In Situ Synthesis of Chitosan-Grafted Polyacrylamide Loaded by TiO2 Nanoparticles for the Adsorption of Sirius Yellow K-CF from Aqueous Media: Isotherm, Kinetic and Thermodynamic Studies

Document Type : Research Paper


1 Assoc. Prof. of Chemical Engineering, Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr, Iran

2 PhD Student of Chemical Engineering, Department of Chemical Engineering, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran

3 Assist. Prof. of Textile Engineering, Department of Textile Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr, Iran

4 Assist. Prof. of Chemical Engineering, Department of Chemical Engineering, Imam Muhammad Bagher Technical University, Sari, Iran


Toxic waste water and infected water are the considerable sources of environmental contaminations . Dyes as the source of toxicity of waste water are used in various industries like dyestuff, textile, paper, plastics and pharmaceutical. Recently, reactive dyes have been commonly used because of their advantages such as better dyeing processing conditions and bright colors. So, removal of dyes from effluents is so important.  Among the materials used as the common adsorbents, chitosan and polyacrylamide are relatively cheap and the promising materials can be used as adsorbents. In the present study, TiO2 nanoparticles dispersed in chitosan grafted polyacrylamide matrix was synthesized by in situ method and used for the removal of Sirius yellow K-CF dye from aqueous solution. The synthesized nano-composite was characterized by FE-SEM, TEM, XRD and FT-IR. The effect of pH, adsorbent dosage, time and temperature were investigated. The results showed that the highest dye removal efficiency was happended in the acidic pH of 2 with 0.05 g of TiO2-PAA-Ch adsorbent. The equilibrium data were compatible very well with the Langmuir isotherm (qm=1000 mg/g, 96.81% of dye removal). The Dubinin-Radushkevich isotherm and thermodynamic studies proved that the adsorption process is physical, endothermic and spontaneous. Kinetic study verifies that pseudo second order kinetic model is the predominant model. In this study, TiO2 nanoparticles dispersed in polymer matrix was synthesized and employed for the removal of Sirius yellow K-CF from aqueous media. Electrostatic attraction between positive charges of adsorbent surface (NH3+) and molecules of anionic dye together with formation of hydrogen bond (Dye-NH3+) cause the adsorption of dye on PAA-Ch. On the other hand, Ti+4 in PAA-Ch structure can intract with the anionic molecules through the electrostatic adsorption. The results of this study interact that the new synthesized TiO2-PAA-Ch composite with high amount of NH2 functional groups and Ti+4 is an efficient adsorbent for an environmental applications to remove many contaminants, dyes and organic pollutants.


