MIL-53(Fe)-derived Fe3O4/HNTs/C Composite for Peroxymonosulfate Activation: Degradation Performance and Mechanism of Tetracycline

doi:10.15541/jim20260088

Abstract

Abstract: Fe₃O₄ is widely used as a heterogeneous catalyst in persulfate advanced oxidation technology due to its abundant availability and low cost. However, the inevitable agglomeration of nano-Fe₃O₄ severely restricts its catalytic activity and stability. In this study, halloysite nanotubes (HNTs) were employed as the carrier, and MIL-53(Fe) precursors were grown in-situ on the outer surface of HNTs via a solvothermal method, followed by calcination under an inert atmosphere to prepare MIL-53(Fe)-derived Fe₃O₄/HNTs/C composites. The performance and mechanism of Fe₃O₄/HNTs/C in activating peroxymonosulfate (PMS) for tetracycline (TC) degradation were systematically investigated. The results showed that the degradation efficiency of TC by Fe₃O₄/HNTs/C activating PMS reached 89.66%, which was 8.37% higher than that of the physically mixed sample of Fe₃O₄/C and HNTs. The Fe₃O₄/HNTs/C+PMS system maintained a TC degradation efficiency above 82% over a wide pH range of 3 to 11, and achieved a degradation efficiency of over 60% in both tap water and simulated seawater matrices. After 5 cycles, the degradation efficiency remained above 80%, demonstrating excellent stability and reusability. Free radical scavenging experiments and electron paramagnetic resonance tests confirmed that ·SO₄^-, ·OH, ·O₂^-, and ¹O₂ were involved in the degradation of TC, among which ·O₂^- played a dominant role. Furthermore, the possible intermediates and the potential degradation pathways of TC were explored. Toxicity evaluation indicated that the acute toxicity, mutagenicity, and developmental toxicity of the intermediates were generally lower than those of TC, effectively reducing the environmental risk.

Key words: halloysite, magnetite, advanced oxidation, peroxymonosulfate, tetracycline

CLC Number:

LEI Xinyu, WU Limei, WANG Xiaolong, CHEN Siquan, NIU Mengmeng, HU Chenkai, WANG Wei, TANG Ning. MIL-53(Fe)-derived Fe₃O₄/HNTs/C Composite for Peroxymonosulfate Activation: Degradation Performance and Mechanism of Tetracycline[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260088.

