Please wait a minute...

Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 563-573
Cube-octameric silsesquioxane (POSS)-capped magnetic iron oxide nanoparticles for the efficient removal of methylene blue
Ali Akbari1(), Nasser Arsalani2(), Bagher Eftekhari-Sis1, Mojtaba Amini1, Gholamreza Gohari3, Esmaiel Jabbari4
1. Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
2. Research Laboratory of Polymer, Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
3. Department of Horticulture, Faculty of Agriculture, University of Maragheh, Maragheh, Iran
4. Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
Download: PDF(1936 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

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 These NPs could be easily withdrawn from water within a few seconds under moderate magnetic field and showed high stability in acid and alkaline aqueous mediums.

Keywords nanomagnetic POSS      surface polymerization      thiol-ene reaction      adsorbent      water treatment     
Corresponding Authors: Ali Akbari,Nasser Arsalani   
Online First Date: 24 April 2019    Issue Date: 22 August 2019
 Cite this article:   
Ali Akbari,Nasser Arsalani,Bagher Eftekhari-Sis, et al. Cube-octameric silsesquioxane (POSS)-capped magnetic iron oxide nanoparticles for the efficient removal of methylene blue[J]. Front. Chem. Sci. Eng., 2019, 13(3): 563-573.
E-mail this article
E-mail Alert
Articles by authors
Ali Akbari
Nasser Arsalani
Bagher Eftekhari-Sis
Mojtaba Amini
Gholamreza Gohari
Esmaiel Jabbari
Fig.1  Scheme 1 The four synthesis steps for Fe3O4@POSS-COOH NPs
Fig.2  FTIR spectra of (a) neat Fe3O4, (b) silan A-modified Fe3O4, (c) Fe3O4@POSS, (d) Fe3O4@POSS-COOH, and (e) pure octavinyl-POSS materials
Fig.3  SEM images of (a) neat Fe3O4, (b) silan A-modified Fe3O4, (c) Fe3O4@POSS, and (d) Fe3O4@POSS-COOH nanomaterials and TEM images of Fe3O4@POSS-COOH hybrid magnetic nanoparticles with different magnifications
Atomic percent/% Weight percent/% Atomic percent/% Weight percent/% Element
53.85 41.51 48.64 38.45 C
38.57 40.14 43.42 45.72 O
6.41 11.72 7.31 13.50 Si
0.49 1.44 0.63 2.33 Fe
0.67 5.19 S
Tab.1  EDX weight and atomic percentages of various elements on the surfaces of Fe3O4@POSS and Fe3O4@POSS-COOH
Fig.4  XRD diffraction patterns of (a) neat Fe3O4, (b) Fe3O4@POSS, (c) Fe3O4@POSS-COOH, and (d) octavinyl-POSS
Fig.5  VSM magnetization curves of (a) neat Fe3O4, (b) silan A-modified Fe3O4, and (c) Fe3O4@POSS-COOH nanomaterials
Fig.6  Optical images of the samples soaked in (a) 0.1 mol/L HCl (Fe3O4@POSS-COOH left, neat Fe3O4 right) and (b) 1 mol/L HCl (Fe3O4@POSS-COOH left, neat neat Fe3O4 right)
Fig.7  Effect of (a) amount of adsorbent, (b) initial dye concentration, (c) solution pH, and (d) contact time on the removal of methylene blue by Fe3O4@POSS-COOH nanocomposites (conditions: 4 mg of adsorbent with 30 mg/L methylene blue in 30 mL water)
Fig.8  Scheme 2 Schematic illustration of the possible interactions between Fe3O4@POSS-COOH and methylene blue dye (A) electrostatic attractions and (B) p-p stacking
Fig.9  Reusability of Fe3O4@POSS-COOH nanocomposite for adsorption of methylene blue
1 H Kaşgöz, A Durmus. Dye removal by a novel hydrogel-clay nanocomposite with enhanced swelling properties. Polymers for Advanced Technologies, 2008, 19(7): 838–845
2 M Rafatullah, O Sulaiman, R Hashim, A Ahmad. Adsorption of methylene blue on low-cost adsorbents: A review. Journal of Hazardous Materials, 2010, 177(1): 70–80
