Sustainable Hydrogel Nanocomposites Based on Grafted Chitosan and Clay for Effective Adsorption of Cationic Dye

Authors: H. Ferfera-Harrar, T. Benhalima, D. Lerari

Abstract:

Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L^-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g^-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (q_m) was found to increase from 2173 mg g⁻¹ until 2221 mg g⁻¹ by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

Keywords: Chitosan, clay, dye adsorption, hydrogels nanocomposites.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.3607898

References:

[1] V. Katheresan, J. Kansedo, S.Y. Lau, “Efficiency of various recent wastewater dye removal methods: A review”, J. Environ. Chem. Eng., vol. 6, pp. 4676–4697, 2018.
[2] W. Yang, J. Wang, Q. Yang, H. Pei, N. Hu, Y. Suo, Z. Li, D. Zhang, J. Wang, “Facile fabrication of robust MOF membranes on cloth via a CMC macromolecule bridge for highly efficient Pb(II) removal, Chem. Eng. J., vol. 339, pp. 230–239, 2018.
[3] P. Kumar, A. Pournara, K.H. Kim, V. Bansal, S. Rapti, M.J. Manos, “Metal-organic frameworks: challenges and opportunities for ion-exchange/sorption applications”, Prog. Mater. Sci., vol. 86, 25–74, 2017.
[4] M.T. Yagub, T.K. Sen, S. Afroze, H.M. Ang, “Dye and its removal from aqueous solution by adsorption: A review”, Adv. Colloid Interface Sci., vol. 209, pp. 172–184, 2014.
[5] S. Shakoor, A. Nasar, “Removal of methylene blue dye from artificially contaminated water using citrus limetta peel waste as a very low cost adsorbent”, J. Taiwan Inst. Chem. Eng., vol. 66, 154–163, 2016.
[6] M.K. Uddin, “A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade”, Chem. Eng. J., vol. 308, pp. 438–462, 2017.
[7] H. Ferfera-Harrar, N. Aiouaz, N. Dairi, “Synthesis and Properties of Chitosan-Graft-Polyacrylamide/Gelatin Superabsorbent Composites for Wastewater Purification”, World Academy of Science, Engineering and Technology Inter. J. Chem., Molecular Nuclear Mater. Metallurgical Eng., vol.9, pp.757–764, 2015.
[8] N.S. V Capanema, A.A.P. Mansur, H.S. Mansur, A.C. de Jesus, S.M. Carvalho, P. Chagas, L.C. de Oliveira, “Eco-friendly and biocompatible cross-linked carboxymethylcellulose hydrogels as adsorbents for the removal of organic dye pollutants for environmental applications”, Environ. Technol., vol. 39, pp. 2856–2872, 2018.
[9] H. Ferfera-Harrar, D. Berdous, T. Benhalima, “Hydrogel nanocomposites based on chitosan-g-polyacrylamide and silver nanoparticles synthesized using Curcuma longa for antibacterial applications”, Polym. Bull., vol. 75, pp. 2819–2846, 2018.
[10] H. Ferfera-Harrar, N. Aouaz, N. Dairi, “Environmental-sensitive chitosan-g-polyacrylamide/carboxymethylcellulose superabsorbent composites for wastewater purification I: synthesis and properties”, Polym. Bull., vol. 73, pp. 815–840, 2016.
[11] T. Benhalima, S. Mounsi, N. Dairi, H. Ferfera-Harrar, “Chitosan-g-poly(acrylamide)/Diatomite superabsorbent composites: synthesis and investigation of swelling properties”, Journal of Materials, Processes and Environment, vol. 4, pp. 21-25, 2016.
[12] H. Ferfera-Harrar, N. Aiouaz, N. Dairi, A.S. Hadj-Hamou, “Preparation of chitosan-g-poly(acrylamide)/montmorillonite superabsorbent polymer composites: Studies on swelling, thermal, and antibacterial properties”, J. Appl. Polym. Sci., vol. 131, pp.39747.
[13] T. Benhalima, D. Lerari, H. Ferfera-Harrar, “Preparation of carboxymethylcellulose-based hydrogel beads and their used as bioadsorbent of dye from aqueous solutions”. Journal of Materials, Processes and Environment, vol. 4, pp.113-118, 2016.
[14] T. Benhalima, H. Ferfera-Harrar, D. Lerari, “Optimization of carboxymethyl cellulose hydrogels beads generated by an anionic surfactant micelle templating for cationic dye uptake: Swelling, sorption and reusability studies”, Int. J. Biol. Macromol., vol. 105, pp. 1025-1042, 2017.
[15] T. Benhalima, H. Ferfera-Harrar, “Eco-friendly porous carboxymethyl cellulose/dextran sulfate composite beads as reusable and efficient adsorbents of cationic dye methylene blue”, Int. J. Biol. Macromol., vol. 132, pp. 126-141, 2019.
[16] H. Ferfera-Harrar, N. Dairi, “Elaboration of cellulose acetate nanobiocomposites using acidified gelatin-montmorillonite as nanofiller: Morphology, properties, and biodegradation studies”, Polym. Composite, vol. 34, pp.1515–1524, 2013.
[17] Y. T. Xie, A. Q. Wang, “Preparation and Swelling Behaviour of Chitosan-g-poly(acrylic acid)/Muscovite Superabsorbent Composites”; Iran. Polym. J., vol. 19, pp. 131-141, 2010.
[18] J. Zhang, Q. Wang, A. Wang, “Synthesis and characterization of chitosan-g-poly(acrylicacid)/attapulgite superabsorbent composites”, Carbohyd. Polym., vol. 68, pp. 367-374, 2007.
[19] S. K. Lagergren, “About the theory of so-called adsorption of soluble substances”, Sven Vetenskapsakad Handingarl., vol. 24 pp.1–39, (1898).
[20] Y.S. Ho, G. Mckay, “Pseudo-second order model for sorption processes”, Process Biochem., vol. 34, pp. 451-465, 1999.
[21] R.R. Pawar, Lalhmunsiama, P. Gupta, S.Y. Sawant, B. Shahmoradi, S.M. Lee, Porous synthetic hectorite clay-alginate composite beads for effective adsorption of methylene blue dye from aqueous solution., Int. J. Biol. Macromol., vol. 114, pp.1315–1324, 2018.
[22] M. V. Nagarpita, P. Roy, S. B. Shruthi, “Synthesis and swelling characteristics of chitosan and CMC grafted sodium acrylate-co-acrylamide using modified nanoclay and examining its efficacy for removal of dyes”, Int. J. Biol. Macromol., vol. 102, pp. 1226-1240, 2017.
[23] S. Han, T. Wang, B. Li, “Preparation of a hydroxyethyl-titanium dioxide-carboxymethyl cellulose hydrogel cage and its effect on the removal of methylene blue”, J. Appl. Polym. Sci. vol. 134, pp.44925, 2017.
[24] H.M. F. “Freundlich, Uber die adsorption in losungen”, Z. Phys. Chem., vol. 57, pp. 385–470, 1906.
[25] I. Langmuir, “The adsorption of gases on plane surface of glass, Mica and Platinum”, J. Am. Chem. Soc., vol. 40, pp. 1361–1403, 1918.
[26] S. Dawood, T.K. Sen, “Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design”, Water Res., vol. 46, pp.1933–1946, 2012.