Adsorption Isotherm and Kinetic Studies of Copper(II) Removal from Aqueous Solutions Using  Graphene Oxide

Raga Izriq; Rokaya Azaga; Mohammed S. Ibrahim; Hamd Moamen

doi:10.54172/k56j7q87

Authors

Raga Izriq Department of Chemistry, Faculty of Science, Sebha University, Libya Author
Rokaya Azaga Department of Chemistry, Faculty of Science, Sebha University, Libya Author
Mohammed S. Ibrahim Department of Chemistry, Faculty of Science, Sebha University, Libya Author
Hamd Moamen Department of Chemistry, Faculty of Science, Sebha University, Libya Author

DOI:

https://doi.org/10.54172/k56j7q87

Keywords:

Graphene oxide, heavy metals, adsorption, adsorption capacity, kinetics, thermodynamic parameters

Abstract

Graphene oxide (GO) exhibits good chemical stability for water purification applications. GO contains abundant oxygen-containing functional groups, such as hydroxyl, epoxy, and carboxyl moieties, which provide active adsorption sites. These features enable the effective capture of pollutants. In this study, GO was used as an adsorbent to remove Cu(II) ions from aqueous solutions. GO was prepared from graphite using a modified Hummers method and characterized using FT-IR and XRD techniques. Cu(II) adsorption onto GO was evaluated using an atomic absorption spectrophotometer (AAS). The kinetic parameters were determined using pseudo-first-order and pseudo-second-order kinetic models; the results showed that the adsorption process followed the pseudo-second-order kinetic model. The Langmuir, Freundlich, and Temkin isotherm models were applied, with a maximum adsorption capacity of 324 mg.g-1. Thermodynamic parameters, including ∆G◦, ∆H◦, and ∆S◦, were calculated, indicating that the adsorption process was spontaneous and endothermic.

References

Abu-Dief, A. M., Abdel-Rahman, L. H., Abd–ElSayed, M., & Zikry, M. M. (2021). Green synthesis of silver nanoparticles using Delonix regia extract, characterization and its application as adsorbent for removal of Cu (II) ions from aqueous solution. Asian Journal of Applied Chemistry Research, 9(1), 1-15.

Ahmed, S., Choudhury, T. R., Alam, M. Z., & Nurnabi, M. (2023). Adsorption of Cu (II) and Cd (II) with graphene based adsorbent: adsorption kinetics, isotherm and thermodynamic studies. Desalination and Water Treatment, 285, 167-179.

Ali, A. H., Kareem, A. B., Al-Rawi, U. A., Khalid, U., Zhang, S., Zafar, F., . . . Sher, F. (2023). Kinetic and equilibrium study of graphene and copper oxides modified nanocomposites for metal ions adsorption from binary metal aqueous solution. Frontiers in Chemistry, 11, 1279948.

Ayach, J., El Malti, W., Duma, L., Lalevée, J., Al Ajami, M., Hamad, H., & Hijazi, A. (2024). Comparing conventional and advanced approaches for heavy metal removal in wastewater treatment: an in-depth review emphasizing filter-based strategies. Polymers, 16(14), 1959.

Benalia, M. C., Youcef, L., Bouaziz, M. G., Achour, S., & Menasra, H. (2022). Removal of heavy metals from industrial wastewater by chemical precipitation: mechanisms and sludge characterization. Arabian Journal for Science and Engineering, 47(5), 5587-5599.

Chen, J., Li, Y., Huang, L., Li, C., & Shi, G. (2015). High-yield preparation of graphene oxide from small graphite flakes via an improved Hummers method with a simple purification process. Carbon, 81, 826-834. doi:10.1016/j.carbon.2014.10.033

Cui, L., Wang, Y., Gao, L., Hu, L., Yan, L., Wei, Q., & Du, B. (2015). EDTA functionalized magnetic graphene oxide for removal of Pb (II), Hg (II) and Cu (II) in water treatment: adsorption mechanism and separation property. Chemical Engineering Journal, 281, 1-10.

Dawam, M., Gobara, M., Oraby, H., Y. Zorainy, M., & Nabil, I. M. (2025). Advances in membrane technologies for heavy metal removal from polluted water: A comprehensive review. Water, Air, & Soil Pollution, 236(7), 461.

Deng, H., Wei, W., Yao, L., Zheng, Z., Li, B., Abdelkader, A., & Deng, L. (2022). Potential‐mediated recycling of copper from brackish water by an electrochemical copper pump. Advanced Science, 9(30), 2203189.

Deshwal, N., Singh, M. B., Bahadur, I., Kaushik, N., Kaushik, N. K., Singh, P., & Kumari, K. (2023). A review on recent advancements on removal of harmful metal/metal ions using graphene oxide: Experimental and theoretical approaches. Science of the Total Environment, 858, 159672.

