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Document Type : Original Article


Department of Textile Engineering, Amirkabir University of Technology, Tehran, Iran.


In this study, the adsorption performance of a modified halloysite for the removal of anionic dye (C.I. Acid Blue 92) was demonstrated. Halloysite was modified in a multistep process by the synthesis of amine terminated dendritic structures on its surface. The transmission electron microscopy images were used to characterize the nanotubes forms of pristine halloysite. The adsorption processes were performed using classical and statistical response surface methodology (RSM) techniques. The effect of important parameters such as pH, adsorbent concentration, and dye dosage was investigated. The results showed that all the independent factors except time were significant to the dye removal efficiency. The dye removal at equilibrium time was well fitted to the Langmuir isotherm model and followed the monolayer adsorption style. The adsorption rate was also described by the pseudo-second-order kinetic model. The adsorption process revealed an exothermic behavior according to the thermodynamic investigations. The removal efficiency of AB92 improved significantly from 8% to 97% after modification.


[1] A.F. Peixoto, A.C. Fernandes, C. Pereira, J. Pires, and C. Freire, “Physicochemical characterization of organosilylated halloysite clay nanotubes”, Micropor. Mesopor. Mater., vol. 219, pp. 145-154, 2016.
[2] Y.M. Chen, L. Yu, and X.W.D. Lou, “Hierarchical tubular structures composed of Co3O4 hollow nanoparticles and carbon nanotubes for lithium storage”, Angew. Chem., Int. Ed., doi:10.1002/ ange.201600133.
[3] Y.M. Lvov, D.G. Shchukin, H. Mohwald, and R.R. Price, “Halloysite clay nanotubes for controlled release of protective agents”, ACS Nano, vol. 2, pp. 814-820, 2008.
[4] G. Cavallaro, “Innovative smart materials designed for environmental purposes”, ph.D dissertation, University of Palermo, Sicily, 2013.
[5] M.T. Dodd, D.A. Jakubovic, C.D. Putman, M.R. Sine, C.P. Thomas, and K.S. Wei, “Skin sanitizing compositions”, EP1152743A1, 2001.
[6] C.K. Choo, X.Y. Kong, T.L. Goh, G.C. Ngoh, B.A. Horri, and B. Salamatinia, “Chitosan/halloysite beads fabricated by ultrasonic-assisted extrusion-dripping and a case study application for copper ion removal”, Carbohyd. Polym., vol. 138, pp. 16-26, 2016.
[7] D. Papoulis, D. Panagiotaras, P. Tsigrou, K. Christoforidis, C. Petit, A. Apostolopoulou et al., “Halloysite and sepiolite-TiO2 nanocomposites: synthesis characterization and photocatalytic activity in three aquatic wastes”, Mat. Sci. Semicon. Proc., vol. 85, pp. 1-8, 2018.
[8] D. Papoulis, “Halloysite based nanocomposites and photocatalysis: a review”, Appl. Clay Sci., vol. 168, pp. 164-174, 2019.
[9] E. Joussein, S. Petit, J. Churchman, B. Theng, D. Righi, and B. Delvaux, “Halloysite clay minerals-a review”, Clay Miner., vol. 40, pp. 383-426, 2005.
[10] C. Chao, J. Liu, J. Wang, Y. Zhang, B. Zhang, Y. Zhang et al., “Surface modification of halloysite nanotubes with dopamine for enzyme immobilization”, ACS Appl. Mater. Inter., vol. 5, pp. 10559-10564, 2013.
[11] F. Shahamati Fard, S. Akbari, E. Pajootan, and M. Arami, “Enhanced acidic dye adsorption onto the dendrimer-based modified halloysite nanotubes”, Desalin. Water Treat., vol. 57, no. 54, pp. 1-18, 2016.
[12] S. Rooj, A. Das, V. Thakur, R. Mahaling, A.K. Bhowmick, and G. Heinrich, “Preparation and properties of natural nanocomposites based on natural rubber and naturally occurring halloysite nanotubes”, Mater. Design, vol. 31, pp. 2151-2156, 2010.