3 M Dai, H X Li, J P Lang. New approaches to the degradation of organic dyes, and nitro-and chloroaromatics using coordination polymers as photocatalysts. CrystEngComm, 2015, 17(26): 4741–4753
4 X Y Wu, H X Qi, J J Ning, J F Wang, Z G Ren, J P Lang. 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
5 B Wu, W H Zhang, Z G Ren, J P A Lang. 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
6 Y Zhang, Z R Tang, X Fu, Y J Xu. 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
7 Y X Shi, W X Li, H H Chen, D J Young, W H Zhang, J P Lang. 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
8 F Wang, F L Li, M M Xu, H Yu, J G Zhang, H T Xia, J P Lang. 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
9 C N Lü, M M Chen, W H Zhang, D X Li, M Dai, J P Lang. 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
10 D Liu, F F Lang, X Zhou, Z G Ren, D J Young, J P Lang. 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
11 S Sekar, M Surianarayanan, V Ranganathan, D R MacFarlane, A B Mandal. Choline-based ionic liquids-enhanced biodegradation of azo dyes. Environmental Science & Technology, 2012, 46(9): 4902–4908
12 I A Salem, M S El-Maazawi. Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces. Chemosphere, 2000, 41(8): 1173–1180
13 M Riera-Torres, C Gutiérrez-Bouzán, M Crespi. Combination of coagulation-flocculation and nanofiltration techniques for dye removal and water reuse in textile effluents. Desalination, 2010, 252(1): 53–59
14 J Labanda, J Sabaté, J Llorens. 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
15 Y Fan, H J Liu, Y Zhang, Y Chen. 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
16 H Kolya, T Tripathy. Hydroxyethyl starch-g-poly-(N,N-dimethylacrylamide-co-acrylic acid): An efficient dye removing agent. European Polymer Journal, 2013, 49(12): 4265–4275
17 L Li, N Hu, D Ding, X Xin, Y Wang, J Xue, H Zhang, Y Tan. Adsorption and recovery of U (VI) from low concentration uranium solution by amidoxime modified Aspergillus niger. RSC Advances, 2015, 5(81): 65827–65839
18 M J Manos, M G Kanatzidis. Layered metal sulfides capture uranium from seawater. Journal of the American Chemical Society, 2012, 134(39): 16441–16446
19 G Cotin, S Piant, D Mertz, D Felder-Flesch, S Begin-Colin. Iron Oxide Nanoparticles for Biomedical Applications: Synthesis, Functionalization, and Application. In: Iron Oxide Nanoparticles for Biomedical Applications. Amsterdam: Elsevier, 2018, 43–88
20 C L Chen, T Y Siow, C H Chou, C H Lin, M H Lin, Y C Chen, W Y Hsieh, S J Wang, C Chen. 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
21 B Eftekhari-Sis, M Akbari, A Akbari, M Amini. 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
22 H Chen, C Deng, X Zhang. 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
23 M Park, S Seo, I S Lee, J H Jung. 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
24 C Kresge, M Leonowicz, W Roth, J Vartuli, J Beck. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature, 1992, 359(6397): 710–712
25 G Wu, L Chen, L Liu. 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
26 R Hojiyev, Y Ulcay, M Hojamberdiev, M S Çelik, W M Carty. Hydrophobicity and polymer compatibility of POSS-modified Wyoming Na-montmorillonite for developing polymer-clay nanocomposites. Journal of Colloid and Interface Science, 2017, 497: 393–401
27 D B Cordes, P D Lickiss, F Rataboul. Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chemical Reviews, 2010, 110(4): 2081–173
