Document Type : Original Research Article


1 Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran

2 Department of Chemistry, Faculty of Science, Islamic Azad University, Shahremajlesi, Iran


Adsorption process has been widely used as one of the efficient methods in removing pollutants that are hardly biodegradable. In this study, new epichlohydrine crosslinked Schiff base chitosan/Fe2O3 nanocomposite was prepared and applied as adsorbent material. The synthesized adsorbent was characterized by FT-IR, XRD, TGA/DTA, DSC, EDS, BET, XRD and FE-SEM to explore morphology, structure and functional groups. The adsorbent was applied for removal of methyl green (MG) from aqueous solutions through batch experiments. Different parameters such as adsorbent dosage, pH and contact time were considered. The removal efficiency of 94.8 % was acquired at the optimum condition of pH = 8, adsorbent dosage of 0.02 g and contact time of 30 min. The adsorption capacity of the sorbent was found to be 47.4 mg/g. This nanocomposite could be a suitable candidate for the removal of other organic dyes.

Graphical Abstract

Synthesis, Characterization, and Methyl Green Removal of Epichlorohydrin Crosslinked Schiff Base Chitosan/Fe2O3 Nanocomposite


Main Subjects

[1] Rahmi, Ismaturrahmi, I. Mustafa, Methylene blue removal from water using H2SO4 crosslinked magnetic chitosan nanocomposite beads. Microchem. J. 144 (2019) 397-402.
[2] D. Yang, L. Qiu, Y. Yang, Efficient adsorption of methyl orange using a modified chitosan magnetic composite adsorbent, J. Chem. Eng. Data 61 (2016) 3933-3940.
[3] F.C. Tsai, N. Ma, T.C. Chiang, L.C. Tsai, J.J. Shi, Y. Xia, T. Jiang, S.K. Su, F.S. Chuang, Adsorptive removal of methyl orange from aqueous solution with crosslinking chitosan microspheres, J. Water Process Eng. 1 (2014) 2-7.
[4] P. Ke, D. Zeng, K. Xu, J. Cui, G. Wang, Preparation of quaternary ammonium salt-modified chitosan michrospheres and their application in dying wastewater treatment, ACS Omega 5 (2020) 24700-24707.
[5] Y. Haldorai, J.J. Shim, An efficient removal of methyl orange dye from aqueous solution by adsorption onto chitosan/MgO composite: A novel reusable adsorbent, App. Surf. Sci. 292 (2014) 447-453.
[6] L. Obeid, A. Bee, D. Talbot, S. Ben Jaafar, V. Dupuis, S. Abramson, V. Cabuil, M. Welschbillig, Chitosan/maghemite composite: A megsorbent for the adsorption of methyl orange, J. Coll. Interface Sci. 410 (2013) 52-58.
[7] G. Yuvaraja, D.Y. Chen, J.L. Pathak, J. Long, M.V. Subbaiah, J.C. Wen, C.L. Pan, Preparation of novel aminated chitosan schiff’s base derivative for the removal of methyl orange dye from aqueous environment and its biological applications, Int. J. Biol. Macromol. 146 (2020) 1100-1110.
[8] L. Zhai, Z. Bai, Y. Zhu, B. Wang, W. Luo, Fabrication of chitosan microspheres for efficient adsorption of methyl orange, Chin. J. Chem. Eng. 26 (2018) 657-666.
[9] A. Foroughnia, A.D. Khalaji , E. Kolvari, N. Koukabi, Synthesis of new chitosan Schiff base and its Fe2O3 nanocomposite: Evaluation of methyl orange removal and antibacterial activity, Int. J. Biol. Macromol. 177 (2021) 83-91.
[10] P.M.O. Silva, J.E. Francisco, J.C.M. Caje, R.J. Cassella, W.F. Pacheco, A bath and fixed bed column study for fluorescein removal using chitosan modified by epichlorohydrin, J. Environ. Sci. Health, A. 53 (2018) 55-64.
[11] W.A. Khanday, F. Marrakchi, M. Asif, B.H. Hameed, Mesoporous zeolite-activated carbon composite from oil palm ash as an effective adsorbent for methylene blue. J. Taiwan Inst. Chem. Eng. 70 (2017) 32-41.
 [12] V. Golob, A. Vinder, M. Simonic, Efficiency of the coagulation/flocculation method for the treatment of dye bath effluents, Dye Pig. 67 (2005) 93-97.
