Abstract
Octavinyl polyhedral oligomeric silsesquioxane (POSS) was polymerized on the surface of Fe3O4 nanoparticles (NPs) and then the NPs were functionalized with carboxylic acid groups using thiol-ene click reactions with thioglycolic acid. The as-prepared Fe3O4@POSS-COOH magnetic hybrid NPs had mesoporous structures with an average particle diameter of 15 nm and a relatively high specific surface area of 447 m2·g−1. Experimental results showed that 4 mg of Fe3O4@POSS-COOH NPs efficiently adsorbed and removed methylene blue from water at 5 min. This is due to the presence of both carboxylic acid and pendant vinyl groups on the Fe3O4@POSS-COOH NPs. These NPs could be easily withdrawn from water within a few seconds under moderate magnetic field and showed high stability in acid and alkaline aqueous mediums.
Similar content being viewed by others
References
Kaşgöz H, Durmus A. Dye removal by a novel hydrogel-clay nanocomposite with enhanced swelling properties. Polymers for Advanced Technologies, 2008, 19(7): 838–845
Rafatullah M, Sulaiman O, Hashim R, Ahmad A. Adsorption of methylene blue on low-cost adsorbents: A review. Journal of Hazardous Materials, 2010, 177(1): 70–80
Dai M, Li H X, Lang J P. New approaches to the degradation of organic dyes, and nitro- and chloroaromatics using coordination polymers as photocatalysts. CrystEngComm, 2015, 17(26): 4741–4753
Wu X Y, Qi H X, Ning J J, Wang J F, Ren Z G, Lang J P. One silver (I)/tetraphosphine coordination polymer showing good catalytic performance in the photodegradation of nitroaromatics in aqueous solution. Applied Catalysis B: Environmental, 2015, 168: 98–104
Wu B, Zhang W H, Ren Z G, Lang J P A. 1D anionic coordination polymer showing superior Congo red sorption and its dye composite exhibiting remarkably enhanced photocurrent response. Chemical Communications, 2015, 51(80): 14893–14896
Zhang Y, Tang Z R, Fu X, Xu Y J. TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant: Is TiO2-graphene truly different from other TiO2-carbon composite materials? ACS Nano, 2010, 4(12): 7303–7314
Shi Y X, Li W X, Chen H H, Young D J, Zhang W H, Lang J P. A crystalline zinc (ii) complex showing hollow hexagonal tubular morphology evolution, selective dye absorption and unique response to UV irradiation. Chemical Communications, 2017, 53 (40): 5515–5518
Wang F, Li F L, Xu M M, Yu H, Zhang J G, Xia H T, Lang J P. Facile synthesis of a Ag (I)-doped coordination polymer with enhanced catalytic performance in the photodegradation of azo dyes in water. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(11): 5908–5916
Lü C N, Chen M M, Zhang W H, Li D X, Dai M, Lang J P. Construction of Zn (ii) and Cd (ii) metal-organic frameworks of diimidazole and dicarboxylate mixed ligands for the catalytic photodegradation of rhodamine B in water. CrystEngComm, 2015, 17(9): 1935–1943
Liu D, Lang F F, Zhou X, Ren Z G, Young D J, Lang J P. A cationic coordination polymer and its orange II anion-exchanged products: Isolation, structural characterization, photocurrent responses, and dielectric properties. Inorganic Chemistry, 2017, 56(20): 12542–12550
Sekar S, Surianarayanan M, Ranganathan V, MacFarlane D R, Mandal A B. Choline-based ionic liquids-enhanced biodegradation of azo dyes. Environmental Science & Technology, 2012, 46(9): 4902–4908
Salem I A, El-Maazawi M S. Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces. Chemosphere, 2000, 41(8): 1173–1180
Riera-Torres M, Gutiérrez-Bouzán C, Crespi M. Combination of coagulation-flocculation and nanofiltration techniques for dye removal and water reuse in textile effluents. Desalination, 2010, 252(1): 53–59
Labanda J, Sabaté J, Llorens J. Experimental and modeling study of the adsorption of single and binary dye solutions with an ion-exchange membrane adsorber. Chemical Engineering Journal, 2011, 166(2): 536–543
