Comparative studies on Fenton-like reactions catalyzed by Fe₃O₄ loaded inside and outside halloysite nanotubes for the removal of organic pollutants

Abstract

In this work, Fe₃O₄ nanoparticles (NPs) loaded inside and outside halloysite nanotubes (HNTs) were prepared and developed as the heterogeneous Fenton-like catalysts for the removal of representative organic pollutants. Characterization results indicated that the samples with Fe₃O₄ NPs loaded outside the HNTs lumen (Fe₃O₄/HNTs) and inside the HNTs lumen (Fe₃O₄@HNTs) were successfully prepared. Both samples had typical magnetic hysteresis loops, while Fe₃O₄@HNTs exhibited higher magnetization intensity. The comparative experiments showed that Fe₃O₄@HNTs had better Fenton-like catalytic ability than that of Fe₃O₄/HNTs in the degradation of various organic pollutants. Taking Rhodamine B (RhB) as an example, the adsorption thermodynamics and kinetics of RhB onto Fe₃O₄/HNTs and Fe₃O₄@HNTs were also investigated. The comparative results demonstrated that the adsorption ability of Fe₃O₄/HNTs was better than that of Fe₃O₄@HNTs. Moreover, the dissolved concentration of Fe²⁺ and production amount of hydroxyl radical (·OH) in the Fe₃O₄@HNTs-H₂O₂ system were significantly higher than those in the Fe₃O₄/HNTs-H₂O₂ system. Based on aforementioned comparison, the nano-confinement effect in the Fe₃O₄@HNTs-H₂O₂ system was verified. This work provides meaningful guidance for the cheap and convenient design of nanoreactors for Fenton-like applications.

Graphical abstract

Keywords

Fe ₃O ₄ / halloysite nanotube / adsorption / Fenton-like reaction / mechanism

References

[1] Wang J L, Tang J T . Fe-based Fenton-like catalysts for water treatment: catalytic mechanisms and applications.Journal of Molecular Liquids, 2021, 332: 115755

[2] Tang Y, Liu Y, Chen Y, . A review: research progress on microplastic pollutants in aquatic environments.Science of the Total Environment, 2021, 766: 142572

[3] Lu F, Astruc D . Nanocatalysts and other nanomaterials for water remediation from organic pollutants.Coordination Chemistry Reviews, 2020, 408: 213180

[4] Liu L M, Chen Z, Zhang J W, . Treatment of industrial dye wastewater and pharmaceutical residue wastewater by advanced oxidation processes and its combination with nanocatalysts: a review.Journal of Water Process Engineering, 2021, 42: 102122

[5] Lai C J, He T Q, Li X W, . Catalytic wet air oxidation of phenols over porous plate Cu-based catalysts.Applied Clay Science, 2019, 181: 105253

[6] Palas B, Ersöz G, Atalay S . Bioinspired metal oxide particles as efficient wet air oxidation and photocatalytic oxidation catalysts for the degradation of acetaminophen in aqueous phase.Ecotoxicology and Environmental Safety, 2019, 182: 109367

[7] Chen X, Teng W, Fan J, . Enhanced degradation of micropollutants over iron-based electro-Fenton catalyst: cobalt as an electron modulator in mesochannels and mechanism insight.Journal of Hazardous Materials, 2022, 427: 127896

[8] Xiao F, Wang Z, Fan J, . Selective electrocatalytic reduction of oxygen to hydroxyl radicals via 3-electron pathway with FeCo alloy encapsulated carbon aerogel for fast and complete removing pollutants.Angewandte Chemie International Edition, 2021, 60(18): 10375–10383

[9] Hu X, Hu X J, Peng Q Q, . Mechanisms underlying the photocatalytic degradation pathway of ciprofloxacin with heterogeneous TiO₂.Chemical Engineering Journal, 2020, 380: 122366

[10] Shi H, Liu Y, Bai Y, . Progress in defect engineering strategies to enhance piezoelectric catalysis for efficient water treatment and energy regeneration.Separation and Purification Technology, 2024, 330(A): 125247

[11] Chen H, Wang J . Degradation and mineralization of ofloxacin by ozonation and peroxone (O₃/H₂O₂) process.Chemosphere, 2021, 269: 128775

[12] Tian S Q, Qi J Y, Wang Y P, . Heterogeneous catalytic ozonation of atrazine with Mn-loaded and Fe-loaded biochar.Water Research, 2021, 193: 116860

[13] Van H T, Nguyen L H, Hoang T K, . Heterogeneous Fenton oxidation of paracetamol in aqueous solution using iron slag as a catalyst: degradation mechanisms and kinetics.Environmental Technology & Innovation, 2020, 18: 100670

[14] Kumar A, Rana A, Sharma G, . Recent advances in nano-Fenton catalytic degradation of emerging pharmaceutical contaminants.Journal of Molecular Liquids, 2019, 290: 111177

