Abstract
A magnetic MnFe2O4/MWNT nanocomposite activated with sodium persulfate (PDS) was investigated for the removal of the widely used antibiotic tetracycline (TC). The best-performing 80 wt.% MnFe2O4/MWNT nanocomposite was screened for catalytic degradation of TC by comparing the catalytic and adsorption processes. The nanocomposite was evaluated using a series of physical characterizations. The effects of catalyst dosage, PDS dosage, temperature, initial pH, and initial concentration of TC on TC removal were investigated. After the reaction for 90 min, the addition of 4 mM PDS to the 80 wt.% MnFe2O4/CNT catalyst at 0.5 g/L degraded 78.85% of TC and 51.97% of TOC at an initial TC concentration of 40 mg/L. The reusability of MnFe2O4/MWNT nanocomposite was evaluated and the structural stability of the material was verified. It was demonstrated that multiple active species (SO4−, ·OH, ·O2−, 1O2) were produced in the MnFe2O4/MWNT/PDS system. The catalytic mechanism was analyzed based on the XPS results. Total organic carbon (TOC) measurement indicated partial TC had completely mineralized. The presumable degradation pathway of TC was proposed according to intermediate products by the LC–MS method.
Similar content being viewed by others
Data availability
The datasets used and analyzed during the current study are available from the corresponding author on reasonable request.
References
Chen P, Chew LM, Kostka A (2013) The structural and electronic promoting effect of nitrogen-doped carbon nanotubes on supported Pd nanoparticles for selective olefin hydrogenation. Catal Sci Technol 3:1964–1971
Chen L, Ding D, Liu C, Cai H, Qu Y, Yang S, Gao Y, Cai T (2018) Degradation of norfloxacin by CoFe 2 O 4-GO composite coupled with peroxymonosulfate: A comparative study and mechanistic consideration. Chem Eng J 334:273–284
Chen Z, Wang L, Xu H, Wen Q (2020) Efficient heterogeneous activation of peroxymonosulfate by modified CuFe 2 O 4 for degradation of tetrabromobisphenol A. Chem Eng J 389:124345
Cheng X, Guo H, Zhang Y, Korshin GV, Yang B (2019) Insights into the mechanism of nonradical reactions of persulfate activated by carbon nanotubes: Activation performance and structure-function relationship. Water Res 157:406–414
Diao Z, Dong F, Yan L, Chen Z, Qian W, Kong L, Zhang Z, Zhang T, Tao X, Du J, Jiang D, Wei Chu (2020) Synergistic oxidation of Bisphenol A in a heterogeneous ultrasound-enhanced sludge biochar catalyst/persulfate process: Reactivity and mechanism. J Hazard Mater 384:121385
Foroutan R, Peighambardoust SJ, Latifi P, Ahmadi A, Alizadeh M, Ramavandi B (2021) Carbon nanotubes/β-cyclodextrin/MnFe 2 O 4 as a magnetic nanocomposite powder for tetracycline antibiotic decontamination from different aqueous environments. J Environ Chem Eng 9(6):106344
Guan Y, Ma J, Li X, Fang J, Chen L (2011) Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system. Environ Sci Technol 45:9308–9314
Guo H, Zhou X, Zhang Y, Yao Q, Qian Y, Chu H, Chen J (2020) Carbamazepine degradation by heterogeneous activation of peroxymonosulfate with lanthanum cobaltite perovskite: Performance, mechanism and toxicity. J Environ Sci 91:10–21
Hu P, Su H, Chen Z, Yu C, Li Q, Zhou B, Alvarez PJJ, Long M (2017) Selective degradation of organic pollutants using an efficient metal-free catalyst derived from carbonized polypyrrole via peroxymonosulfate activation. Environ Sci Technol 51:11288–11296
Ji P, Zhu F, Zhou J, Ma J, Wang H, Xu G (2022) Synthesis of superparamagnetic MnFe 2 O 4 /mSiO 2 nanomaterial for degradation of perfluorooctanoic acid by activated persulfate. Environ Sci Pollut Res 29:37071–37083
Jiang X, Guo Y, Zhang L, Jiang W, Xie R (2018) Catalytic degradation of tetracycline hydrochloride by persulfate activated with nano Fe 0 immobilized mesoporous carbon. Chem Eng J 341:392–401
Kang J, Duan X, Wang C, Sun H, Tan X, Tade MO, Wang S (2018) Nitrogen-doped bamboo-like carbon nanotubes with Ni encapsulation for persulfate activation to remove emerging contaminants with excellent catalytic stability. Chem Eng J 332:398–408
Kim SC, Wang GS (2010) Catalytic combustion of VOCs over a series of manganese oxide catalysts. Appl Catal B Environ 98:180–185