Fan Y, Liu H J, Zhang Y, Chen Y. Adsorption of anionic MO or cationic MB from MO/MB mixture using polyacrylonitrile fiber hydrothermally treated with hyperbranched polyethylenimine. Journal of Hazardous Materials, 2015, 283: 321–328
Kolya H, Tripathy T. Hydroxyethyl starch-g-poly-(N, N-dimethylacrylamide-co-acrylic acid): An efficient dye removing agent. European Polymer Journal, 2013, 49(12): 4265–4275
Li L, Hu N, Ding D, Xin X, Wang Y, Xue J, Zhang H, Tan Y. Adsorption and recovery of U (VI) from low concentration uranium solution by amidoxime modified Aspergillus niger. RSC Advances, 2015, 5(81): 65827–65839
Manos M J, Kanatzidis M G. Layered metal sulfides capture uranium from seawater. Journal of the American Chemical Society, 2012, 134(39): 16441–16446
Cotin G, Piant S, Mertz D, Felder-Flesch D, Begin-Colin S. Iron Oxide Nanoparticles for Biomedical Applications: Synthesis, Functionalization, and Application. In: Iron Oxide Nanoparticles for Biomedical Applications. Amsterdam: Elsevier, 2018, 43–88
Chen C L, Siow T Y, Chou C H, Lin C H, Lin M H, Chen Y C, Hsieh W Y, Wang S J, Chen C. Targeted superparamagnetic iron oxide nanoparticles for in vivo magnetic resonance imaging of T-cells in rheumatoid arthritis. Molecular Imaging & Biology, 2017, 19(2): 233–44
Eftekhari-Sis B, Akbari M, Akbari A, Amini M. Vanadium (V) and tungsten (VI) oxoperoxo-complexes anchored on Fe3O4 magnetic nanoparticles: Versatile and efficient catalysts for the oxidation of alcohols and sulfides. Catalysis Letters, 2017, 147(8): 2106–2115
Chen H, Deng C, Zhang X. Synthesis of Fe3O4@SiO2@PMMA core-shell-shell magnetic microspheres for highly efficient enrichment of peptides and proteins for MALDI-ToF MS analysis. Angewandte Chemie International Edition, 2010, 49(3): 607–611
Park M, Seo S, Lee I S, Jung J H. Ultraefficient separation and sensing of mercury and methylmercury ions in drinking water by using aminonaphthalimide-functionalized Fe3O4@SiO2 core/shell magnetic nanoparticles. Chemical Communications, 2010, 46(25): 4478–4480
Kresge C, Leonowicz M, Roth W, Vartuli J, Beck J. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature, 1992, 359(6397): 710–712
Wu G, Chen L, Liu L. Direct grafting of octamaleamic acid-polyhedral oligomeric silsesquioxanes onto the surface of carbon fibers and the effects on the interfacial properties and anti-hydrothermal aging behaviors of silicone resin composites. Journal of Materials Science, 2017, 52(2): 1057–1070
Hojiyev R, Ulcay Y, Hojamberdiev M, Çelik M S, Carty W M. Hydrophobicity and polymer compatibility of POSS-modified Wyoming Na-montmorillonite for developing polymer-clay nano-composites. Journal of Colloid and Interface Science, 2017, 497: 393–401
Cordes D B, Lickiss P D, Rataboul F. Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chemical Reviews, 2010, 110(4): 2081–173
Kuo S W, Chang F C. POSS related polymer nanocomposites. Progress in Polymer Science, 2011, 36(12): 1649–1696
Lu T L, Liang G Z, Kou K C, Guo Z A. Review synthesis and characterization of cage octa (cyclohexylsilsesquioxane). Journal of Materials Science, 2005, 40(18): 4721–4726
Zhang L, Abbenhuis H C, Yang Q, Wang Y M, Magusin P C M M, Mezari B, Santen R A V, Li C. Mesoporous organic–inorganic hybrid materials built using polyhedral oligomeric silsesquioxane blocks. Angewandte Chemie International Edition, 2007, 46(26): 5003–5006
Qin Y, Ren H, Zhu F, Zhang L, Shang C, Wei Z, Luo M. Preparation of POSS-based organic-inorganic hybrid mesoporous materials networks through Schiff base chemistry. European Polymer Journal, 2011, 47(5): 853–860
Kim Y, Koh K, Roll M F, Laine R M, Matzger A J. Porous networks assembled from octaphenylsilsesquioxane building blocks. Macromolecules, 2010, 43(17): 6995–7000