Dutta, S., Gupta, B., Srivastava, S. K., & Gupta, A. K. (2021). Recent advances on the removal of dyes from wastewater using various adsorbents: A critical review. Materials Advances, 2(14), 4497-4531.

Elewa, A., Amer, A., Attallah, M., Gad, H., Al-Ahmed, Z., & Ahmed, I. (2023). Chemically activated carbon based on biomass for adsorption of Fe (III) and Mn (II) ions from aqueous solution. Materials, 16 (3), 1–21. In.

Gomes, B. F. M. L., de Araújo, C. M. B., do Nascimento, B. F., Freire, E. M. P. d. L., Da Motta Sobrinho, M. A., & Carvalho, M. N. (2022). Synthesis and application of graphene oxide as a nanoadsorbent to remove Cd (II) and Pb (II) from water: adsorption equilibrium, kinetics, and regeneration. Environmental Science and Pollution Research, 29(12), 17358-17372.

Guerrero-Contreras, J., & Caballero-Briones, F. (2015). Graphene oxide powders with different oxidation degree, prepared by synthesis variations of the Hummers method. Materials Chemistry and Physics, 153, 209-220.

Guerrero-Fajardo, C. A., Giraldo, L., & Moreno-Piraján, J. C. (2020). Preparation and characterization of graphene oxide for Pb (II) and Zn (II) ions adsorption from aqueous solution: Experimental, thermodynamic and kinetic study. Nanomaterials, 10(6), 1022.

Gupta, V. K., Carrott, P. J. M., Ribeiro Carrott, M. M. L., & Suhas. (2009). Low-cost adsorbents: growing approach to wastewater treatment—a review. Critical reviews in environmental science and technology, 39(10), 783-842.

Hu, X.-j., Liu, Y.-g., Wang, H., Chen, A.-w., Zeng, G.-m., Liu, S.-m., . . . Wang, Y.-q. (2013). Removal of Cu (II) ions from aqueous solution using sulfonated magnetic graphene oxide composite. Separation and Purification Technology, 108, 189-195.

Imamoglu, M., & Tekir, O. (2008). Removal of copper (II) and lead (II) ions from aqueous solutions by adsorption on activated carbon from a new precursor hazelnut husks. Desalination, 228(1-3), 108-113.

Kara, M., Yuzer, H., Sabah, E., & Celik, M. (2003). Adsorption of cobalt from aqueous solutions onto sepiolite. Water research, 37(1), 224-232.

Katiyar, R., Patel, A. K., Nguyen, T.-B., Singhania, R. R., Chen, C.-W., & Dong, C.-D. (2021). Adsorption of copper (II) in aqueous solution using biochars derived from Ascophyllum nodosum seaweed. Bioresource technology, 328, 124829.

Kaushal, A., Dhawan, S., & Singh, V. (2019). Determination of crystallite size, number of graphene layers and defect density of graphene oxide (GO) and reduced graphene oxide (RGO). Paper presented at the AIP Conference Proceedings.

Khan, M., Muhammad, M., AlOthman, Z. A., Cheong, W. J., & Ali, F. (2022). Synthesis of monolith silica anchored graphene oxide composite with enhanced adsorption capacities for carbofuran and imidacloprid. Scientific Reports, 12(1), 21027.

Kumar, A. S. K., & Jiang, S.-J. (2016). Chitosan-functionalized graphene oxide: A novel adsorbent an efficient adsorption of arsenic from aqueous solution. Journal of environmental chemical engineering, 4(2), 1698-1713.

Liu, Y., Zhong, Q., & Zhang, T. (2015). Preparation of cationic surfactant intercalated graphene oxide and quantitative determination of the interlamellar spacing. Fullerenes, Nanotubes and Carbon Nanostructures, 23(3), 196-202.

Marcano, D. C., Kosynkin, D. V., Berlin, J. M., Sinitskii, A., Sun, Z., Slesarev, A., . . . Tour, J. M. (2010). Improved synthesis of graphene oxide. ACS nano, 4(8), 4806-4814.

Mi, X., Huang, G., Xie, W., Wang, W., Liu, Y., & Gao, J. (2012). Preparation of graphene oxide aerogel and its adsorption for Cu2+ ions. Carbon, 50(13), 4856-4864.

Musah, M., Azeh, Y., Mathew, J. T., Umar, M. T., Abdulhamid, Z., & Muhammad, A. I. (2022). Adsorption kinetics and isotherm models: a review. CaJoST, 4(1), 20-26.

Nassef, H. M., Al-Hazmi, G. A., Alayyafi, A. A., El-Desouky, M. G., & El-Bindary, A. A. (2024). Synthesis and characterization of new composite sponge combining of metal-organic framework and chitosan for the elimination of Pb (II), Cu (II) and Cd (II) ions from aqueous solutions: Batch adsorption and optimization using Box-Behnken design. Journal of Molecular Liquids, 394, 123741.

Oladoja, N., Aboluwoye, C., & Oladimeji, