu.cn/CN/Y2022/V28/I4/2107141

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参考文献 24

[1]	Xu S S, Lü Y P, Zhang Y. 3D hydrangea-like Mn₃O₄@(PSS/PDDA/Pt)_n with ultrafine Pt nanoparticles modified anode for electrochemical oxidation of tetracycline[J]. J. Taiwan Inst. Chem. E., 2020, 112: 240-250. doi: 10.1016/j.jtice.2020.06.009 URL
[2]	Tang S F, Zhao M Z, Yuan D L, Li X, Wang Z T, Zhang X Y, Jiao T F, Ke J. Fe₃O₄ nanoparticles three-dimensional electro-peroxydisulfate for improving tetracycline degradation[J]. Chemosphere, 2021, 268: 129315. doi: 10.1016/j.chemosphere.2020.129315 URL
[3]	Ren F J, Wang T, Liu H T, Liu D S, Zhong R, You C Y, Zhang W J, Lv S Y, Liu S S, Zhu H, Chang L, Wang B. CoMn₂O₄ nanoparticles embed in graphene oxide aerogel with three-dimensional network for practical application prospects of oxytetracycline degradation[J]. Sep. Purif. Te-chnol., 2021, 259: 118179.
[4]	Halling-Sorensen B, Sengelov G, Tjornelund J. Toxicity of tetracyclines and tetracycline degradation products to environmentally relevant bacteria, including selected tetracycline-resistant bacteria[J]. Arch. Environ. Contam. Toxicol., 2002, 42(3): 263-271. doi: 10.1007/s00244-001-0017-2 URL
[5]	Daghrir R, Drogui P. Tetracycline antibiotics in the environment: a review[J]. Environ Chem Lett., 2013, 11(3): 209-227. doi: 10.1007/s10311-013-0404-8 URL
[6]	Gao Y, Li Y, Zhang L, Huang H, Hu J J, Shah S M, Su X G. Adsorption and removal of tetracycline antibiotics from aqueous solution by graphene oxide[J]. J. Colloid Interface Sci., 2012, 368: 540-546. doi: 10.1016/j.jcis.2011.11.015 URL
[7]	Khan M H, Bae H, Jung J Y. Tetracycline degradation by ozonation in the aqueous phase: proposed degradation intermediates and pathway[J]. J. Hazard. Mater., 2010, 181(1-3): 659-665. doi: 10.1016/j.jhazmat.2010.05.063 URL
[8]	Yang Q X, Yang X F, Yan Y, Sun C, Wu H J, He J, Wang D S. Heterogeneous activation of peroxymonosulfate by different ferromanganese oxides for tetracycline degradation: Structure dependence and catalytic mechanism[J]. Chem. Eng. J., 2018, 348: 263-270. doi: 10.1016/j.cej.2018.04.206 URL
[9]	Wang J B, Zhi D, Zhou H, He X W, Zhang D Y. Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti₄O₇ anode[J]. Water Res., 2018, 137: 324-334. doi: 10.1016/j.watres.2018.03.030 URL
[10]	Zhang Y Q, Zuo S J, Zhang Y, Ren G B, Pan Y W, Zhang Q Z, Zhou M H. Simultaneous removal of tetracycline and disinfection by a flow-through electro-peroxone process for reclamation from municipal secondary effluent[J]. J. Hazard. Mater., 2019, 368: 771-777. doi: 10.1016/j.jhazmat.2019.02.005 URL
[11]	Xie L B, Mi X Y, Liu Y G, Li Y, Sun Y, Zhan S H, Hu W P. Highly efficient degradation of polyacrylamide by an Fe-doped Ce_0.75Zr_0.25O₂ solid solution/CF composite cathode in a heterogeneous electro-fenton process[J]. ACS Appl. Mater. Interfaces., 2019, 11(34): 30703-30712. doi: 10.1021/acsami.9b06396 URL
[12]	Guo P C, Qiu H B, Yang C W, Zhang X, Shao X Y, Lai Y L, Sheng G P. Highly efficient removal and detoxification of phenolic compounds using persulfate activated by MnO_x@OMC: Synergistic mechanism and kinetic analysis[J]. J. Hazard. Mater., 2021, 402(15): 123846-123855. doi: 10.1016/j.jhazmat.2020.123846 URL
[13]	Guo H, Su S, Liu Y, Ren X H, Guo W L. Enhanced catalytic activity of MIL-101(Fe) with coordinatively unsaturated sites for activating persulfate to degrade organic pollutants[J]. Environ. Sci. Pollut. Res., 2020, 27: 17194-17204. doi: 10.1007/s11356-020-08316-z URL
[14]	Gao Y, Wang Q, Ji G Z, Li A M. Degradation of antibiotic pollutants by persulfate activated with various carbon materials[J]. Chem. Eng. J., 2022, 429: 132387-132400. doi: 10.1016/j.cej.2021.132387 URL
[15]	Song H R, Yan L X, Jiang J, Ma J, Pang S Y, Zhai X D, Zhang W, Li D. Enhanced degradation of antibiotic sulfamethoxazole by electrochemical activation of PDS using carbon anodes[J]. Chem. Eng. J., 2018, 344: 12-20. doi: 10.1016/j.cej.2018.03.050 URL
[16]	Cao M H, Hou Y Z, Zhang E, Tu S X, Xiong S L. Ascorbic acid induced activation of persulfate for pentachloro-phenol degradation[J]. Chemosphere, 2019, 229: 200-205. doi: 10.1016/j.chemosphere.2019.04.135 URL
[17]	Matzek L W, Carter K E. Activated persulfate for organic chemical degradation: A review[J]. Chemosphere, 2016, 151: 178-188. doi: 10.1016/j.chemosphere.2016.02.055 pmid: 26938680
[18]	Keyikoglu R, Karatas O, Khataee A, Kobya M, Can O T, Soltani R D C, Isleyen M. Peroxydisulfate activation by in-situ synthesized Fe₃O₄ nanoparticles for degradation of atrazine: Performance and mechanism[J]. Sep. Purif. Te-chnol., 2020, 247: 116925.
[19]	Ganiyu S O, Zhou M H, Martínez-Huitle C A. Heterogeneous electro-Fenton and photoelectro-Fenton processes: A critical review of fundamental principles and application for water/wastewater treatment[J]. Appl. Catal. B., 2018, 235: 103-129. doi: 10.1016/j.apcatb.2018.04.044 URL
[20]	Bagheri S, TermehYousefi A, Do T O. Photocatalytic pathway toward degradation of environmental pharmaceutical pollutants: structure, kinetics and mechanism approach[J]. Catal. Sci. Technol., 2017, 7: 4548-4569. doi: 10.1039/C7CY00468K URL
[21]	Ike I A, Linden K G, Orbell J D, Duke M. Critical review of the science and sustainability of persulphate advanced oxidation processes[J]. Chem. Eng. J., 2018, 338: 651-669. doi: 10.1016/j.cej.2018.01.034 URL
[22]	Zhang C, Li F, Wen R B, Zhang H K, Elumalai P, Zheng Q, Chen H Y, Yang Y J, Huang M Z, Ying G. G. Heterogeneous electro-Fenton using three-dimension NZVI-BC electrodes for degradation of neonicotinoid wastewater[J]. Water Res., 2020, 182: 115975. doi: 10.1016/j.watres.2020.115975 URL
[23]	Poblete R, Oller I, Maldonado M I, Cortes E. Improved landfill leachate quality using ozone, UV solar radiation, hydrogen peroxide, persulfate and adsorption processes[J]. J. Environ. Manage., 2019, 232: 45-51. doi: 10.1016/j.jenvman.2018.11.030 URL
[24]	Dong Z Y, Zhang Q, Chen B Y, Hong J M. Oxidation of bisphenol A by persulfate via Fe₃O₄-α-MnO₂ nanoflower-like catalyst: Mechanism and efficiency[J]. Chem. Eng. J., 2019, 357: 337-347. doi: 10.1016/j.cej.2018.09.179 URL