References

[1] HUANG Y H, CAI J S, YE Z L,et al. Morphological crystal adsorbing tetracyclines and its interaction with magnesium ion in the process of struvite crystallization by using synthetic wastewater. Water Research, 2022, 215: 118253.
[2] ZHENG H S, HOU Y Y, LI S,et al. Study on catalytic mechanisms of Fe₃O₄-rGO_x in three typical advanced oxidation processes for tetracycline hydrochloride degradation. Chinese Chemical Letters, 2023, 34(1): 107253.
[3] GUSAIN R, GUPTA K, JOSHI P,et al. Adsorptive removal and photocatalytic degradation of organic pollutants using metal oxides and their composites: a comprehensive review. Advances in Colloid and Interface Science, 2019, 272: 102009.
[4] XIAO Y, JIANG Y H, WANG Q Y,et al. Hydrophobic recoverable flower-like ZnIn₂S₄/Sn₃O₄ as photocatalytic heterostructure for efficient photocatalytic hydrogen production and sewage decontamination. Journal of Environmental Chemical Engineering, 2025, 13(6): 119806.
[5] MAO J S, HONG W, LI Q,et al. The application strategies and progresses of silicon-based minerals in advanced oxidation processes for water decontamination. Coordination Chemistry Reviews, 2024, 511: 215871.
[6] DAI M, NIU Q Y, WU S H,et al. Hydroxyl radicals in ozone-based advanced oxidation of organic contaminants: a review. Environmental Chemistry Letters, 2024, 22(6): 3059.
[7] SUN N, CHEN J, ZHANG Z L,et al. A bifurcated dendritic SrCO₃-TiO₂/CdS heterostructure with oxygen vacancy for boosting photocatalytic 2e- ORR of H₂O₂ production and simultaneous antibiotic degradation: synergy and mechanism insight. Fuel, 2025, 386: 134185.
[8] ZHANG S J, ZOU Y L, CHEN J,et al. Interfacial modulation of superior visible-light responsive CdIn₂S₄/Sn₃O₄ photocatalysts for wastewater purification. Journal of Water Process Engineering, 2025, 69: 106729.
[9] LI Y P, ZHOU Y B, ZHOU Y.Ultrasonic enhancement of persulfate oxidation system governs emerging pollutants decontamination.Green Energy & Environment, 2024, 9(11): 1666.
[10] CHENG S X, LIANG J, CHENG Z W,et al. Persulfate activation by inherent soil constituents for sulfamethoxazole degradation: synergistic roles of iron minerals and organic matter. Chemical Engineering Journal, 2025, 517: 164357.
[11] SUN W, WANG S, YU Z C,et al. Characteristics and application of iron-based materials in heterogeneous Fenton oxidation for wastewater treatment: a review. Environmental Science: Water Research & Technology, 2023, 9(5): 1266.
[12] XIAO S, ZHANG L N, ZHOU L,et al. The long-term effect of Fe₃O₄ in activating persulfate to degrade refractory organic contaminants for groundwater remediation. Chemical Engineering Journal, 2024, 482: 148801.
[13] CAO C, GUO Y J, CHEN D D,et al. A MOF-derived Fe₃O₄/Fe⁰/Fe₃C-2-600 dual-cathode electro-Fenton system construction: revealing the mechanism for active centers linked by Fe⁰ as an electronic transfer station for enhancing Fenton reaction. Chemical Engineering Journal, 2025, 507: 160710.
[14] HE Z G, LIU Y Q, WANG J L,et al. Enhanced degradation of old landfill leachate in heterogeneous electro-Fenton catalyzed using Fe₃O₄ nano-particles encapsulated by metal organic frameworks. Journal of Cleaner Production, 2021, 321: 128947.
[15] LIU T, WANG Q, LI C X,et al. Synthesizing and characterizing Fe₃O₄ embedded in N-doped carbon nanotubes-bridged biochar as a persulfate activator for sulfamethoxazole degradation. Journal of Cleaner Production, 2022, 353: 131669.
[16] ZHU K, BIN Q, SHEN Y Q,et al. In-situ formed N-doped bamboo-like carbon nanotubes encapsulated with Fe nanoparticles supported by biochar as highly efficient catalyst for activation of persulfate (PS) toward degradation of organic pollutants. Chemical Engineering Journal, 2020, 402: 126090.
[17] HE P, XIONG Y, CHEN Y Z,et al. One-step synthesis of natural montmorillonite/hematite composites with enhanced persulfate catalytic activity for sulfamethoxazole degradation: efficiency, kinetics, and mechanism. Environmental Research, 2022, 204: 112326.
[18] NIVEDITHA S V, GANDHIMATHI R.Flyash augmented Fe₃O₄ as a heterogeneous catalyst for degradation of stabilized landfill leachate in Fenton process.Chemosphere, 2020, 242: 125189.
[19] ZHAO M, LIU P.Halloysite nanotubes/polystyrene (HNTs/PS) nanocompositesvia in situ bulk polymerization. Journal of Thermal Analysis and Calorimetry, 2008, 94(1): 103.
[20] DE ABREU PEREIRA V, DOS SANTOS PAZ I, GOMES A L,et al. Effects of acid activation on the halloysite nanotubes for curcumin incorporation and release. Applied Clay Science, 2021, 200: 105953.