[15] Wang M, Mei Y, Chen S L, . Porous N-doped carbon nanospheres with encapsulated cobalt nanocrystals for persulfate activation to degrade tetracycline.Ceramics International, 2022, 48(19): 27622–27630

[16] Hu Z H, Guo B Y, Wu H Q, . Activation of Na₂S₂O₈ by MIL-101(Fe)/MoS₂ composite for the degradation of tetracycline with visible light assistance.Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 654: 130202

[17] Wang J, Tang J . Fe-based Fenton-like catalysts for water treatment: preparation, characterization and modification.Chemosphere, 2021, 276: 130177

[18] Jain B, Singh A K, Kim H, . Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes.Environmental Chemistry Letters, 2018, 16(3): 947–967

[19] Yang S J, He H P, Wu D Q, . Decolorization of methylene blue by heterogeneous Fenton reaction using Fe_3−xTi_xO₄ (0 ≤ x ≤ 0.78) at neutral pH values.Applied Catalysis B: Environmental, 2009, 89(3–4): 527–535

[20] Huang R X, Fang Z Q, Yan X M, . Heterogeneous sono-Fenton catalytic degradation of bisphenol A by Fe₃O₄ magnetic nanoparticles under neutral condition.Chemical Engineering Journal, 2012, 197: 242–249

[21] Xue X F, Hanna K, Despas C, . Effect of chelating agent on the oxidation rate of PCP in the magnetite/H₂O₂ system at neutral pH.Journal of Molecular Catalysis A: Chemical, 2009, 311(1–2): 29–35

[22] Tao Q, Bi J, Huang X, . Fabrication, application, optimization and working mechanism of Fe₂O₃ and its composites for contaminants elimination from wastewater.Chemosphere, 2021, 263: 127889

[23] Yang S T, Zhang W, Xie J R, . Fe₃O₄@SiO₂ nanoparticles as a high-performance Fenton-like catalyst in a neutral environment.RSC Advances, 2015, 5(7): 5458–5463

[24] Shao Y M, Zhou L C, Bao C, . A facile approach to the fabrication of rattle-type magnetic carbon nanospheres for removal of methylene blue in water.Carbon, 2015, 89: 378–391

[25] Deng J H, Wen X H, Wang Q N . Solvothermal in situ synthesis of Fe₃O₄‒multi-walled carbon nanotubes with enhanced heterogeneous Fenton-like activity.Materials Research Bulletin, 2012, 47(11): 3369–3376

[26] Massaro M, Noto R, Riela S . Past, present and future perspectives on halloysite clay minerals.Molecules, 2020, 25(20): 4863

[27] Joussein E, Petit S, Churchman J, . Halloysite clay minerals: a review.Clay Minerals, 2005, 40(4): 383–426

[28] Idumah C I, Hassan A, Ogbu J, . Recently emerging advancements in halloysite nanotubes polymer nanocomposites.Composite Interfaces, 2019, 26(9): 751–824

[29] Massaro M, Lazzara G, Noto R, . Halloysite nanotubes: a green resource for materials and life sciences.Rendiconti Lincei: Scienze Fisiche e Naturali, 2020, 31(2): 213–221

[30] Yuan P, Tan D, Annabi-Bergaya F . Properties and applications of halloysite nanotubes: recent research advances and future prospects.Applied Clay Science, 2015, 112: 75–93

[31] Goda E S, Gab-Allah M A, Singu B S, . Halloysite nanotubes based electrochemical sensors: a review.Microchemical Journal, 2019, 147: 1083–1096

[32] Danyliuk N, Tomaszewska J, Tatarchuk T . Halloysite nanotubes and halloysite-based composites for environmental and biomedical applications.Journal of Molecular Liquids, 2020, 309: 113077

[33] Vergaro V, Abdullayev E, Lvov Y M, . Cytocompatibility and uptake of halloysite clay nanotubes.Biomacromolecules, 2010, 11(3): 820–826

[34] Yah W O, Xu H, Soejima H, . Biomimetic dopamine derivative for selective polymer modification of halloysite nanotube lumen.Journal of the American Chemical Society, 2012, 134(29): 12134–12137

[35] Bugatti V, Sorrentino A, Gorrasi G . Encapsulation of Lysozyme into halloysite nanotubes and dispersion in PLA: structural and physical properties and controlled release analysis.European Polymer Journal, 2017, 93: 495–506

[36] Xu H Y, Wang Y, Shi T N, . Heterogeneous Fenton-like discoloration of methyl orange using Fe₃O₄/MWCNTs as catalyst: kinetics and Fenton-like mechanism.Frontiers of Materials Science, 2018, 12(1): 34–44

[37] Lee J K, Walker K L, Han H S, . Spontaneous generation of hydrogen peroxide from aqueous microdroplets.Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(39): 19294–19298