Nischang I, Brüggemann O, Teasdale I. Facile, single-step preparation of versatile, high-surface-area, hierarchically structured hybrid materials. Angewandte Chemie International Edition, 2011, 50(20): 4592–4596
Eftekhari-Sis B, Rahimkhoei V, Akbari A, Araghi H Y. Cubic polyhedral oligomeric silsesquioxane nano-cross-linked hybrid hydrogels: Synthesis, characterization, swelling and dye adsorption properties. Reactive & Functional Polymers, 2018, 128: 47–57
Eftekhari-Sis B, Akbari A, Motlagh P Y, Bahrami Z, Arsalani N. Dye adsorption on cubic polyhedral oligomeric silsesquioxane-Based poly(acrylamide-co-itaconic acid) hybrid nanocomposites: Kinetic, thermodynamic and isotherms studies. Journal of Inorganic and Organometallic Polymers and Materials, 2018, 28(5): 1728–1738
Hoyle C E, Bowman C N. Thiol-ene click chemistry. Angewandte Chemie International Edition, 2010, 49(9): 1540–1573
Lowe A B. Thiol-ene “click” reactions and recent applications in polymer and materials synthesis. Polymer Chemistry, 2010, 1(1): 17–36
He H B, Li B, Dong J P, Lei Y Y, Wang T L, Yu Q W, Feng Y Q, Sun Y B. Mesostructured nanomagnetic polyhedral oligomeric silsesquioxanes (POSS) incorporated with dithiol organic anchors for multiple pollutants capturing in wastewater. ACS Applied Materials & Interfaces, 2013, 5(16): 8058–8066
Wang X, Peng R, He H, Yan X, Zhu S, Zhao H, Deng D, Yu Q, Lei Y, Luo L. Nanomagnetic polyhedral oligomeric silsesquioxanes composite derived sulfur-containing adsorbents for effective elimination of hexavalent chromium and organic cationic dyes from water. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2018, 550: 1–8
Arsalani N, Fattahi H, Laurent S, Burtea C, Elst L V, Muller R N. Polyglycerol-grafted superparamagnetic iron oxide nanoparticles: Highly efficient MRI contrast agent for liver and kidney imaging and potential scaffold for cellular and molecular imaging. Contrast Media & Molecular Imaging, 2012, 7(2): 185–194
Arsalani N, Fattahi H, Nazarpoor M. Synthesis and characterization of PVP-functionalized superparamagnetic Fe3O4 nanoparticles as an MRI contrast agent. Express Polymer Letters, 2010, 4(6): 329–338
Goganian A M, Hamishehkar H, Arsalani N, Khiabani H K. Microwave-promoted synthesis of smart superporous hydrogel for the development of gastroretentive drug delivery system. Advances in Polymer Technology, 2015, 34(2), DOI: https://doi.org/10.1002/adv.21490
Akbari A, Arsalani N. Preparation and characterization of novel hybrid nanocomposites by free radical copolymerization of vinyl pyrrolidone with incompletely condensed polyhedral oligomeric silsesquioxane. Journal of Inorganic and Organometallic Polymers and Materials, 2016, 26(3): 536–544
Akbari A, Arsalani N. Organic-inorganic incompletely condensed polyhedral oligomeric silsesquioxane-based nanohybrid: Synthesis, characterization and dye removal properties. Polymer-Plastics Technology and Engineering, 2016, 55(15), DOI: https://doi.org/10.1080/03602559.2016.1163591
Akbari A, Arsalani N, Amini M, Jabbari E. Cube-octameric silsesquioxane-mediated cargo copper Schiff base for efficient click reaction in aqueous media. Journal of Molecular Catalysis A Chemical, 2016, 414: 47–54
Arsalani N, Akbari A, Amini M, Jabbari E, Gautam S, Chae K H. POSS-based covalent networks: Supporting and stabilizing Pd for Heck reaction in aqueous media. Catalysis Letters, 2017, 147(4): 1086–1094
Eftekhari-Sis B, Akbari A, Motlagh P Y, Bahrami Z, Arsalani N. Dye adsorption on cubic polyhedral oligomeric silsesquioxane-Based poly(acrylamide-co-itaconic acid) hybrid nanocomposites: Kinetic, thermodynamic and isotherms studies. Journal of Inorganic and Organometallic Polymers and Materials, 2018, 28(5): 1728–1738