[13] R. Kamble, M. Ghag, S. Gaikawad, and B.K. Panda, “Halloysite nanotubes and applications: a review”, J. Adv. Sci. Res., vol. 3, no. 2, pp. 25-29, 2012.
[14] S. Cataldo, G. Lazzara, M. Massaro, N. Muratore, A. Pettignano, and S. Riela, “Functionalized halloysite nanotubes for enhanced removal of lead (II) ions from aqueous solutions”, Appl. Clay Sci., vol. 156, pp. 8795, 2018.
[15] J. Zhang, D. Zhang, A. Zhang, Z. Jia, and D. Jia, “Dendritic polyamidoamine-grafted halloysite nanotubes for fabricating toughened epoxy composites”, Iran. Polym. J., vol. 22, pp. 501-510, 2013.
[16] B. Theng, M. Russell, G. Churchman, and R. Parfitt, “Surface properties of allophane, halloysite, and imogolite”, Clay. Clay Miner., vol. 30, pp. 143-149, 1982.
[17] C.L. Grady Jr, G.T. Daigger, N.G. Love, and C.D. Filipe, Biological Wastewater Treatment: CRC Press, 2011.
[18] E. Riser-Roberts, Remediation of Petroleum Contaminated Soils: Biological, Physical, and Chemical Processes: CRC Press, 1998.
[19] M.A. Bezerra, R.E. Santelli, E.P. Oliveira, L.S. Villar, and L.A. Escaleira, “Response surface methodology (RSM) as a tool for optimization in analytical chemistry”, Talanta, vol. 76, pp. 965-977, 2008.
[20] B. Noroozi, G. Sorial, H. Bahrami, and M. Arami, “Equilibrium and kinetic adsorption study of a cationic dye by a natural adsorbent-silkworm pupa”, 
J. Hazard. Mater., vol. 139, pp. 167-174, 2007.
[21] N.G. Veerabadran, R.R. Price, and Y.M. Lvov, “Clay nanotubes for encapsulation and sustained release of drugs”, Nano, vol. 2, pp. 115-120, 2007.
[22] S. Levis and P. Deasy, “Characterisation of halloysite for use as a microtubular drug delivery system”, Int. J. Pharm., vol. 243, pp. 125-134, 2002.
[23] L. Liu, Y. Wan, Y. Xie, R. Zhai, B. Zhang, and J. Liu, “The removal of dye from aqueous solution using alginate-halloysite nanotube beads”, Chem. Eng. J., vol. 187, pp. 210-216, 2012.
[24] M. Bhaumik, R.I. McCrindle, A. Maity, S. Agarwal, and V.K. Gupta, “Polyaniline nanofibers as highly effective re-usable adsorbent for removal of reactive black 5 from aqueous solutions”, J. Colloid Interface Sci., vol. 466, pp. 442-451, 2016. [25] T. Anirudhan and M. Ramachandran, “Adsorptive removal of basic dyes from aqueous solutions by surfactant modified bentonite clay (organoclay): Kinetic and competitive adsorption isotherm”, Process Saf. Environ., vol. 95, pp. 215-225, 2015.
[26] J. Fu, Z. Chen, M. Wang, S. Liu, J. Zhang, J. Zhang et al., “Adsorption of methylene blue by a highefficiency adsorbent (polydopamine microspheres): kinetics, isotherm, thermodynamics and mechanism analysis”, Chem. Eng. J., vol. 259, pp. 53-61, 2015.
[27] D.A. Giannakoudakis, G.Z. Kyzas, A. Avranas, and N.K. Lazaridis, “Multi-parametric adsorption effects of the reactive dye removal with commercial activated carbons”, J. Mol. Liq., vol. 213, pp. 381-389, 2016.
[28] F. Gomri, M. Boutahala, H. Zaghouane-Boudiaf, S.A. Korili, and A. Gil, “Removal of acid blue 80 from aqueous solutions by adsorption on chemical modified bentonites”, Desalin. Water Treat., pp. 1-10, 2016.
[29] T. Madrakian, A. Afkhami, and M. Ahmadi, “Adsorption and kinetic studies of seven different organic dyes onto magnetite nanoparticles loaded tea waste and removal of them from wastewater samples”, Spectrochim. Acta A: Mol. Biomol. Spectrosc., vol. 99, pp. 102-109, 2012.
[30] M. Viseras, C. Aguzzi, P. Cerezo, C. Viseras, and C. Valenzuela, “Equilibrium and kinetics of 5-aminosalicylic acid adsorption by halloysite”, Micropor. Mesopor. Mat., vol. 108, pp. 112-116, 2008.
[31] R. Liu, B. Zhang, D. Mei, H. Zhang, and J. Liu, “Adsorption of methyl violet from aqueous solution by halloysite nanotubes”, Desalination, vol. 268, pp. 111-116, 2011.