Preparation of a Novel Magnetic Nanocomposite Hydrogel Based on Carboxymethyl Chitosan for the Adsorption of Crystal Violet as Cationic Dye

Document Type: Original Article


1 Department of Chemistry, Tabriz Branch, Islamic Azad University, Tabriz, Iran

2 Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran


The novel magnetic carboxymethyl chitosan/poly (acrylic amide) hydrogel (m-CMC-PAMH) was prepared using magnetic montmorillonite (m-MMT) and characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) techniques. Results showed that m-CMC-PAMH has been prepared successfully properties without damaging the crystal structure of Fe3O4. Adsorption capacity of Crystal Violet (CV) on the m-CMC-PAMH was 72.4 mg/g. The CV adsorption well described by the pseudo-second-order kinetics and Langmuir isotherm equations. The positive value of the enthalpy change ΔH° (23.5 kJ/mol) showed that the adsorption was endothermic and physical in nature. The value of Gibbs free energy change ΔG° was found to be -9.7 kJ/mol at 295 K for m-CMC-PAMH, which shows spontaneity of the CV adsorption. So, m-CMC-PAMH can be used as a low-cost alternative to other adsorbents for the removal of dyes from aqueous solutions.


1. Singh V., Sharma A.K., Sanghi R., 2009.  Poly (acrylamide) functionalized chitosan: an efficient adsorbent for azo dyes from aqueous solutions. J Hazard Mater. 166 , 327-335.

2. Chatterjee S., Lee M.W., Woo S.H., 2010 Adsorption of Congo Red by chitosan hydrogel beads impregnated with carbon nanotubes. Bioresour Technol. 101, 1800-1806.

3. Idaka E., Ogawa T., Yatome C., Horitsu H., 1985. Behavior of activated sludge with dyes. Bull Environ. Contam Toxicol. 35, 729-734.

6. Zahrim A.Y., Tizaoui C., Hilal N., 2011. Coagulation with polymers for nanofiltration pre-treatment of highly concentrated dyes: a review, Desalination. 266, 1-16.

7. Wan Ngah W.S., Teong L.C., Hanafiah M.A.K.M., 2011, Adsorption of dyes and heavy metal ions by chitosan composites: A review, Carbohydr Polym. 83, 1446-1456.

8. Gozmen B., Kayan B., Gizir A.M., Hesenov A., 2009. Oxidative degradations of reactive blue 4 dye by different advanced oxidation methods. J Hazard Mater. 168, 129-136.

9. Li S., 2010, Removal of crystal violet from aqueous solution by sorption into semi-interpenetrated networks hydrogels constituted of poly (acrylic acid-acrylamide-methacrylate) and amylose. Bioresour Technol. 101, 2197-2202.

10. Srinivasan A., Viraraghavan T., 2010. Decolorization of dye wastewaters by biosorbents: a review. J Environ Manage. 91, 1915-1929.

11. Gholami M., Vardini M.T., Mahdavinia G.R., 2016. Investigation of the effect of magnetic particles on the Crystal Violet adsorption onto a novel nanocomposite based on k-carrageenan-g-poly (methacrylic acid), Carbohydr Polym. 136, 772-781.

12. Debrassi A., Correa A.F., Baccarin T., Nedelko N., Slawska-Waniewska A., Sobczak K., 2012. Removal of cationic dyes from aqueous solutions using N-benzyl-O-carboxymethyl chitosan magnetic nanoparticles. Chem Eng J. 183, 284-293.

13. Mahdavinia G.R., Aghaie H., Sheykhloie H., Vardini M.T., Etemadi H., 2013. Synthesis of CarAlg/MMt nanocomposite hydrogels and adsorption of cationic Crystal Violet. Carbohydr Polym. 98, 358-365.

14. Bardajee G.R., Pourjavadi A., Ghavami S., Soleyman R., Jafarpour F., 2011. UV-prepared salep-based nanoporous hydrogel for controlled release of tetracycline hydrochloride in colon. J Photochem Photobiol B. 102, 232-240.

15. Zhu H.Y., Fu Y.Q., Jiang R., Jiang J.H., Xiao L., Zeng G.M., Zhao S.L., Wang Y., 2011. Adsorption removal of Congo Red onto magnetic cellulose/Fe3O4/activated carbon composite: Equilibrium, kinetic and thermodynamic studies. Chem Eng J. 173, 494-502.

16. Sari M., Akgol S., Karatas M., Denizli A., 2006. Reversible immobilization of catalase by metal chelate affinity interaction on magnetic beads. Ind Eng Chem Res. 45, 3036-3043.

17. Akutsu J., Tojo Y., Segawa O., Obata K., Okochi M., Tajima H., 2004. Development of an integrated automation system with a magnetic bead-mediated nucleic acid purification device for genetic analysis and gene manipulation. Biotechnol Bioeng. 86, 667-671.

18. Singh K., Gupta S., Singh A.K., Sinha S., 2011. Optimizing adsorption of Crystal Violet dye from water by magnetic nanocomposite using response surface modeling approach. J Hazard Mater. 186, 1462-1473.

