Keggin-type heteropoly acid H3PW12O40 supported on magnetic amine-grafted Graphene oxide: A new magnetically separable adsorbent for rapid and selective removal of cationic organic pollutants in aqueous solutions

Document Type : Reasearch Paper

Authors

• Saeed Farhadi ¹
• Mansoureh Maleki ²
• Ladan Nirumand ¹
• Farzaneh Moradifard ¹

¹ Department of Chemistry, Lorestan University, Khorramabad 68151-44316, Iran.

² Department of Chemistry, Payame Noor University, Tehran 19395-4697, Iran.

10.22034/ijnd.2022.684341

Abstract

In the present study, phosphotungstic acid decorated on magnetic amine-grafted graphene oxide (GO-Amine/Fe₃O₄/H₃PW₁₂O₄₀; GOA/Fe₃O₄/HPW) was prepared and evaluated as a new adsorbent for removal and separation of organic dyes from water. The obtained nanocomposite was fully characterized by means of XRD, FT-IR, Raman, VSM, SEM, EDX, AFM and BET surface area analysis. The results demonstrated the successful loading of HPW (~34 wt.%) on the surface of magnetic aminosilanized graphene oxide. The adsorption ability of the nanocomposite was tested towards cationic methylene blue (MB) and anionic methyl orange (MO) dyes. The nanocomposite exhibited very good adsorption performance for cationic organic pollutants; it could absorb approximately 100% of methylene blue (MB) from an aqueous solution within only 5 min. The removal rate of GOA/Fe₃O₄/HPW nanocomposite was greater than that of pure GOA, Fe₃O₄ and HPW. Further study revealed that the GOA/Fe₃O₄/HPW exhibited a fast adsorption rate and selective adsorption ability towards the cationic dyes from dyes mixtures.The effect of adsorbent dosage, initial concentration of dye and pH were studied in detail. Due to the existence of the Fe₃O₄, the GOA/Fe₃O₄/HPW nanocomposite could be magnetically separated from the reaction mixture and reused without any change in structure. This research could provide a new easy platform for wastewater purification.   

Keywords

• Aminated Graphene Oxide
• Keggin-Type H3PW12O40
• Magnetic Adsorbent
• Nanocomposite
• Organic Dyes
• Polyoxometalate

20.1001.1.20088868.2022.13.1.3.5

---

References

[1] Hajavazzade R., Kargar-Razi M., Mahjoub A. R., (2021), Synthesis and characterization  of and their photocatalytic behaviors towards Congo red under UV light irradiation. Int. J. Nano Dimens. 2: 67-75.

[2] Golshan  Tafi A.,  Rashidi A.,  Tayebi H. A.,  Yazdanshenas M. E.,  (2018), Comparison of different kinetic models  for adsorption of acid blue 62 as an environmental pollutant from  aqueous  solution  onto mesoporous  Silicate  SBA-15 modifed by Tannic acid. Int. J. Nano Dimens. 9: 79-88

[3] Rahdar S., Rahdar A., Zafar M. N., Shafqat S. S., Ahmadi S., (2019), Synthesis and characterization of MgO  supported Fe–Co–Mn  nanopartcles with exceptionally high adsorption capacity for Rhodamine B dye. J. Mater. Res. Technol. 8: 3800-3810.

[4] Ahmadi S., Mohammadi L., Rahdar A., Rahdar S., Dehghani R., Igwegbe C. A., Kyzas G. Z., (2020), Acid  aqueous solution by using neodymium (III) oxide nanoadsorbents. Nanomater. 10: 556-561.

[5] Rezayati Z., Moosavi B., Taheri A., (2020), Synthesis of monodisperse magnetic hydroxyapatite/Fe₃O₄ nanospheres for removal of Brilliant Green (BG) and Coomassie Brilliant Blue (CBB) in the single and binary systems. Adv. J. of Chem. Section B. 2: 159-171.