[13] M. Tabatabaee, S.A. Mirrahimi, Photodegradation of dye pollutant on Ag/ZnO nanocatalyst under UV-irradiation. Orient. J. Chem. 27 (2011) 65.
[14] M.H. Mahaninia, Sorption study of water vapor and a dye on chitosan-based framework materials, ACS Omega 5 (2020) 21836-21843.
[15] F. Gu, J. Geng, M. Li, J. Chang, Y. Dui, Synthesis of chitosan-lignosulfonate composite as an adsorbent for dyes and metal ions removal from wastewater, ACS Omega 4 (2019) 21421-21430.
[16] J. Wang, X. Yang, D. Zheng, A. Yao, D. Hua, V. Srinivasapriyan, G. Zhan, Fabrication of bioinspired gallic acid-grafted chitosan/polysulfone composite membranes for dye removal via nanofiltration, ACS Omega 5 (2020) 13077-13086.
[17] V.K. Saharan, M.P. Badve, A.B. Pandit, Degradation of reactive red 120 dye using hydrodynamic cavitation, Chem. Eng. J. 178 (2011) 100-107.
[18] A.N. Kulkarni, A.A. Kadam, M.S. Kachole, S.P. Govindwar, Lichen permelia perlata: a novel system foe biodegradation and detoxcification of disperse dye solvent red 24, J. Hazard. Mater. 276 (2014) 461-468.
[19] L. Arjomandi-Behzad, M.K. Rofouei, A. Badiei, J. B. Ghasemi. "Simultaneous removal of crystal violet and methyl green in water samples by functionalised SBA-15." Int. J. Environ. Anal. Chem. (2020) 1-17.
[20] M. Sahin, N. Kocak, G. Arslan, H.I. Ucan, Synthesis of crosslinked chitosan with epichlorohydrin possessing two novel polymeric ligands and its use in metal removal, J. Inorg. Organomet. Polym. 21 (2011) 69-80.
[21] M. Li, Z. Zhang, R. Li, J.J. Wang, A. Ali, Removal of Pb(II) and Cd(II) ions from aqueous solution by thiosemicarbazide modified chitosan, Int. J. Biol. Macromol. 86 (2016) 876-884.
[22] R. Ahmad, A. Mirza, Facile one pot green synthesis of chitosan-iron oxide (CS-Fe2O3) nanocomposite: Removal of Pb(II) and Cd(II) from synthetic and industrial wastewater, J. Clean. Prod. 186 (2018) 342-352.
[23] M. Sajid, M.K. Nazal, N. Baig, A.M. Osman. "Removal of heavy metals and organic pollutants from water using dendritic polymers based adsorbents: a critical review." Sep. Purif. Technol. 191 (2018) 400-423.
[24] U. Habiba, T.A. Siddique, S.J.L. Lee, T.C. Joo, B.C. Ang, A.M. Afifi. Adsorption study of methyl orange by chitosan/polyvinyl alcohol/zeolite electrospun composite nanofibers membrane, Carbohydr. Polym. 191 (2018) 79-85.
[25] S. Kumar, B. Krishnakumar, A.J.F.N. Sobral, J. Koh, Bio-based (chitosan/PVA/ZnO) nanocomposites filem: Thermally stable and photoluminescence material for removal of organic dye, Carbohydr. Polym. 205 (2019) 559-564.
[26] N. Parshi, D. Pan, V. Dhavle, B. Jana, S. Maity, J. Ganguly, Fabrication of lightweight and reusable salicylaldehyde finctionalized chitosan as adsorbent for dye removal and its mechanism, Int. J. Biol. Macromol. 141 (2019) 626-635.
[27] S.A. Hosseini, S. Daneshvar e Asl, M. Vossoughi, A. Simchi, M. Sadrzadeh, Green electrospun membrances based on chitosan/amino functionalized nanoclay composite fibers for cationic dye removal: Synthesis and kinetic studies, ACS Omega 6 (2021) 10816-10827.
[28] S. Cinar, U.H. Kaynar, T. Aydemir, S.C. Kaynar, M. Ayvacikli, An efficient removal of RB5 from aqueous solution by adsorption onto nano-ZnO/chitosan composite beads, Int. J. Biol. Macromol. 96 (2017) 459-465.
[29] M.S. Hussain, S.G. Musharraf, M.I. Bhanger, M.I. Malik, Salicylaldehyde derivative of nano-chitosan as an efficient adsorbent for lead(II), copper(II), and cadmium(II) ions, Int. J. Biol. Macromol. 147 (2020) 643-652.
[30] M. Sanati, A.D. Khalaji, A. Mokhtari, M. Keyvanfard, Fast removal of methyl green from aqueous solution by adsorption onto new modified chitosan Schiff base, Prog. Chem. Biochem. Res, 4(3) (2021) 319-330.