28 S W Kuo, F C Chang. POSS related polymer nanocomposites. Progress in Polymer Science, 2011, 36(12): 1649–1696
29 T L Lu, G Z Liang, K C Kou, Z A Guo. Review synthesis and characterization of cage octa (cyclohexylsilsesquioxane). Journal of Materials Science, 2005, 40(18): 4721–4726
30 L Zhang, H C Abbenhuis, Q Yang, Y M Wang, P C M M Magusin, B Mezari, R A V Santen, C Li. Mesoporous organic–inorganic hybrid materials built using polyhedral oligomeric silsesquioxane blocks. Angewandte Chemie International Edition, 2007, 46(26): 5003–5006
31 Y Qin, H Ren, F Zhu, L Zhang, C Shang, Z Wei, M Luo. Preparation of POSS-based organic-inorganic hybrid mesoporous materials networks through Schiff base chemistry. . European Polymer Journal, 2011, 47(5): 853–860
32 Y Kim, K Koh, M F Roll, R M Laine, A J Matzger. Porous networks assembled from octaphenylsilsesquioxane building blocks. Macromolecules, 2010, 43(17): 6995–7000
33 I Nischang, O Brüggemann, I Teasdale. Facile, single-step preparation of versatile, high-surface-area, hierarchically structured hybrid materials. Angewandte Chemie International Edition, 2011, 50(20): 4592–4596
34 B Eftekhari-Sis, V Rahimkhoei, A Akbari, H Y Araghi. Cubic polyhedral oligomeric silsesquioxane nano-cross-linked hybrid hydrogels: Synthesis, characterization, swelling and dye adsorption properties. Reactive & Functional Polymers, 2018, 128: 47–57
35 B Eftekhari-Sis, A Akbari, P Y Motlagh, Z Bahrami, N Arsalani. 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
36 C E Hoyle, C N Bowman. Thiol-ene click chemistry. Angewandte Chemie International Edition, 2010, 49(9): 1540–1573
37 A B Lowe. Thiol-ene “click” reactions and recent applications in polymer and materials synthesis. Polymer Chemistry, 2010, 1(1): 17–36
38 H B He, B Li, J P Dong, Y Y Lei, T L Wang, Q W Yu, Y Q Feng, Y B Sun. 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
39 X Wang, R Peng, H He, X Yan, S Zhu, H Zhao, D Deng, Q Yu, Y Lei, L Luo. 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
40 N Arsalani, H Fattahi, S Laurent, C Burtea, L V Elst, R N Muller. 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
41 N Arsalani, H Fattahi, M Nazarpoor. Synthesis and characterization of PVP-functionalized superparamagnetic Fe3O4 nanoparticles as an MRI contrast agent. Express Polymer Letters, 2010, 4(6): 329–338
42 A M Goganian, H Hamishehkar, N Arsalani, H K Khiabani. Microwave-promoted synthesis of smart superporous hydrogel for the development of gastroretentive drug delivery system. Advances in Polymer Technology, 2015, 34(2), 10.1002/adv.21490
43 A Akbari, N Arsalani. 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
44 A Akbari, N. ArsalaniOrganic-inorganic incompletely condensed polyhedral oligomeric silsesquioxane-based nanohybrid: Synthesis, characterization and dye removal properties. Polymer-Plastics Technology and Engineering, 2016, 55(15),
45 A Akbari, N Arsalani, M Amini, E Jabbari. 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
46 N Arsalani, A Akbari, M Amini, E Jabbari, S Gautam, K H Chae. POSS-based covalent networks: Supporting and stabilizing Pd for Heck reaction in aqueous media. Catalysis Letters, 2017, 147(4): 1086–1094
47 B Eftekhari-Sis, V Rahimkhoei, A Akbari, H Y Araghi. Reactive & Functional Polymers, 2018,128: 47–57
48 B Eftekhari-Sis, A Akbari, P Y Motlagh, Z Bahrami, N Arsalani. 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
49 F Kazeminava, N Arsalani, A Akbari. POSS nanocrosslinked poly(ethylene glycol) hydrogel as hybrid material support for silver nanocatalyst. Applied Organometallic Chemistry, 2018, 32(6): e4359
