Elucidating Adsorption Mechanisms of Copper Ions on Surfactant-Modified Zeolites: An Integrated Study of Isotherm Modeling and Surface Characterization

Kazemi, Razieh; Kasaei, Abbas

doi:10.22111/cpd.2026.52973.1073

Elucidating Adsorption Mechanisms of Copper Ions on Surfactant-Modified Zeolites: An Integrated Study of Isotherm Modeling and Surface Characterization

Document Type : Research Article

Authors

Department of Chemistry, Do.C., Islamic Azad University, Doroud, Iran.

10.22111/cpd.2026.52973.1073

Abstract

This research examines the adsorption mechanisms pertaining to copper ions on clinoptilolite zeolite that has been modified with cationic (CTAB) and anionic (SDS) surfactants. Given that the fundamental principles that dictate adsorption phenomena, particularly the influence of surfactant charge, are not thoroughly comprehended, this investigation adopts a comprehensive methodology that integrates isotherm modeling alongside surface characterization data to scrutinize the adsorption dynamics. Equilibrium data were subjected to analysis through a variety of isotherm models. The findings indicated that the SDS-modified zeolite demonstrated a significantly enhanced adsorption capacity (19.56 mg/g), which is more than twice that of the unmodified zeolite (8.98 mg/g). The adsorption behavior was most accurately represented by the Redlich-Peterson isotherm, with the observed performance improvement ascribed to the synergistic effects resulting from an increased specific surface area and favorable electrostatic interactions. In contrast, zeolite modified with CTAB exhibited a diminished adsorption capacity of 7.08 mg/g, while the Frumkin isotherm suggested the presence of repulsive interactions. For the unaltered zeolite, the Weber-van Vliet model yielded the most accurate representation, indicating a hybrid mechanism of adsorption. This research underscores the notion that the charge of the surfactant is a pivotal determinant of the adsorption mechanism. By disentangling the influences of surface area from electrostatic interactions, it establishes a quantitative framework for the development of effective adsorbents.

Keywords

References

[1] Briffa, J., Sinagra, E., Blundell, R., 2020. Heavy metal pollution in the environment and their toxicological effects on humans, Heliyon, 6, e04691. http://dx.doi.org/10.1016/j.heliyon.2020.e04691

[2] Ali, H., Khan, E., Ilahi, I., 2019. Environmental chemistry and ecotoxicology of hazardous heavy metals: Environmental persistence, toxicity, and bioaccumulation, Journal of Chemistry, 2019, 6730305. http://dx.doi.org/10.1155/2019/6730305

[3] El-Sherif, I.Y., Tolani, S., Ofosu, K., Mohamed, O.A., Wanekaya, A.K., 2013. Polymeric nanofibers for the removal of Cr(III) from tannery wastewater, Journal of Environmental Management, 129, 410-413. http://dx.doi.org/10.1016/j.jenvman.2013.06.001

[4] Tchounwou, P.B., Yedjou, C.G., Patlolla, A.K., Sutton, D.J., 2012. Heavy metal toxicity and the environment, Experientia Supplementum, 101, 133-164. http://dx.doi.org/10.1007/978-3-7643-8340-4_6

[5] Senila, M., Cadar, O., Senila, L., Hoaghia, A., Miu, I., 2019. Mercury determination in natural zeolites by thermal decomposition atomic absorption spectrometry: Method validation in compliance with requirements for use as dietary supplements, Molecules, 24, 4023. http://dx.doi.org/10.3390/molecules24244023

[6] Rahmany-Samani, A., Ghobadinia, M., Tabatabaei, S.-H., Nourmahnad, N., Danesh-Shahraki, A., 2023. The effect of irrigation and zeolite management on the reduction of cadmium accumulation in rice, Agricultural Water Management, 287, 108448. http://dx.doi.org/10.1016/j.agwat.2023.108448

[7] Kaya, C., Okant, M., Ugurlar, F., Alyemeni, M.N., Ashraf, M., Ahmad, P., 2019. Melatonin-mediated nitric oxide improves tolerance to cadmium toxicity by reducing oxidative stress in wheat plants, Chemosphere, 225, 627-638. http://dx.doi.org/10.1016/j.chemosphere.2019.03.026

[8] Zou, Y., et al., 2016. Environmental remediation and application of nanoscale zero-valent iron and its composites for the removal of heavy metal ions: A review, Environmental Science & Technology, 50, 7290-7304. http://dx.doi.org/10.1021/acs.est.6b00497

[9] Tjandraatmadja, G., et al., 2008. Sources of critical contaminants in domestic wastewater: Contaminant contribution from household products.