Kong Y, Zhuang Y, Han K, Shi B (2020) Enhanced tetracycline adsorption using alginate-graphene-ZIF67 aerogel. Colloids Surf A Physicochem Eng Asp 588:124360
Lei Y, He J, Su S, Cui Y, Huang D, Wang G (2017) Occurrence, distribution, and attenuation of pharmaceuticals and personal care products in the riverside groundwater of the Beiyun River of Beijing, China. Environ Sci Pollut Res Int 24:15838–15851
Li Z, Guo C, Lyu J, Hu Z, Ge M (2019) Tetracycline degradation by persulfate activated with magnetic Cu/CuFe 2 O 4 composite: Efficiency, stability, mechanism and degradation pathway. J Hazard Mater 373:85–96
Li X, Zhang D, Liu Z, Lyu C, Niu S, Dong Z, Lyu C (2020) Enhanced catalytic oxidation of benzotriazole via peroxymonosulfate activated by CoFe 2 O 4 supported onto nitrogen-doped three-dimensional graphene aerogels. Chem Eng J 400:125897
Liu L, Mi H, Zhang M, Sun F, Zhan R, Zhao H, He S, Zhou L (2020) Efficient moxifloxacin degradation by CoFe 2 O 4 magnetic nanoparticles activated peroxymonosulfate: Kinetics, pathways and mechanisms. Chem Eng J 407:127201
Lou Y, Ye Z, Chen S, Ye X, Deng Y, Zhang J (2018) Sorption behavior of tetracyclines on suspended organic matters originating from swine wastewater. J Environ Sci 65:144–152
Luo H, Lin Q, Zhang X, Huang Z, Fu H, Xiao R, Liu S (2020) Determining the key factors of nonradical pathway in activation of persulfate by metal-biochar nanocomposites for bisphenol A degradation. Chem Eng J 391:123555
Lv C, Liang H, Chen H, Wu L (2019) Hydroxyapatite supported Co 3 O 4 catalyst for enhanced degradation of organic contaminants in aqueous solution: Synergistic visible-light photo-catalysis and sulfate radical oxidation process. Microchem J 149:103959
Ma Q, Zhang H, Zhang X, Li B, Guo R, Cheng Q, Cheng X (2019) Synthesis of magnetic CuO/MnFe 2 O 4 nanocompisite and its high activity for degradation of levofloxacin by activation of persulfate. Chem Eng J 360:848–860
Matzek LW, Carter KE (2016) Activated persulfate for organic chemical degradation: A review. Chemosphere 151:178–188
Nawaz M, Shahzad A, Tahir K, Kim J, Moztahida M, Jang J, Alam MB, Lee S-H, Jung H-Y, Lee DS (2020) Photo-Fenton reaction for the degradation of sulfamethoxazole using a multi-walled carbon nanotube-NiFe 2 O 4 composite. Chem Eng J 382:123053
Oh W-D, Dong Z, Lim T-T (2016) Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects. Appl Catal B Environ 194:169–201
Ren W, Nie G, Zhou P, Zhang H, Duan X, Wang S (2020a) The intrinsic nature of persulfate activation and n-doping in carbocatalysis. Environ Sci Technol 54:6438–6447
Ren W, Xiong L, Nie G, Zhang H, Duan X, Wang S (2020b) Insights into the electron-transfer regime of peroxydisulfate activation on carbon nanotubes: the role of oxygen functional groups. Environ Sci Technol 54:1267–1275
Ruan X, Xiang Y, Shang C, Cheng S, Liu J, Hao Z, Yang X (2021) Molecular characterization of transformation and halogenation of natural organic matter during the UV/chlorine AOP using FT-ICR mass spectrometry. J Environ Sci 102:24–36
Sahoo S, Sahoo PK, Sharma A, Satpati AK (2020) Interfacial polymerized RGO/MnFe 2 O 4 /polyaniline fibrous nanocomposite supported glassy carbon electrode for selective and ultrasensitive detection of nitrite. Sens Actuators B Chemical 309:127763
Sara R (2014) Antibiotic resistance sweeping developing world. Nature 509:141–142
Song C, Liu H-Y, Guo S, Wang S-G (2020) Photolysis mechanisms of tetracycline under UV irradiation in simulated aquatic environment surrounding limestone. Chemosphere 244:125582
Sun P, Liu H, Feng M, Zhai Z, Fang Y, Zhang X, Sharma VK (2020) Strategic combination of N-doped graphene and g-C 3 N 4 : efficient catalytic peroxymonosulfate-based oxidation of organic pollutants by non-radical-dominated processes. Appl Catal B 272:119005
Tan C, Gao N, Fu D, Deng J, Deng L (2017) Efficient degradation of paracetamol with nanoscaled magnetic CoFe2O4 and MnFe2O4 as a heterogeneous catalyst of peroxymonosulfate. Sep Purif Technol 175:47–57
Tang S, Zhao M, Yuan D, Li X, Zhang X, Wang Z, Jiao T, Wang K (2021) MnFe 2 O 4 nanoparticles promoted electrochemical oxidation coupling with persulfate activation for tetracycline degradation. Sep Purif Technol 255:117690