50 J Fu, L Shi, Y Chen, S Yuan, J Wu, X Liang. Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology, thermal properties, and toughening mechanism. Journal of Applied Polymer Science, 2008, 109(1): 340–349
51 Jt Hu, A Gu, Z Jiang, G Liang, D Zhuo, L Yuan. High efficiency synthesis of octavinylsilsesquioxanes and its high performance hybrids based on bismaleimide-triazine resin. Polymers for Advanced Technologies, 2012, 23(8): 1219–1228
52 H He, Z Zhou, C Dong, X Wang, Q W Yu, Y Lei, L Luo, Y Feng. 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
53 J Wang, Z Ye, H Joly. 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
54 H B He, C Dong, B Li, J P Dong, T Y Bo, T L Wang, Q W Yu, Y Q Feng. 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
55 K Tanaka, Y Chujo. Advanced functional materials based on polyhedral oligomeric silsesquioxane (POSS). Journal of Materials Chemistry, 2012, 22(5): 1733–1746
56 A Akbari, N Arsalani. 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
57 L Ai, C Zhang, F Liao, Y Wang, M Li, L Meng, J Jiang. Removal of methylene blue from aqueous solution with magnetite loaded multi-wall carbon nanotube: Kinetic, isotherm and mechanism analysis. Journal of Hazardous Materials, 2011, 198: 282–290
58 L Zhou, J Jin, Z Liu, X Liang, C Shang. Adsorption of acid dyes from aqueous solutions by the ethylenediamine-modified magnetic chitosan nanoparticles. Journal of Hazardous Materials, 2011, 185(2-3): 1045–1052
59 N N Nassar, A Ringsred. Rapid adsorption of methylene blue from aqueous solutions by goethite nanoadsorbents. Environmental Engineering Science, 2012, 29(8): 790–797
60 A Badruddoza, G S S Hazel, K Hidajat, M Uddin. Synthesis of carboxymethyl-b-cyclodextrin conjugated magnetic nano-adsorbent for removal of methylene blue. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2010, 367(1-3): 85–95
61 L Gao, Y Wang, T Yan, L Cui, L Hu, L Yan, L Yan, Q Wei, B Du. A novel magnetic polysaccharide–graphene oxide composite for removal of cationic dyes from aqueous solution. New Journal of Chemistry, 2015, 39(4): 2908–2916
[1] FCE-18061-OF-AA_suppl_1 Download
Related articles from Frontiers Journals
[1] Leila Ouni, Ali Ramazani, Saeid Taghavi Fardood. An overview of carbon nanotubes role in heavy metals removal from wastewater[J]. Front. Chem. Sci. Eng., 2019, 13(2): 274-295.
[2] Yixiu WANG,Chao LI,Fanchao MENG,Shuling LV,Jintao GUO,Xiaoqin LIU,Chongqing WANG,Zhengfei MA. CuAlCl4 doped MIL-101 as a high capacity CO adsorbent with selectivity over N2[J]. Front. Chem. Sci. Eng., 2014, 8(3): 340-345.
[3] Shuna LI, Huawei YANG, Donghui ZHANG. Enrichment of CO from syngas with Cu(I)Y adsorbent by five-bed VPSA[J]. Front Chem Sci Eng, 2013, 7(4): 472-481.
[4] Gautam SEN, G. Usha RANI, Sumit MISHRA. Microwave assisted synthesis of poly(2-hydroxyethylmethacrylate) grafted agar (Ag-g-P(HEMA)) and its application as a flocculant for wastewater treatment[J]. Front Chem Sci Eng, 2013, 7(3): 312-321.
[5] Jing DONG, Huilong WANG. A study on rapid acid chrome black (MB 7) spectrophotometric determination of ClO2 and catalytic degradation of 2,6-dinitro-p-cresol (DNPC) by ClO2[J]. Front Chem Sci Eng, 2011, 5(2): 245-251.
[6] QI Jingyao, LI Xin, LI Ying, ZHU Jianhua, QIANG Liangsheng. Selective removal of Cu(II) from contaminated water using molecularly imprinted polymer[J]. Front. Chem. Sci. Eng., 2008, 2(1): 109-114.
Full text