[6] Rahimian A., Zarinabadi S., (2020), A review of studies on the removal of methylene blue dye from industrial wastewater using activated carbon adsorbents made from almond bark. Prog. Chem. Biochem. Res. 3: 251-268.

[7]  Thomas O. E., Adegoke O. A., Kazeem A. F., Ezeuchenne I. C., (2019), Preferential solvation of mordant               black  and solochrome dark blue in mixed solvent systems. Prog. Chem. Biochem. Res. 2: 40-52.

[8] Abdollahi F., Yousef M., Hekmat M., Khajehnezhad A., Seyyed-Afghahi S. S., (2020), Adsorption and photodegrading of Methylene Blue by using of BaLa_xGd_xFe_12-2xO₁₉ (x=0.2, 0.4, 0.6 and 0.8)/PANI nanocomposites. Int. J. Nano Dimens. 11: 41-49.

[9] Jarrah A., Farhadi S., (2018),  K₆P₂W₁₈O₆₂ encapsulated into magnetic Fe₃O₄/MIL-101 (Cr) metal–organic framework: a novel magnetically recoverable nanoporous adsorbent for ultrafast treatment of aqueous organic pollutants solutions. RSC Adv. 8: 37976–37992.

[10] Pourzare K., Farhadi S., Mansourpanah Y., (2017), Graphene oxide/Co₃O₄ nanocomposite: Synthesis, characterization, and its adsorption capacity for the removal of organic dye pollutants from water. Acta Chim. Slov. 15: 945–958.

[11] Golshan-Tafi A., Rashidi A., Tayebi  H. A., Yazdanshenas M. E., (2018), Comparison of diferent kinetc models  for adsorpton of acid blue 62 as an environmental pollutant from aqueous soluton onto mesoporous  Silicate  SBA-15 modifed by Tannic acid. Int. J. Nano Dimens. 9: 79–88.

[12] Wang H., Gao H., Chen M., Xu X., Wang X., Pan C., (2016),  Microwave-assisted synthesis of reduced graphene oxide/titania nanocomposites as an adsorbent for methylene blue adsorption. Appl. Surf. Sci. 360: 840–848.

[13] Mohammadi M., Sedighi M., Alimohammadi V., (2019), Modeling and optimization of nitrate and total iron removal from wastewater by TiO₂/SiO₂ nanocomposites. Int. J. Nano Dimens. 10: 195–208.

[14] Wang Y. S., Hsieh S. H., Lee C. H., Horng J. J., (2013), Adsorption of complex pollutants from aqueous solutions by nanocomposite materials. CLEAN  Soil Air Water. 41: 574–580.

[15] Wang S., Li H., Xu L., (2006), Application of zeolite MCM-22 for basic dye removal from wastewater. J. Colloid. Interf. Sci. 295: 71–78.

[16] Farhadi S., Mahmoudi F., Amini M. M., Dusek M., Jarosova M., (2017), Synthesis and characterization of a series of novel perovskite-type LaMnO₃/Keggin-type polyoxometalate hybrid nanomaterials for fast and selective removal of cationic dyes from aqueous solutions. Dalton Trans. 46: 3252–3264.

[17] Lazaridis N. K., Kyzas G. Z., Vassiliou A. A., Bikiaris D. N., (2007), Chitosan derivatives as biosorbents for basic dyes. Langmuir. 23: 7634–7643.

[18] Smith A. T., LaChance A. M., Zeng S., Sun B. L., (2019), Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites. Nano Mater. Sci. 1: 31-47

[19] Allgayer R., Yousefi N., Tufenkji N., (2020), Graphene oxide sponge as adsorbent for organic contaminants: Comparison with granular activated carbon and influence of water chemistry.Environ. Sci.: Nano. 7: 2669–2680.

[20] Khodadadi-Dizaji A., Mortaheb H. R., Mokhtarani B., (2017), Preparation of supported catalyst by adsorption of polyoxometalate on graphene oxide/reduced graphene oxide. Mater. Chem. Phys. 199: 424–434.