[21] PASBAKHSH P, CHURCHMAN G J, KEELING J L.Characterisation of properties of various halloysites relevant to their use as nanotubes and microfibre fillers.Applied Clay Science, 2013, 74: 47.
[22] DEB A K, HASSAN M, BISWAS B,et al. Functionalization of halloysite nanotubes as remediation agents for organic and inorganic contaminants: insights into synthesis routes, removal techniques, and eco-friendly perspectives. Science of the Total Environment, 2025, 989: 179771.
[23] HUANG Z F, LIN Q T, CAI N,et al. Coexistence of free radical and nonradical mechanisms for triclosan degradation by CuO/HNTs. Separation and Purification Technology, 2021, 276: 119318.
[24] PRIYADARSHINI M, AHMAD A, GHANGREKAR M M.Efficient upcycling of iron scrap and waste polyethylene terephthalate plastic into Fe₃O₄@C incorporated MIL-53(Fe) as a novel electro-Fenton catalyst for the degradation of salicylic acid.Environmental Pollution, 2023, 322: 121242.
[25] WU H D, ZHANG J H, ZHOU Z H.Effect of heat treatment on structure, morphology and surface properties of halloysite.IOP Conference Series: Materials Science and Engineering, 2019, 678(1): 012111.
[26] HAMZA H, FERRETTI A M, INNOCENTI C,et al. An approach for magnetic halloysite nanocomposite with selective loading of superparamagnetic magnetite nanoparticles in the lumen. Inorganic Chemistry, 2020, 59(17): 12086.
[27] LIU N, WANG J L, WU J X,et al. Magnetic Fe₃O₄@MIL-53(Fe) nanocomposites derived from MIL-53(Fe) for the photocatalytic degradation of ibuprofen under visible light irradiation. Materials Research Bulletin, 2020, 132: 111000.
[28] PENG K, WAN P F, WANG H J,et al. Unraveling the morphology effect of kandite supporting MoS₂ nanosheets for enhancing electrocatalytic hydrogen evolution. Applied Clay Science, 2021, 212: 106211.
[29] WANG G S, GENG J H, QI X W,et al. Rheological performances and enhanced sedimentation stability of mesoporous Fe₃O₄ nanospheres in magnetorheological fluid. Journal of Molecular Liquids, 2021, 336: 116389.
[30] ZHANG W Y, WANG L, SU Y G,et al. Indium oxide/Halloysite composite as highly efficient adsorbent for tetracycline removal: key roles of hydroxyl groups and interfacial interaction. Applied Surface Science, 2021, 566: 150708.
[31] SONG H R, YAN L X, WANG Y W,et al. Electrochemically activated PMS and PDS: radical oxidation versus nonradical oxidation. Chemical Engineering Journal, 2020, 391: 123560.
[32] ZHANG W Y, YAN X, LIU Z L,et al. Halloysite nanotubes supported copper oxide composites used as efficient catalysts for bisphenol A removal. Applied Clay Science, 2022, 224: 106509.
[33] WANG Q, LIU H B, ZHAI P X,et al. Utilization of methylene blue-adsorbed halloysite after carbonization to activate peroxymonosulfate degrading phenol: performance and mechanism. Chemosphere, 2022, 305: 135326.
[34] ZHANG Y Q, LI Y X, BI H L,et al. Nanomanganese cobaltate-decorated halloysite nanotubes for the complete degradation of ornidazole via peroxymonosulfate activation. Journal of Colloid and Interface Science, 2023, 630: 855.
[35] SONG J B, ZHANG Q Y, GUO H L,et al. Unraveling the mechanism and the key role of amorphous structure C-O-Fe in tetracycline degradation by activation of persulfate in lotus leaf-based red mud-modified biochar. Chemical Engineering Journal, 2024, 499: 156078.
[36] HUO B J, MENG F Q, YANG J W,et al. High efficiently piezocatalysis degradation of tetracycline by few-layered MoS₂/GDY: mechanism and toxicity evaluation. Chemical Engineering Journal, 2022, 436: 135173.
[37] GUO T, JIANG L S, WANG K,et al. Efficient persulfate activation by hematite nanocrystals for degradation of organic pollutants under visible light irradiation: facet-dependent catalytic performance and degradation mechanism. Applied Catalysis B: Environmental, 2021, 286: 119883.
[38] XIN S S, HUO S Y, XIN Y J,et al. Heterogeneous photo-electro-Fenton degradation of tetracycline through nitrogen/oxygen self-doped porous biochar supported CuFeO₂ multifunctional cathode catalyst under visible light. Applied Catalysis B: Environmental, 2022, 312: 121442.
[39] XIN S S, HUO S Y, ZHANG C L,et al. Coupling nitrogen/oxygen self-doped biomass porous carbon cathode catalyst with CuFeO₂/biochar particle catalyst for the heterogeneous visible-light driven photo-electro-Fenton degradation of tetracycline. Applied Catalysis B: Environmental, 2022, 305: 121024.