[38] Zhang R, Bao S, Tan Q, . Facile synthesis of a rod-like porous carbon framework confined magnetite nanoparticle composite for superior lithium-ion storage.Journal of Colloid and Interface Science, 2021, 600: 602–612

[39] Jia R, Zhang R, Yu L, . Engineering a hierarchical carbon supported magnetite nanoparticles composite from metal organic framework and graphene oxide for lithium-ion storage.Journal of Colloid and Interface Science, 2023, 630(Pt B): 86–98

[40] Xu H Y, Li B, Han X, . Synergic enhancement of the anticorrosion properties of an epoxy coating by compositing with both graphene and halloysite nanotubes.Journal of Applied Polymer Science, 2019, 136(21): 47562

[41] Wang Q, Zhang J, Wang A . Alkali activation of halloysite for adsorption and release of ofloxacin.Applied Surface Science, 2013, 287: 54–61

[42] Wang L, Chen J L, Ge L, . Halloysite-nanotube-supported Ru nanoparticles for ammonia catalytic decomposition to produce CO_x-free hydrogen.Energy & Fuels, 2011, 25(8): 3408–3416

[43] Wang W S, Xu H Y, Li B, . Preparation, catalytic efficiency and mechanism of Fe₃O₄/HNTs heterogeneous Fenton-like catalyst.Materials Today: Communications, 2023, 36: 106821

[44] Fuentes-Pérez M, Sotelo-Lerma M, Fuentes-Ríos J L, . Synthesis and study of physicochemical properties of Fe₃O₄@ZnFe₂O₄ core/shell nanoparticles.Journal of Materials Science: Materials in Electronics, 2021, 32(12): 16786–16799

[45] Xu H Y, Li B, Shi T N, . Nanoparticles of magnetite anchored onto few-layer graphene: a highly efficient Fenton-like nanocomposite catalyst.Journal of Colloid and Interface Science, 2018, 532: 161–170

[46] Wang C F, Pan X L, Bao X H . Direct production of light olefins from syngas over a carbon nanotube confined iron catalyst.Chinese Science Bulletin, 2010, 55(12): 1117–1119

[47] Cheng Y, Tan R Q, Wang W Y, . Controllable synthesis and magnetic properties of Fe₃O₄ and Fe₃O₄@SiO₂ microspheres.Journal of Materials Science, 2010, 45(19): 5347–5352

[48] Zhang J, Müller J O, Zheng W, . Individual Fe–Co alloy nanoparticles on carbon nanotubes: structural and catalytic properties.Nano Letters, 2008, 8(9): 2738–2743

[49] Santiso E E, Kostov M K, George A M, . Confinement effects on chemical reactions — toward an integrated rational catalyst design.Applied Surface Science, 2007, 253(13): 5570–5579

[50] Bao S, Tu M, Huang H, . Heterogeneous iron oxide nanoparticles anchored on carbon nanotubes for high-performance lithium-ion storage and fenton-like oxidation.Journal of Colloid and Interface Science, 2021, 601: 283–293

[51] Egbosiuba T C, Abdulkareem A S, Kovo A S, . Ultrasonic enhanced adsorption of methylene blue onto the optimized surface area of activated carbon: adsorption isotherm, kinetics and thermodynamics.Chemical Engineering Research & Design, 2020, 153: 315–336

[52] Chen S, Qin C X, Wang T, . Study on the adsorption of dyestuffs with different properties by sludge-rice husk biochar: adsorption capacity, isotherm, kinetic, thermodynamics and mechanism.Journal of Molecular Liquids, 2019, 285: 62–74

[53] Lu M C, Chen J N, Huang H H . Role of goethite dissolution in the oxidation of 2-chlorophenol with hydrogen peroxide.Chemosphere, 2002, 46(1): 131–136

[54] Wang J, Guo X . Adsorption kinetic models: physical meanings, applications, and solving methods.Journal of Hazardous Materials, 2020, 390: 122156

[55] Wan Z, Wang J . Degradation of sulfamethazine antibiotics using Fe₃O₄–Mn₃O₄ nanocomposite as a Fenton-like catalyst.Journal of Chemical Technology and Biotechnology, 2017, 92(4): 874–883

[56] Chen W, Fan Z, Pan X, . Effect of confinement in carbon nanotubes on the activity of Fischer–Tropsch iron catalyst.Journal of the American Chemical Society, 2008, 130(29): 9414–9419

[57] Pan X, Bao X . The effects of confinement inside carbon nanotubes on catalysis.Accounts of Chemical Research, 2011, 44(8): 553–562

[58] Zhang S, Sun M, Hedtke T, . Mechanism of heterogeneous Fenton reaction kinetics enhancement under nanoscale spatial confinement.Environmental Science & Technology, 2020, 54(17): 10868–10875

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