[21] Hajavazzadeh R., Kargar Razi M., Mahjoub A. R., (2019), Aliphatic alcohols oxidation with hydrogen peroxide in water catalyzed by supported Phosphotungstic acid (PTA) on Silica coated MgAl₂O₄ nanoparticles as a recoverable catalyst. Int. J. Nano Dimens. 10: 69–77.

[22] Liu C. G., Zheng T., Liu S., Zhang H. Y., (2016), Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: Transition metal substituted effects. J. Mol. Struct. 1110: 44–52.

[23] Wang S. M., Hwang J., Kim E., (2019), Polyoxometalates as promising materials for electrochromic devices. J. Mater. Chem. C. 7: 7828-7850.

[24]  Jarrah A., Farhadi S., (2020), Encapsulation of K₆P₂W₁₈O₆₂ into magnetic nanoporous Fe₃O₄/MIL-101 (Fe) for highly enhanced removal of organic dyes. J. Solid State Chem. 285: 121264-121268.

[25] Abroshan E., Farhadi S., Zabardasti A., (2018), Novel magnetically separable Ag₃PO₄/MnFe₂O₄ nanocomposite and its high photocatalytic degradation performance for organic dyes under solar-light irradiation. Sol. Energy Mater. Sol. Cells. 178: 154–163.

[26] Sajjadifar S., Arzehgar Z., Rezayati S., (2019), Metal-Organic Framework Zn₃(BTC)₂: As Recyclable and heterogeneous catalyst for the synthesis of 1, 5-Benzodiazepine compounds. J. Appl. Chem. 14: 211-220.

[27] Sadegh-Malvajerd S., Arzehgar  Z., Nikpour F., (2013), Regio- and chemoselective synthesis of 5-Aroyl-NH-1, 3-oxazolidine-2-thiones. Zeitschrift für Naturforschung B. 68: 182-186.

[28] Zamani A., Seyed-Sadjadi M., Mahjoub A. R., Yousef M., Farhadyar N., (2020), Synthesis  and  characterizaton ZnFe₂O₄@MnO and MnFe₂O₄@ZnO magnetc nanocomposites: Investgatigation of  photocatalytc actvity for  the degradaton of Congo Red under visible light irradiaton. Int. J. Nano Dimens. 11: 58–73.

[29] Aparna M. L., Grace A. N., Sathyanarayanan P., Sahu N. K., (2018), A comparative study on the supercapacitive behaviour of solvothermally prepared metal ferrite (MFe₂O₄, M=Fe Co, Ni, Mn, Cu, Zn) nanoassemblies. J. Alloys Comp. 745: 385–395.

[30] Beiranvand M., Farhadi S., Mohammadi A., (2019), Graphene Oxide/Hydroxyapatite/Silver               (rGO/HAP/Ag) nanocomposite: synthesis, characterization, catalytic and antibacterial activity. Int. J. Nano Dimens. 10: 180–194.

[31] Farhadi S., Hakimi M., Maleki M., (2018), Molybdophosphoric acid anchored on aminopropylsilanized magnetic graphene oxide nanosheets (Fe₃O₄/GrOSi(CH₂)₃–NH₂/H₃PMo₁₂O₄₀): A novel magnetically recoverable solid catalyst for H₂O₂-mediated oxidation of benzylic alcohols under solvent-free conditions. RSC Adv. 8: 6768–6780.

[32] Feng C., Xu G., Liu X., (2013), Photocatalytic degradation of imidacloprid by composite catalysts H₃PW₁₂O₄₀/La-TiO₂. J. Rare Earth. 31: 44–48.

[33] Nirumand L., Farhadi S., Zabardasti A., Khataee A., (2018), Synthesis and sonocatalytic performance of     a ternary magnetic MIL-101(Cr)/RGO/ZnFe₂O₄ nanocomposite for degradation of dye pollutants. Ultrason Sonochem. 42: 647–658.