Kazeminava F, Arsalani N, Akbari A. POSS nanocrosslinked poly (ethylene glycol) hydrogel as hybrid material support for silver nanocatalyst. Applied Organometallic Chemistry, 2018, 32(6): e4359
Fu J, Shi L, Chen Y, Yuan S, Wu J, Liang X. Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology, thermal properties, and toughening mechanism. Journal of Applied Polymer Science, 2008, 109(1): 340–349
Hu Jt, Gu A, Jiang Z, Liang G, Zhuo D, Yuan L. High efficiency synthesis of octavinylsilsesquioxanes and its high performance hybrids based on bismaleimide-triazine resin. Polymers for Advanced Technologies, 2012, 23(8): 1219–1228
He H, Zhou Z, Dong C, Wang X, Yu Q W, Lei Y, Luo L, Feng Y. Facile synthesis of a boronate affinity sorbent from mesoporous nanomagnetic polyhedral oligomeric silsesquioxanes composite and its application for enrichment of catecholamines in human urine. Analytica Chimica Acta, 2016, 944: 1–13
Wang J, Ye Z, Joly H. Synthesis and characterization of hyperbranched polyethylenes tethered with polyhedral oligomeric silsesquioxane (POSS) nanoparticles by chain walking ethylene copolymerization with acryloisobutyl-POSS. Macromolecules, 2007, 40(17): 6150–6163
He H B, Dong C, Li B, Dong J P, Bo T Y, Wang T L, Yu Q W, Feng Y Q. Fabrication of enrofloxacin imprinted organic-inorganic hybrid mesoporous sorbent from nanomagnetic polyhedral oligomeric silsesquioxanes for the selective extraction of fluoroquinolones in milk samples. Journal of Chromatography. A, 2014, 1361: 23–33
Tanaka K, Chujo Y. Advanced functional materials based on polyhedral oligomeric silsesquioxane (POSS). Journal of Materials Chemistry, 2012, 22(5): 1733–1746
Akbari A, Arsalani N. Organic-inorganic incompletely condensed polyhedral oligomeric silsesquioxane-based nanohybrid: Synthesis, characterization and dye removal properties. Polymer-Plastics Technology and Engineering, 2016, 55(15): 1586–1594
Ai L, Zhang C, Liao F, Wang Y, Li M, Meng L, Jiang J. Removal of methylene blue from aqueous solution with magnetite loaded multiwall carbon nanotube: Kinetic, isotherm and mechanism analysis. Journal of Hazardous Materials, 2011, 198: 282–290
Zhou L, Jin J, Liu Z, Liang X, Shang C. Adsorption of acid dyes from aqueous solutions by the ethylenediamine-modified magnetic chitosan nanoparticles. Journal of Hazardous Materials, 2011, 185 (2–3): 1045–1052
Nassar N N, Ringsred A. Rapid adsorption of methylene blue from aqueous solutions by goethite nanoadsorbents. Environmental Engineering Science, 2012, 29(8): 790–797
Badruddoza A, Hazel G S S, Hidajat K, Uddin M. Synthesis of carboxymethyl-β-cyclodextrin conjugated magnetic nano-adsorbent for removal of methylene blue. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2010, 367(1–3): 85–95
Gao L, Wang Y, Yan T, Cui L, Hu L, Yan L, Yan L, Wei Q, Du B. A novel magnetic polysaccharide–graphene oxide composite for removal of cationic dyes from aqueous solution. New Journal of Chemistry, 2015, 39(4): 2908–2916
Acknowledgements
The authors A.A. and N.A. thank the research council of the University of Tabriz and the Iran Science Elite Federation (ISEF) for supporting this work.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
11705_2018_1784_MOESM1_ESM.pdf
Cube-octameric silsesquioxane (POSS)-capped magnetic iron oxide nanoparticles for the efficient removal of methylene blue
Rights and permissions
About this article
Cite this article
Akbari, A., Arsalani, N., Eftekhari-Sis, B. et al. Cube-octameric silsesquioxane (POSS)-capped magnetic iron oxide nanoparticles for the efficient removal of methylene blue. Front. Chem. Sci. Eng. 13, 563–573 (2019). https://doi.org/10.1007/s11705-018-1784-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11705-018-1784-x