Main Subjects

 Akkaya, R. & Ulusoy, U. 2008. Adsorptive features of chitosan entrapped in polyacrylamide hydrogel for Pb2+, UO22+ and Th4+. Journal of Hazardous Materials, 151, 380-388.
Asouhidou, D. D., Triantafyllidis, K. S., Lazaridis., N. K. & Matis, K. A. 2009. Adsorption of  remazol red 3BS from aqueous solutions using APTES- and cyclodextrin-modified HMS-type mesoporous silicas. Colloids and Surfaces A: Physicochem. Engineering Aspects, 346, 83-90.
Binaeian, E., Seghatoleslami, N., Chaichi, M. J. & Tayebi, H. 2016. Preparation of titanium dioxide nanoparticles supported on hexagonal mesoporous silicate (HMS) modified by oak gall tannin and its photocatalyti performance in degradation of azo dye. Advanced Powder Technology, 27, 1047-1055.
Calvete, T., Lima, E. C., N.F., C., Silvio, L. P. D. & Flavio, A. P. 2009. Application of carbon adsorbents prepared from the Brazilian pine-fruit-shell for the removal of Procion red MX 3B from aqueous solution—kinetic,  equilibrium, and thermodynamic studies. Chemical Engineering Journal, 155, 627-636.
Cetinkaya, T., Neuwirthova, L., Kutlakova, K. M. T., V. & Akbulut, H. 2013. Synthesis of nanostructured TiO2/SiO2 as an effective photocatalyst for degradation of acid orange. Applied Surface Science, 279, 384-390.
Cho, D. W., Jeon, B. H., Chon, C. M., Schwartz, F. W., Jeong, Y. & Song, H. 2015. Magnetic chitosan composite for adsorption of cationic and anionic dyes in aqueous solution. Journal of Industrial and Engineering Chemistry, 28, 60-66.
Chun, H., Yizhong, W. & Hongxiao, T. 2001. Preparation and characterization of surface bond-conjugated TiO2/SiO2 and photocatalysis for azo dyes. Applied Catalysis B: Environmental , 30, 277-285.
Darvishi Cheshmeh Soltani, R., Khataee, A. R., Safari, M. & Joo, S. W. 2013. Preparation of bio-silica/chitosan nanocomposite for adsorption of a textile dye in aqueous solutions. International Biodeterioration and Biodegradation, 85, 383-391.
Gao, Q., Zhu, H., Luo, W. J., Wang, S. & Zhou, C. G. 2014. Preparation, characterization, and adsorption evaluation of chitosan-functionalized mesoporous composites. Microporous and Mesoporous Materials, 193, 15-26.
Ghasemi, Z., Younesi, H. & Zinatizadeh, A. 2016. Efficiency of immobilized nano TiO2 on Fe-ZSM-5 zeolite in organic pollutants removal from petroleum refinery wastewater. Journal of Water and Wastewater, 27 (2), 22-33. (In Persian)
Hashemzadeh, F., Hasani, A. H., Ahmad Panahi, H. & Borghei, S. M. 2018. Evaluation of the removal of heavy metals (cadmium lead, and zinc) from aqueous solutions using multi-walled carbon nanotubes modified with chitosan. Journal of Water  and Wastewater, 29 (3), 31-41. (In Persian)
Huang, X., Liao, X. & Shi, B. 2010. Tannin-immobilized mesoporous silica bead (BT–SiO2) as an effective adsorbent of Cr(III) in aqueous solutions.  Journal of Hazardous Materials, 173, 33-39.
Kamal, N. A. 2009. Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel: adsorption equilibrium and kinetic. Journal of Hazardous Materials, 165, 52-62.
Li, K., Wang, Y., Huang, M., Yan, H., Yang, H., Xiao, S et al. 2015. Preparation of chitosan-graft-polyacrylamide magnetic composite microspheres for enhanced selective removal of mercury ions from water. Journal of Colloid and Interface Science, 455, 261-270.
Liu, J., Ma, J. & Zang, L. 2013. Preparation and characterization of ammonium-functionalized silica  nanoparticle as a new adsorbent to remove methyl orange from aqueous solution. Applied Surface Science, 265, 393-398.
Mahdavinia, G. R. & Vijayalakshmi, P. 2017. Reparation and characterization of magnetic chitosan/κ-carrageenan nanocomposite and its application for removal of eriochrome black-t from aqueous solutions. Journal of Water and Wastewater, 29 (5), 12-26. (In Persian)
Rafiei, H. R. & Shirvani, M. 2016. Sorption of lead (Pb) from aqueous solutions by sepiolite and bentonite modified with chitosan biopolymers: isotherms and kinetics. Journal of Water  and Wastewater, 27 (3), 75-87. (In Persian)
Ramakul, P., Yanachawakul, Y., Leepipatpiboon, N. & Sunsandee, N. 2012. Biosorption of palladium (II) and platinum(IV) from aqueous  solution using tannin from indian almond (Terminalia catappa L.) leaf biomass: kinetic and equilibrium studies. Chemical Engineering Journal, 193, 102-111.
Ramezanpour, A. H., Farrokhian Firouzi, A., Sayyad, G. A. & Kiyasat, A. 2012. Investigation of Pb(II) removal from aqueous solutions using modified nano zero-valent iron particles.  Journal of Water and Wastewater, 25(2), 68-76. (In Persian)
Samarghandi, M. R., Nouri, J., Mesdaghinia, A. R., Mahvi, A. H., Nasseri, S. & Vaezi, F. 2007. Efficiency removal of phenol, lead and cadmium by means of UV/TiO2/H2O2, processes. International Journal of Environmental Science and Technology, 4, 19-25.
Sanchez-Martin, J., Beltran-Heredia, J. & J., G.-C. 2011. Caesalpinia spinosa and Castanea sativa tannins: a new source of biopolymers with adsorbent  capacity. preliminary assessment on cationic dye removal. Industrial Crops and  Products, 34, 1238-1240.
Senthil kumar, P., Ramalingam, S., Senthamarai, C., Niranjanaa, M., Vijayalakshmi, P. & Sivanesan, S. 2010. Adsorption of dye from aqueous solution by cashew nut shell: studies on equilibrium isotherm, kinetics and thermodynamics of interactions. Desalination, 261, 52-60.
Smitha, T., Santhi, T., Prasad, A. L. & Manonmani, S. 2012. Cucumis sativus  used as adsorbent for the removal of dyes from aqueous solution. Arabian Journal of  Chemistry, 38, 248-253.
Suparna, S., Priyabrata, S. 2012. Arsenic remediation from drinking water by synthesized nano-alumina dispersed in chitosan-grafted polyacrylamide. Journal of  Hazardous Materials, 228, 68-78.
Yurtsever, M. & Şengl, A. 2012. Adsorption and desorption behavior of  silver ions onto valonia tannin resin. Transactions of Nonferrous Metals Society of China, 22, 2846-2854.
Zhong, Q.-Q., Yue, Q.-Y., Li, Q., Xu, X. & Gao, B.-Y. 2011. Preparation,  characterization of modified wheat residue and its utilization for the anionic dye removal. Desalination, 267, 193-200.