[34] Pourzare K., Farhadi S., Mansourpanah Y., (2018), Anchoring H₃PW₁₂O₄₀ on aminopropylsilanized spinel‐typecobalt oxide (Co₃O₄‐SiPrNH₂/H₃PW₁₂O₄₀): A novelnanohybrid adsorbent for removing cationic organic dye pollutants from aqueous solutions. Appl. Organomet. Chem. 32: 1-15.

[35] Nirumand L., Farhadi S., Zabardasti A., (2018), Magnetically separable Ag/CuFe₂O₄/Reduced Graphene Oxide ternary nanocomposite with high performance for the removal of nitrophenols and dye Pollutants from aqueous media. Acta Chim. Slov. 65: 919–931.

[36] Liu G., Jiang W., Wang Y., Zhong S., Sun D., Liu J., (2015), One-pot synthesis of Ag@Fe₃O₄/reduced graphene oxide composite with excellent electromagnetic absorption properties. Ceram. Int. 41: 4982–49888.

[37] Hazhir N., Chekin F., Raoof J. B, Fathi S., (2021), Anticancer activity of Doxorubicin conjugated to polymer/carbon based-nanohybrid against MCF-7 breast and HT-29 colon cancer cells. Int. J. Nano Dimens. 12: 11–19.

[38] Lu L. T., Dung N. T., Tung L. D., (2015), Synthesis of magnetic cobalt ferrite nanoparticles with controlled morphology, monodispersity and composition: the influence of solvent, surfactant, reductant and synthetic conditions. Nanoscale. 7: 19596–19610.

[39] Kumar A. S. K., Jiang S. J., (2017), Synthesis of magnetically separable and recyclable magnetic nanoparticles decorated with β-cyclodextrin functionalized graphene oxide an excellent adsorption of As(V)/(III). J. Mol. Liq. 237: 387–401.

[40] Mahmoudi F., Amini M. M., (2020), Confined crystallization of microporous metal-organic framework within mesoporous silica with enhanced hydrostability: Ultrafast removal of organic dyes from aqueous solutions by MIL-68(Al)@SBA-15 composite. J. Water Process Eng. 35: 101227-101231.

[41] Aboelfetoh E. F., Gemeay A. H.,  El-Sharkawy R. G., (2021), Effective disposal of methylene blue using  green  immobilized silver nanoparticles on graphene oxide and reduced graphene oxide sheets through    one-potsynthesis. Environ. Monit. Assess. 192: 355-361.

[42] Zhu T-T., Zhang Z.-M., Chen W-L., Liu Z-J., Wang E-B., (2016), Encapsulation of tungstophosphoric acid into harmless MIL-101(Fe) for effectively removing cationic dye from aqueous solution. RSC Adv. 6: 81622–81630.

[43] Sun H., Cao L., Lu L., (2011), Magnetite/reduced graphene oxide nanocomposites: one step solvothermal synthesis and use as a novel platform for removal of dye pollutants. Nano Res. 4: 550–562.

[44] Jiang Z., Li Y., (2016), Facile synthesis of magnetic hybrid Fe₃O₄/MIL-101 via heterogeneous coprecipitation assembly for efficient adsorption of anionic dyes. J. Taiwan Inst. Chem Eng. 59: 373–379.

[45] Li R., Ren X., Zhao J., Feng X., Jiang X., Fan X., (2014), Polyoxometallates trapped in a zeolitic imidazolate framework leading to high uptake and selectivity of bioactive molecules. J. Mater. Chem. A. 2: 2168–2173.

[46] Das R. T., Sharma K. P., (2020), Bimetal oxide decorated graphene oxide (Gd₂O₃/Bi₂O₃@GO) nanocomposite as an excellent adsorbent in the removal of methyl orange dye. Mater. Sci. Semicon. Proc. 105: 104721-104725.