[10] Taseidifar, M., Makavipour, F., Pashley, R.M., Rahman, A.F.M.M., 2017. Removal of heavy metal ions from water using ion flotation, Environmental Technology & Innovation, 8, 182-190. http://dx.doi.org/10.1016/j.eti.2017.05.002

[11] García-Niño, W.R., Pedraza-Chaverrí, J., 2014. Protective effect of curcumin against heavy metals-induced liver damage, Food and Chemical Toxicology, 69, 182-201. http://dx.doi.org/10.1016/j.fct.2014.04.019

[12] Borba, C.E., Guirardello, R., Silva, E.A., Veit, M.T., Tavares, C.R.G., 2006. Removal of nickel(II) ions from aqueous solution by biosorption in a fixed bed column: Experimental and theoretical breakthrough curves, Biochemical Engineering Journal, 30, 184-191. http://dx.doi.org/10.1016/j.bej.2006.04.008

[13] Vardhan, K.H., Kumar, P.S., Panda, R.C., 2019. A review on heavy metal pollution, toxicity and remedial measures: Current trends and future perspectives, Journal of Molecular Liquids, 290, 111197. http://dx.doi.org/10.1016/j.molliq.2019.111197

[14] Kim, J.-J., Kim, Y.-S., Kumar, V., 2019. Heavy metal toxicity: An update of chelating therapeutic strategies, Journal of Trace Elements in Medicine and Biology, 54, 226-231. http://dx.doi.org/10.1016/j.jtemb.2019.05.003

[15] Qasem, N.A.A., Mohammed, R.H., Lawal, D.U., 2021. Removal of heavy metal ions from wastewater: A comprehensive and critical review, npj Clean Water, 4, 36. http://dx.doi.org/10.1038/s41545-021-00127-0

[16] Ugwu, E.I., Othmani, A., Nnaji, C.C., 2022. A review on zeolites as cost-effective adsorbents for removal of heavy metals from aqueous environment, International Journal of Environmental Science and Technology, 19, 8061-8084. http://dx.doi.org/10.1007/s13762-021-03560-3

[17] Hedstrom, A., 2001. Ion exchange of ammonium in zeolites: A literature review, Journal of Environmental Engineering, 127, 673-681. http://dx.doi.org/10.1061/(ASCE)0733-9372(2001)127:8(673)

[18] Kesraoui-Ouki, S., Cheeseman, C.R., Perry, R., 1994. Natural zeolite utilization in pollution control: A review of applications to metals effluents, Journal of Chemical Technology & Biotechnology, 59, 121-126. http://dx.doi.org/10.1002/jctb.280590202

[19] Caputo, D., Pepe, F., 2007. Experiments and data processing of ion exchange equilibria involving Italian natural zeolites: A review, Microporous and Mesoporous Materials, 105, 222-231. http://dx.doi.org/10.1016/j.micromeso.2007.04.024

[20] Shi, J., Yang, Z., Dai, H., Lu, X., Peng, L., Tan, X., Shi, L., Fahim, R., 2018. Preparation and application of modified zeolites as adsorbents in wastewater treatment, Water Science and Technology, 77, 621-635. http://dx.doi.org/10.2166/wst.2018.249

[21] Wang, S., Peng, Y., 2010. Natural zeolites as effective adsorbents in water and wastewater treatment, Chemical Engineering Journal, 156, 11-24. http://dx.doi.org/10.1016/j.cej.2009.10.029

[22] Ugwu, E.I., Othmani, A., Nnaji, C.C., 2022. A review on zeolites as cost-effective adsorbents for removal of heavy metals from aqueous environment, International Journal of Environmental Science and Technology, 19, 8061-8084. http://dx.doi.org/10.1007/s13762-021-03560-3