MIL-53(Fe)-derived Fe₃O₄/HNTs/C Composite for Peroxymonosulfate Activation: Degradation Performance and Mechanism of Tetracycline

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LI Jianjun, CHEN Fangming, ZHANG Lili, WANG Lei, ZHANG Liting, CHEN Huiwen, XUE Changguo, XU Liangji. Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic [J]. Journal of Inorganic Materials, 2025, 40(4): 440-448.
[2]	CAO Qingqing, CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi. Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂ [J]. Journal of Inorganic Materials, 2024, 39(7): 787-792.
[3]	CAI Heqing, HAN Lu, YANG Songsong, XUE Xinyu, ZHANG Kou, SUN Zhicheng, LIU Ruping, HU Kun, WEI Yan. Fe₃O₄-DMSA-PEI Magnetic Nanoparticles with Small Particle Size: Preparation and Gene Loading [J]. Journal of Inorganic Materials, 2024, 39(5): 517-524.
[4]	WANG Zhaoyang, QIN Peng, JIANG Yin, FENG Xiaobo, YANG Peizhi, HUANG Fuqiang. Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation [J]. Journal of Inorganic Materials, 2024, 39(4): 383-389.
[5]	YE Maosen, WANG Yao, XU Bing, WANG Kangkang, ZHANG Shengnan, FENG Jianqing. II/Z-type Bi₂MoO₆/Ag₂O/Bi₂O₃ Heterojunction for Photocatalytic Degradation of Tetracycline under Visible Light Irradiation [J]. Journal of Inorganic Materials, 2024, 39(3): 321-329.
[6]	GUO Chunxia, CHEN Weidong, YAN Shufang, ZHAO Xueping, YANG Ao, MA Wen. Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material [J]. Journal of Inorganic Materials, 2023, 38(5): 529-536.
[7]	WANG Lei, LI Jianjun, NING Jun, HU Tianyu, WANG Hongyang, ZHANG Zhanqun, WU Linxin. Enhanced Degradation of Methyl Orange with CoFe₂O₄@Zeolite Catalyst as Peroxymonosulfate Activator: Performance and Mechanism [J]. Journal of Inorganic Materials, 2023, 38(4): 469-476.
[8]	WEI Xin, LU Zhanhui, WANG Luping, FANG Ming. Mechanism Study of Tetracycline High Efficient Photodegradation by Bi₂WO₆ Nanosheets under Visible Light Irradiation [J]. Journal of Inorganic Materials, 2020, 35(3): 324-328.
[9]	QIN Shi-Lin, LI Ji-Cheng, LI Zhao-Hui, HU Zhong-Liang, DING Yan-Huai, LEI Gang-Tie, XIAO Qi-Zhen. Ferric Oxide-reduced Graphene Oxide Composite Material: Synthesis Based on Covalent Binding and Its Lithium-storage Property [J]. Journal of Inorganic Materials, 2018, 33(7): 741-748.
[10]	SUN Qing, QI Qi, ZHANG Jian, PAN Fang-Zhen, SHENG Jia-Wei. Structure and Adsorption Property of Magnetic ZnFe₂O₄-halloysite Composite Material [J]. Journal of Inorganic Materials, 2018, 33(4): 390-396.
[11]	LI Yong-Sheng, CHEN Ling. Controlled Synthesis of Gold-based Magnetic Nanocomposites and Their Catalytic Performance [J]. Journal of Inorganic Materials, 2018, 33(2): 221-228.
[12]	CHEN Meng-Qiu, CHEN Yun, SHU Zhu, WANG Yu, WU Hong-Juan, GUO Li-Min. Template-free Synthesis of Mesoporous Silica with High Specific Surface Area from Natural Halloysite and Its Application in Methylene Blue Adsorption [J]. Journal of Inorganic Materials, 2018, 33(12): 1365-1370.
[13]	LI Min, LUO Yuan, XU Wei-Jia, LIU Jia-Xiang. DMFC Anode Catalyst Fe₃O₄@Pt Particles: Synthesis and Catalytic Performanc [J]. Journal of Inorganic Materials, 2017, 32(9): 916-922.
[14]	LIU Ke, WANG Ji-Tong, LONG Dong-Hui, LING Li-Cheng. Scalable Preparation and Microwave Absorption of Lightweight Fe₃O₄/Mesoporous Carbon Microsphere Composites [J]. Journal of Inorganic Materials, 2017, 32(10): 1023-1028.
[15]	ZHAI Yun-Gang, DONG Wen-Jie, GAO Yong-Ping, NIU De-Chao, CHEN Jian-Zhuang, GU Jin-Lou, LI Yong-Sheng, SHI Jian-Lin. Preparation of Superparamagnetic Gold Nanocomposites with Different Diameters and Their Imaging and Therapy Applications [J]. Journal of Inorganic Materials, 2015, 30(9): 950-956.