Removal of methylene blue from aqueous solutions by beta-cyclodextrin / Zinc oxide composite

Document Type : Complete scientific research article


1 Department of Chemistry, Payam Noor University, Tehran, Iran

2 Assistant Professor, Department of Chemistry, Payame Noor Universtiy, PO BOX 19395-3697 Tehran, IRAN


BACKGROUND AND OBJECTIVE: The high use of pesticides in agriculture and the entry of some of these compounds in water and products has led to one of the main strategies in agriculture, increasing the health of the community using less pesticides and, consequently, producing a healthy product and in the future, isolation of pesticides in contaminated water before release in the environment. The poison in agriculture is a chemical substance designed to kill pests. The poison in the food chain is sometimes condensed up to many thousand times, and most of them, especially if they have an aromatic ring, cannot be easily decomposed. The purpose of the study was to remove methylene blue from aqueous solution by beta-cyclodextrin / Zinc oxide composite.

MATERIALS AND METHODS: Beta-cyclodextrin / Zinc oxide nanocomposite was synthesized by sol-gel method in aqueous solution under nitrogen atmosphere and successfully identified using FTIR, SEM and XRD techniques. The maximum methylene blue absorbance wavelength was determined using a UV-VIS spectrophotometer and a range of 400 to 800 nm wavelength range at 665 nm. The methylene blue adsorption on β-cyclodextrin /Zinc oxide composite was evaluated discontinuously. The initial pH (1, 4, 7, 9 and 12), the initial amount of adsorbent (0.005, 0.01, 0.015 and 0.02 grams), the initial methylene blue concentration (5, 10, 20 and 30 mg/L), and contact time up to 40 minutes as well as the desorption process were studied. Langmuir, Freundlich, and Tempkin isotherm adsorption models were investigated. Experimental data were studied with different kinetic models. Thermodynamic parameters in surface adsorption including Gibbs free energy change (ΔG0), entropy change (ΔS0) and enthalpy change (ΔH0) were measured by examining the adsorption process at several different temperatures.

RESULTS: The lowest amount of adsorption was observed at pH 7 and highest in acidic pH=1. It seems that increasing methylene blue adsorption in acidic pH is due to the conversion of the pigment to anion, which results in more potent adsorption. Up to 15 minutes after the start of the process, adsorption is performed at more and then performed at a lower rate. The adsorption takes to equilibrium after 30 minutes. The maximum adsorption capacity occurs at a concentration of 5 milligrams per liter than the contaminant in the presence of 0.005 grams per liter of absorbent material at 20 degrees Celsius. The process of adsorption is accompanied by the reduction of entropy. The thermodynamic constants of ΔH0 and ΔS0 are 55.15 kJ / mol and 195.62 j/k.mol respectively. At 20 ° C, the amount of ΔG0 is 2131.65 j/k.mol and increases with increasing temperature up to 37 ° to 5457.19 j/k.mol. The Tempkin isotherm has a good correlation with experimental data with a correlation coefficient of 0.9818 and a constant KT of 0.493. The kinetic model of pseudo-second order with a correlation coefficient of 0.9578 and a constant speed of 0.07 min-1M-1 is a suitable kinetic model for describing absorption.