[23] Velarde, L., Nabavi, M.S., Escalera, E., Antti, M.L., Akhtar, F., 2023. Adsorption of heavy metals on natural zeolites: A review, Chemosphere, 328, 138508. http://dx.doi.org/10.1016/j.chemosphere.2023.138508

[24] Irannajad, M., Haghighi, H.K., 2021. Removal of heavy metals from polluted solutions by zeolitic adsorbents: A review, Environmental Processes, 8, 7-35. http://dx.doi.org/10.1007/s40710-020-00476-x

[25] Belviso, C., 2020. Zeolite for potential toxic metal uptake from contaminated soil: A brief review, Processes, 8, 820. http://dx.doi.org/10.3390/pr8070820

[26] Kallo, D., 2001. Applications of natural zeolites in water and wastewater treatment, In: Bish, D.L., Ming, D.W. (Eds.), Natural Zeolites: Occurrence, Properties, Applications, Mineralogical Society of America, Washington, DC, pp. 519-550.

[27] Bish, D.L., Ming, D.W., 2001. Applications of natural zeolites in water and wastewater treatment, In: Natural Zeolites: Occurrence, Properties, Applications, Mineralogical Society of America, Washington, DC, pp. 519-550.

[28] Krstić, V., 2021. Role of zeolite adsorbent in water treatment, In: Handbook of Nanomaterials for Wastewater Treatment, Elsevier, Amsterdam, pp. 417-481.

[29] Bouffard, S.C., Duff, S.J.B., 2000. Uptake of dehydroabietic acid using organically tailored zeolites, Water Research, 34, 2469-2476. http://dx.doi.org/10.1016/S0043-1354(99)00385-4

[30] Sullivan, E.J., Carey, J.W., Bowman, R.S., 1998. Thermodynamics of cationic surfactant sorption onto natural clinoptilolite, Journal of Colloid and Interface Science, 206, 369-380. http://dx.doi.org/10.1006/jcis.1998.5703

[31] Karadag, D., Akgul, E., Tok, S., Erturk, F., Kaya, M.A., Turan, M., 2007. Basic and reactive dye removal using natural and modified zeolites, Journal of Chemical & Engineering Data, 52, 2436-2441. http://dx.doi.org/10.1021/je700392e

[32] Karadag, D., Turan, M., Akgul, E., Tok, S., Faki, A., 2007. Adsorption equilibrium and kinetics of reactive black 5 and reactive red 239 in aqueous solution onto surfactant-modified zeolite, Journal of Chemical & Engineering Data, 52, 1615-1620. http://dx.doi.org/10.1021/je700107n

[33] Benkli, Y.E., Can, M.F., Turan, M., Celik, M.S., 2005. Modification of organo-zeolite surface for the removal of reactive azo dyes in fixed-bed reactors, Water Research, 39, 487-493. http://dx.doi.org/10.1016/j.watres.2004.10.008

[34] Bowman, R.S., 2003. Applications of surfactant-modified zeolites to environmental remediation, Microporous and Mesoporous Materials, 61, 43-56. http://dx.doi.org/10.1016/S1387-1811(03)00354-8

[35] Cortes-Martinez, R., Martinez-Miranda, V., Solache-Rios, M., Garcia-Sosa, I., 2004. Evaluation of natural and surfactant-modified zeolites in the removal of cadmium from aqueous solutions, Separation Science and Technology, 39, 2711-2730. http://dx.doi.org/10.1081/SS-200026784

[36] Cortes-Martinez, R., Solache-Rios, M., Martinez-Miranda, V., Alfaro-Cuevas, R., 2007. Sorption behavior of 4-chlorophenol from aqueous solutions by a surfactant-modified Mexican zeolitic rock in batch and fixed bed systems, Water, Air, and Soil Pollution, 183, 85-94. http://dx.doi.org/10.1007/s11270-006-9319-3

[37] Haggerty, G.M., Bowman, R.S., 1994. Sorption of chromate and other inorganic anions by organo-zeolite, Environmental Science & Technology, 28, 452-458. http://dx.doi.org/10.1021/es00052a015