19. Wang L., Wang A., 2007. Removal of Congo Red from aqueous solution using a chitosan/organo-montmorillonite nanocomposites. J Chem Technol Biotechnol. 82, 711-720.

20. Islam A.M., Phillips G.O., Sljivo A., Snowden M.J., Williams P.A., 1997. A review of recent developments on the regulatory, structural and functional aspects of gum Arabic. Food Hydrocolloid. 11, 493-505.

21. Aoki H., Al-Assaf S., Katayama T., Phillips G.O., 2007. Characterization and properties of Acacia Senegal (L.) Willd. Var. Senegalwith enhanced properties (Acacia (sen) SUPER GUM™): Part 2-Mechanism of the maturation process. Food Hydrocolloid. 21, 329-337.

22. Said H.M., Alla S.G.A., El-Naggar A.W.M., 2004. Synthesis and characterization of novel gels based on carboxymethyl cellulose/acrylic acid prepared by electron beam irradiation. React Funct Polym. 61, 397-404.

23. Zhai M., Yoshii F., Kume T., Hashim K., 2002. Syntheses of PVA/starch grafted hydrogels by irradiation. Carbohydr Polym. 50, 295-303.

24. Lugao A.B., Malmonge S.M., 2001. Use of radiation in the production of hydrogels, Nucl. Instrum. Methods Phys Res Sect B. 185, 37-42.

25. Spinelli L.S., Aquino A.S., Lucas E., d'Almeida, A.R.,  Leal R., Martins A.L., 2008. Adsorption of polymers used in drilling fluids on the inner surfaces of carbon steel pipes. Polym Eng Sci. 48, 1885-1891.

26. Bajpai A.K., Shukla S.K., Bhanu S., Kankane S., 2008. Responsive polymers in controlled drug delivery. Prog Polym Sci. 33, 1088-1118.

27. Aoki H., Katayama T., Ogasawara T., Sasaki Y., Al-Assaf S., Phillips G.O., 2007. Characterization and properties of Acacia senegal (L.) Willd. Var. Senegal with enhanced properties (Acacia (sen) SUPER GUM): Part 5. Factors affecting the emulsification of Acacia Senegal and Acacia (sen) SUPER GUM™. Food Hydrocolloid. 21, 353-358.

28. Tang S.C.N., Lo I.M.C., 2013. Magnetic nanoparticles: Essential factors for sustainable environmental applications. Water Res. 47, 2613-2632.

29. Mahdavinia G.R., Bagheri Marandi G., Pourjavadi A., Kiani G., 2010. Semi-IPN Carrageenan-based nanocomposite hydrogels: synthesis and swelling behavior. J Appl Polym Sci. 118, 2989-2997.

30. Mahdavinia G.R., Zohuriaan-Mehr M.J., Pourjavadi A., 2004. Modified chitosan III, superabsorbency, salt- and pH-sensitivity of smart ampholytic hydrogels from chitosan-g-PAN. Polym Adv Technol. 15, 173-180.

31. Al-Degs Y.S., Barghouthi M.I., El-Sheikh A.H., Walker G.M., 2007. Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon. Dyes Pigm. 77, 16-23.

32. Ho Y.S., Mckay G., 1999. Pseudo-second order for sorption processes. Process Biochem. 34, 451-465.

33. Foo K.Y., Hameed B.H., 2010. Insights into the modeling of adsorption isotherm systems. Chem Eng J. 156, 2-10.

34. Ho Y.S., McKay G., 2003. Sorption of dyes and copper ions onto biosorbents. Process Biochem. 38, 1047-1061.

35. Liu Y., 2009. Is the free energy change of adsorption correctly calculated?, J Chem Eng Data. 54, 1981-1985.

36. Porkodi K., Kumar K.V., 2007. Equilibrium, kinetics and mechanism modeling and simulation of basic and

acid dyes sorption onto jute fiber carbon: Eosin yellow, malachite green and crystal violet single component systems. J Hazard Mater. 143, 311-327.

37. Saeed A., Sharif M., Iqbal M., 2010. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption. J Hazard Mater. 179, 564-572.

38. Shirsath S.R., Hage A.P., Zhou M., Sonawane S.H., Ashokkumar M., 2011. Ultrasound assisted preparation of nanoclay Bentonite-FeCo nanocomposite hybrid hydrogel: A potential responsive sorbent for removal of organic pollutant from water. Desalination. 281, 429-437.

39. Mahdavinia G.R., Massoumi B., Jalili K., Kiani G., 2012. Effect of sodium montmorillonite nanoclay on the water absorbency and cationic dye removal of carrageenan-based nanocomposite superabsorbents. J Polym Res. 19, 9947-9959.

 40. Pourjavadi A., Hosseini S.H., Seid F.i, Soleyman R., 2013. Magnetic removal of crystal violet from aqueous solutions using polysaccharide-based magnetic nanocomposite hydrogels. Polym Int. 62, 1038-1044.