[31] M. Setoodehkhah, S. Momeni. "Water Soluble Schiff Base Functinalized Fe 3 O 4 Magnetic Nano-Particles as a Novel Adsorbent for the Removal of Pb (II) and Cu (II) Metal Ions from Aqueous Solutions." J. Inorg. Organomet. Polym. Mater. 28 (2018) 1098-1106.
[32] E.M. El-Sayed, T. M. Tamer, A. M. Omer, M. S. Mohy Eldin. "Development of novel chitosan schiff base derivatives for cationic dye removal: methyl orange model." Desalin. Water Treat. 57 (2016) 22632-22645.
[33] S.M. Alardhi, T.M. Albayati, J.M. Alrubaye, Adsorption of the methyl green dye pollutant from aqueous solution using mesoporous materials MCM-41 in a fixed-bed column, Heliyon 6 (2020) e03253.
[34] P. Sharma, b.K. Saikia, M.R. Das, Removal of methyl green dye molecule from aqueous system using reduced graphene oxide as an efficient adsorbent: kinetics, isotherm and thermodynamic parameters, Coll. Surf. A. 457 (2014) 125-133.
[35] A. Maghni, M. Ghelamallah, A. Benghalem, Sorptive removal of methyl green from aqueous solutions using activated bentonite, Acta Phys. Pol. A. 132 (2017) 448-450.
[36] M. Bahgat, A.A. Farghali, W. El Rouby, M. Khedr, M.Y. Mohassab-Ahmed, Adsorption of methyl green dye onto multi-walled carbon nanotubes decorated with Ni nanoferrite, App. Nanosci. 3 (2013) 251-261.
[37] K. Rida, K. Chaibedra, K. Cheraitia, Adsorption of cationic dye methyl green from aqueous solution onto activated carbon prepared from Brachychiton Populneus fruit shell, Ind. J. Chem. Technol. 27 (2020) 51-59.
[38] A.D. Khalaji, S.M. Mousavi, M. Jarosova, P. Machek, The effect of calcination on the morphology, size and the crystalline phase of the as-synthesized products by direct calcination of FeSO4 at the presence of benzoic acid, J. Surf. Invest. X-ray, Synch. Neut. Tech. 14 (2020) 1191-1194.
[39] K.R. Ansari, D.S. Chauhan, M.A. Quraishi, M.A.J. Mazumder, A. Singh, Chitosan Schiff base: an environmentally benign biological macromolecule as a new corrosion inhibitor for oil & gas industries, Int. J. Biol. Macromol. 144 (2020) 305-315.
[40] S. Shahraki, H.S. Delarami, F. Khosravi, Synthesis and characterization of an adsorptive Schiff base – chitosan nanocomposite for removal of Pb(II) ion from aqueous media, Int. J. Biol. Macromol. 139 (2019) 577-586.
[41] M.M. Iftime, S. Morarium L. Marin, Salicyl-imine-chitosan hydrogels: supramolecular architeturings as a crosslinking method toward multifunctional hydrogels, Carbohydr. Polym. 165 (2017) 39-50.
[42] W.S. Wan Ngah, M.A.K.M. Hanafiah, S.S. Yong, Adsorption of humic acid from aqueous solutions on crosslinked chitosan-epichlorohydrin beads: Kinetics and isotherm studies, Coll. Surf. B. 65 (2008) 18-24.
[43] Z. Weijiang, Z. Yace, G. Yuvaraja, X. Jiao, Adsorption of Pb(II) from aqueous environment using eco-friendly chitosan Schiff’s base@Fe3O4 (CSB@Fe3O4) as an adsorbent: kinetic, isotherm and thermodynamic studies, Int. J. Biol. Macromol. 105 (2017) 422-430.
[44] Y. Yan, G. Yuvaraja, C. Liu, L. Kong, K. Guo, G.M. Reddy, G.V. Zyryanov, Removl of Pb(II) ions from aqueous media using epichlorohydrin crosslinked chitosan Schiff’s base@Fe3O4 (ECCSB@Fe3O4), Int. J. Biol. Macromol. 117 (2018) 1305-1313.
[45] R. Ahmad, A. Mirza, Facile one pot green synthesis of chitosan-iron oxide (CD-Fe2O3) nanocomposite: Removal of Pb(II) and Cd(II) from synthetic and industrial wastewater, J. Clean Produc. 186 (2018) 342-352.
[46] A.A. Atshan, "Adsorption of methyl green dye onto bamboo in batch and continuous system." Iraqi J. Chem. Pet. Eng. 15 (2014) 65-72.
[47] Y. Satlaoui, M. Trifi, D.F. Romdhane, A. Charef, R. Azouzi. "Removal properties, mechanisms, and performance of methyl green from aqueous solution using raw and purified Sejnane clay type." J. Chem. 2019 (2019) 4121864.