[38] Kuleyin, A., 2007. Removal of phenol and 4-chlorophenol by surfactant-modified natural zeolite, Journal of Hazardous Materials, 144, 307-315. http://dx.doi.org/10.1016/j.jhazmat.2006.10.036

[39] Dakovic, A., Tomasevic-Canovic, M., Rottinghaus, G., Dondur, V., Masic, Z., 2003. Adsorption of ochratoxin A on octadecyldimethyl benzyl ammonium exchanged-clinoptilolite-heulandite tuff, Colloids and Surfaces B: Biointerfaces, 30, 157-165. http://dx.doi.org/10.1016/S0927-7765(03)00070-1

[40] Dakovic, A., Tomasevic-Canovic, M., Rottinghaus, G.E., Matijasevic, S., Sekulic, Z., 2007. Fumonisin B-1 adsorption to octadecyldimethylbenzyl ammonium-modified clinoptilolite-rich zeolitic tuff, Microporous and Mesoporous Materials, 105, 285-290. http://dx.doi.org/10.1016/j.micromeso.2007.03.029

[41] Dakovic, A., Matijasevic, S., Rottinghaus, G.E., Dondur, V., Pietrass, T., Clewett, C.F.M., 2007. Adsorption of zearalenone by organomodified natural zeolitic tuff, Journal of Colloid and Interface Science, 311, 8-13. http://dx.doi.org/10.1016/j.jcis.2007.02.033

[42] Ghiaci, M., Abbaspur, A., Kia, R., Seyedeyn-Azad, F., 2004. Equilibrium isotherm studies for the sorption of benzene, toluene, and phenol onto organo-zeolites and as-synthesized MCM-41, Separation and Purification Technology, 40, 217-229. http://dx.doi.org/10.1016/j.seppur.2004.03.003

[43] Lemic, J., Tomasevic-Canovic, M., Adamovic, M., Kovacevic, D., Milicevic, S., 2007. Competitive adsorption of polycyclic aromatic hydrocarbons on organo-zeolites, Microporous and Mesoporous Materials, 105, 317-323. http://dx.doi.org/10.1016/j.micromeso.2007.04.003

[44] Lemic, J., Kovacevic, D., Tomasevic-Canovic, M., Kovacevic, D., Stanic, T., Pfend, R., 2006. Removal of atrazine, lindane and diazinone from water by organo-zeolites, Water Research, 40, 1079-1085. http://dx.doi.org/10.1016/j.watres.2006.01.008

[45] Noroozifar, M., Khorasani-Motlagh, M., Abbaspur, A., 2005. Sorption of phenol from aqueous solutions by cetylpyridinium modified natural zeolite, Journal of Hazardous Materials, 124, 211-216. http://dx.doi.org/10.1016/j.jhazmat.2005.05.002

[46] Misaelides, P., Zamboulis, D., Sarridis, P., Warchol, J., Godelitsas, A., 2008. Chromium(VI) uptake by polyhexamethylene-guanidine-modified natural zeolitic materials, Microporous and Mesoporous Materials, 108, 162-167. http://dx.doi.org/10.1016/j.micromeso.2007.03.038

[47] Bagheri, A., Khabbaz, S.H., Rafati, A.A., 2024. Comparison of the natural and surfactant-modified zeolites in the adsorption efficiency of sunset yellow food dye from aqueous solutions, Scientific Reports, 14, 22511. http://dx.doi.org/10.1038/s41598-024-72515-8

[48] Ma, L., Chen, Q., Zhu, J., Xi, Y., He, H., Zhu, R., Tao, Q., Ayoko, G.A., 2016. Adsorption of phenol and Cu(II) onto cationic and zwitterionic surfactant modified montmorillonite in single and binary systems, Chemical Engineering Journal, 283, 880-888. http://dx.doi.org/10.1016/j.cej.2015.08.009