1.Ayad, M.M., and El-Nasr, A.A. 2010. Adsorption of Cationic Dye (Methylene Blue) from Water Using Polyaniline Nanotubes Base. J. Phys. Chem. C.114: 34. 14377-14383.
2.Banerjee, S.S., and Chen, D.H. 2007. Fast removal of copper ions by gum Arabic modified magnetic nano-adsorbent.
J. Hazard. Mater. 147: 3. 792-799.
3.Chen, Y., Ma, Y., Lu, W., Guo, Y.,Zhu, Y., Lu, H., and Song, Y. 2018. Environmentally Friendly Gelatin/b-Cyclodextrin Composite Fiber Adsorbents for the Efficient Removal of Dyes from Wastewater. Molecules. 23: 2473-2490.
4.Colak, F., Atar, N., and Olgun, A. 2009. Biosorption of acidic dyes from aqueous solution by paenibacillus macerans: Kinetic, thermodynamic and equilibrium studies. J. Chem. Eng. 150: 1. 122-130.
5.Damalas, C.A., and Eleftherohorinos, I.G. 2011. Pesticide Exposure, Safety Issues, and Risk Assessment Indicators. Int. J. Environ. Res. Public Health. 8: 1402-1419.
6.Dehaghi, S.M., Rahmanifar, B., Mashinchian Moradi, A., and Aberoomand Azar, P. 2014. Removal of permethrin pesticide from water by chitosan-zinc oxide nanoparticles composite as an adsorbent. J. Saudi Chem. Soc.18: 348-355.
7.El Nemr, A. 2009. Potential of pomegranate husk carbon for Cr(VI) removal from wastewater: Kinetic and isotherm studies. J. Hazard. Mater.161: 1. 132-141.
8.Iram, M., Guo, C.Y., and Guan, Y. 2010. Adsorption and magnetic removal of neutral red dye from aqueous solution using Fe3O4 hollow nanospheres. J. Hazard. Mater. 181: 1039-1050.
9.Kakavandi, B., Jonidi, A., Rezaei, R., Nasseri, S., Ameri, A., and Esrafili, A. 2013. Synthesis and Properties of Fe3O4 activated carbon magnetic nanoparticles for removal of aniline from aqeous solution: Equilibrium, Kinetic and thermodynamic studies. J. Environ. Health Sci. Engin. 10: 1-9.
10.Khashei-Siuki, A., Shahidi, A., Taherian, P., and Zeraatkar, Z. 2017. Exploring the possibility of removing chromium (IV) from aqueous solution using zeolite clinoptilolite. J. Water Soil Cons. 24: 4. 243-258. (In Persian)
11.Lima, E.C., Royer, B., Vaghetti, J.C.P., Simon, N.M., Cunha, B.M., Pavan, F.A., Benvenutti, E.V., Catalunaveses, R., and Airoldi, C. 2008. Application of Brazilian pine-fruit shell as a biosorbent to removal of reactive red 194 textile dye from aqueous solution kinetics and equilibrium study. J. Hazard. Mater. 155: 536-550.
12.Liu, L., Fan, S., and Li, Y. 2018. Removal Behavior of Methylene Blue from Aqueous Solution by Tea Waste: Kinetics. Isotherms and Mechanism, Inter. J. Environ. Res. Pub. Health.15: 1321-1336.
13.Loftsson, T., and Masson, M. 2001. Cyclodextrins in Topical Drug Formulations: Theory and Practice. Int. J. Pharm. 225: 15-30.
14.Madaeni, S.S., and Salehi, E. 2009. Adsorption of cations on nanofiltration membrane: Separation mechanism, isotherm confirmation and thermodynamic analysis. J. Chem. Engin. 150: 1. 114-130.
15.Massoudi Nejad, M.R., Khashij, M., and Soltanian, M. 2014. Survey of Electrocoagulation Process in the Removal of Pathogen Bacteria from wastewater before Discharge in the Acceptor Water. J. Prom. Int. Pre.2: 1. 9-14. (In Persian)
16.Mosafer, E., and Rezaei, B. Adsorption of Cadmium from aqueous solutions using modified silicon dioxide nanoparticles. J. Water Soil Cons.24: 4. 179-193. (In Persian)
17.Mousavi, S.H., and Mohammadi, A. 2018. A cyclodextrin/glycine-functionalized TiO2 nanoadsorbent: Synthesis, characterization and application for the removal of organic pollutants from water and real textile wastewater, Process Safety and Environmental Protection. 114: 1-15.
18.Paul, J., Rawat, K.P., Sarma, K.S.S., and Sabharwal, S. 2011. Decoloration and degradation of Reactive Red 120 dye by electron beam  irradiation in aqueous solution, Applied Radiation and Isotopes. 69: 982-987.
19.Ponnusami, V., Madhuram, R., Krithika, V., and Srivastava, S.N. 2008. Effectsof process Variables on Kinetics of Methylene Blue Sorption onto Untreated Guava (psidium guajava) Leaf Powder: Statistical Analysis. Chem. Engin. J. 140: 609-617.
20.Rezaee-Mofrad, M.R., Miranzadeh, M.B., Pourgholi, M., Akbari, H., and Dehghani, R. 2013. Evaluating the efficiency of advanced oxidation methods on dye removal from textile wastewater. J. Kashan Univ. Med. Sci. 17: 1. 12-19. (In Persian)
21.Royer, B., Cardoso, N.F., Lima, E.C., Vaghetti, J.C.P., Simon, N.M., Calvete, T., and Veses, R.C. 2009. Applications of Brazilian-pine fruit shell in natural and carbonized forms as adsorbents to removal of methylene blue from aqueous solutions- kinetic and equilibrium study . J. Hazard. Mater. 164: 1213-1222.
22.Saeed, S.M., Zandi, M., and Mirzadeh, H. 2012. Effect of solution surface tension on morphology of PLGA and gelatin electrospun fibers. Iran. J. Polymer Sci. Technol. 25: 3-10.
23.Sánchez-Bayo, F., Van den Brink, P.J., and Mann, R.M. 2011. Ecological Impacts of Toxic Chemicals, P 63-87, Bentham Science Publishers Ltd.(Eds), Impacts of Agricultural Pesticides on Terrestrial Ecosystems. Centre for Ecotoxicology, University of Technology Sydney, Australia.
24.Shaban, M., Abukhadraa, M.R., Parwaz Khan, A.A., and Jibali, B.M. 2017. Removal of Congo red, methylene blue and Cr (VI) ions from water using natural serpentine. J. Taiwan Inst. Chem. Engin. 18: 1-15.
25.Srinivasa, R.K., Chaudhury, R.G., and Mishra, B.K. 2010. Kinetics and equilibrium studies for the removal of cadmium ions from aqueous solutions using Duolite ES 467 resin. J. Miner. Process. 97: 68-73.
26.Wang, H., Baek, S., Lee, J., and Lim, S. 2009. High photocatalytic activity of Silver-loaded Zno-SnO2 Coupled catalysts. Chem. Engin. J. 146: 355-361.
27.Ways, T.M.M., Lau, W.M., and Khutoryanskiy, V.V. 2018. Chitosan and its derivatives for application in
muco-adhesive drug delivery systems. Polymers. 10: 3. 267-305.