Tian T, Zhu X, Song Z, Li X, Zhang W, Mao Y, Chen S, Wu J, Ouyang G (2022) The potential of a natural iron ore residue application in the efficient removal of tetracycline hydrochloride from an aqueous solution: insight into the degradation mechanism. Environ Sci Pollut Res 29:76782–76792
Wang Bo, Li Yan-ni, Wang Li (2019) Metal-free activation of persulfates by corn stalk biochar for the degradation of antibiotic norfloxacin: activation factors and degradation mechanism. Chemosphere 237:124454
Wang J, Wang S (2018) Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chem Eng J 334:1502–1517
Wang X, Lian W, Sun X, Ma J, Ning P (2018) Immobilization of NZVI in polydopamine surface-modified biochar for adsorption and degradation of tetracycline in aqueous solution. Front Environ Sci Eng 12:1–11
Wang J, Yue M, Han Y, Xing Xu, Yue Q, Shiping Xu (2020) Highly-efficient degradation of triclosan attributed to peroxymonosulfate activation by heterogeneous catalyst g-C3N4/MnFe2O4. Chem Eng J 391:123554
Xu H, Quan X, Chen L (2019) A novel combination of bioelectrochemical system with peroxymonosulfate oxidation for enhanced azo dye degradation and MnFe 2 O 4 catalyst regeneration. Chemosphere 217:800–807
Yang K, Yue Q, Kong J, Zhao P, Gao Y, Fu K, Gao B (2016) Microbial diversity in combined UAF–UBAF system with novel sludge and coal cinder ceramic fillers for tetracycline wastewater treatment. Chem Eng J 285:319–330
Yin R, Guo W, Wang H, Juanshan D, Qinglian W, Chang J-S, Ren N (2019) Singlet oxygen-dominated peroxydisulfate activation by sludge-derived biochar for sulfamethoxazole degradation through a nonradical oxidation pathway: performance and mechanism. Chem Eng J 357:589–599
Zhang H, Cheng S, Li B, Cheng X, Cheng Q (2018) Fabrication of magnetic Co/BiFeO 3 composite and its advanced treatment of pharmaceutical waste water by activation of peroxysulphate. Sep Purif Technol 202:242–247
Zhang N, Tsang EP, Wang K, Fang J, Li Y, Zhou G, Fang Z (2020a) Iron-nitrogen co-doped carbon nanotubes decorated with Cu 2 O possess enhanced electronic properties for effective peroxymonosulfate activation. Sci Total Environ 764:142813
Zhang T, Zhou T, He L, Xu D, Bai L (2020b) Oxidative degradation of rhodamine B by Ag@CuO nanocomposite activated persulfate. Synth Met 267:116479
Zhang X, Li C, Chen T, Tan Ye, Liu X, Yuan F, Zheng S, Sun Z (2021) Enhanced visible-light-assisted peroxymonosulfate activation over MnFe2O4 modified g-C3N4/diatomite composite for bisphenol A degradation. Int J Min Sci Technol 31:1169–1179
Zhang H, Tong X, Xiao H, Wang H, Zhang M, Xiuguo Lu, Liu Z, Zhou W (2022) Promoting the performance of electrooxidation-PMS system for degradation of tetracycline by introduction of MnFe2O4/CNT as a third-electrode. Sep Purif Technol 294:121171
Zhou Y, Xiao B, Liu S-Q, Meng Z, Chen Z-G, Zou C-Y, Liu C-B, Chen F, Zhou X (2016) Photo-Fenton degradation of ammonia via a manganese–iron double-active component catalyst of graphene–manganese ferrite under visible light. Chem Eng J 283:266–275
Zrinyi N, Pham AL-T (2017) Oxidation of benzoic acid by heat-activated persulfate: effect of temperature on transformation pathway and product distribution. Water Res 120:43–51
Funding
This work was supported by the NSFC (51768019).
Author information
Authors and Affiliations
Contributions
All authors contributed to the study’s conception and design. Material preparation, data collection, and analysis were performed by Huimin Zhang, Xing Tong, and Huoqing Xiao. The first draft of the manuscript was written by Huoqing Xiao, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Ethics approval
Not applicable.
Consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Ricardo A. Torres-Palma
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhang, H., Tong, X., Xiao, H. et al. Utility and mechanism of magnetic nano-MnFe2O4/MWNT activation for oxidative degradation of tetracycline by persulfate. Environ Sci Pollut Res 30, 48999–49013 (2023). https://doi.org/10.1007/s11356-023-25727-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-023-25727-w