[49] Harutyunyan, L.R., Tangamyan, L.S., Manukyan, A.V., Harutyunyan, R.S., 2023. Characterization of both anionic and cationic surfactant-modified natural zeolite and its application for removal of metal-ions from aqueous medium, Voprosy Khimii i Khimicheskoi Tekhnologii, (2), 31-40. http://dx.doi.org/10.32434/0321-4095-2023-147-2-31-40

[50] Majidi Trojeni, M., Samadi-Maybodi, A., Shafiei, H., 2025. Investigating the adsorption of volatile organic compounds from kerosene using clinoptilolite (natural zeolite) modified by cationic surfactant cetyltrimethylammonium bromide, MethodsX, 14, 103354. http://dx.doi.org/10.1016/j.mex.2025.103354

[51] Shirendev, N., Bat-Amgalan, M., Kano, N., Kim, H.-J., Gunchin, B., Ganbat, B., Yunden, G., 2022. A Natural Zeolite Developed with 3-Aminopropyltriethoxysilane and Adsorption of Cu(II) from Aqueous Media, Applied Sciences, 12, 11344. http://dx.doi.org/10.3390/app122211344

[52] Zekavat, S.R., Raouf, F., Talesh, S.S.A., 2020. Simultaneous adsorption of Cu2+ and Cr (VI) using HDTMA-modified zeolite: isotherm, kinetic, mechanism, and thermodynamic studies, Water Science and Technology, 82, 1808–1824. http://dx.doi.org/10.2166/wst.2020.448

[53] Oter, O., Akcay, H., 2007. Use of natural clinoptilolite to improve water quality: Sorption and selectivity studies of lead(II), copper(II), zinc(II), and nickel(II), Water Environment Research, 79, 329-335. http://dx.doi.org/10.2175/106143007X172633

[54] Doula, M.K., 2006. Removal of Mn²⁺ ions from drinking water by using clinoptilolite and a clinoptilolite-Fe oxide system, Water Research, 40, 3167-3176. http://dx.doi.org/10.1016/j.watres.2006.06.021

[55] Dimirkou, A., 2007. Uptake of Zn²⁺ ions by a fully iron-exchanged clinoptilolite: Case study of heavily contaminated drinking water samples, Water Research, 41, 2763-2773. http://dx.doi.org/10.1016/j.watres.2007.04.003

[56] Dimirkou, A., Doula, M.K., 2008. Use of clinoptilolite and an Fe-overexchanged clinoptilolite in Zn²⁺ and Mn²⁺ removal from drinking water, Desalination, 224, 280-292. http://dx.doi.org/10.1016/j.desal.2007.08.004

[57] Saadi, R., Saadi, Z., Fazaeli, R., Fard, N.E., 2015. Monolayer and multilayer adsorption isotherm models for sorption from aqueous media, Korean Journal of Chemical Engineering, 32, 787-799. http://dx.doi.org/10.1007/s11814-015-0045-z

[58] Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm systems, Chemical Engineering Journal, 156, 2-10. http://dx.doi.org/10.1016/j.cej.2009.09.013

[59] Lim, L.B.L., Priyantha, N., Hei, C.W., Zehra, T., Then, C.W., 2015. Comprehensive study on adsorption behavior and mechanism of methylene blue by activated carbon derived from Enteromorpha prolifera, Arabian Journal of Chemistry, 13, 3031-3044. http://dx.doi.org/10.1016/j.arabjc.2018.08.009

[60] Wang, J., Guo, X., 2020. Adsorption isotherm models: Classification, physical meaning, and application, Journal of Environmental Chemical Engineering, 8, 104261. http://dx.doi.org/10.1016/j.jece.2020.104261

Article View: 92
PDF Download: 65

Elucidating Adsorption Mechanisms of Copper Ions on Surfactant-Modified Zeolites: An Integrated Study of Isotherm Modeling and Surface Characterization

References

Volume 5, Issue 2
December 2026
Pages 27-47

Files

Share

How to cite

Statistics

Elucidating Adsorption Mechanisms of Copper Ions on Surfactant-Modified Zeolites: An Integrated Study of Isotherm Modeling and Surface Characterization

References

Volume 5, Issue 2December 2026Pages 27-47

Files

Share

How to cite

Statistics

Volume 5, Issue 2
December 2026
Pages 27-47