Parameter		Degradation efficiency	Rate constant (k_a, min^-1)	R²
PDS concentration(mmol·L^-1)	2.0	75.88%	0.02949	0.995
	3.0	80.03%	0.03077	0.962
	4.0	80.62%	0.03400	0.993
pH	5.0	76.99%	0.03014	0.979
	3.0	75.57%	0.02993	0.999
	4.0	83.5%	0.03715	0.994
	6.0	83.99	0.04454	0.986
	7.0	84.67%	0.05018	0.954
	9.0	83.2%	0.04276	0.989
Current density j (mA·cm^-2)	15	84.67%	0.05018	0.954
	20	85.84%	0.04766	0.979
	30	87.18%	0.05369	0.995
	40	85.90%	0.05092	0.974
Catalyst dosage (g·L^-1)	0.05	72.61%	0.02622	0.96
	0.10	87.18%	0.05369	0.995
	0.15	83.53%	0.04896	0.977
Initial OTC Concentration (mg·L^-1)	50	87.18%	0.05369	0.995
	70	88.75%	0.06069	0.976
	90	77.31%	0.02350	0.858

Fe₃O₄磁性纳米颗粒催化电化学降解土霉素的研究

Electrochemical Degradation of Oxytetracycline Catalyzed by Fe₃O₄ Magnetic Nanoparticles

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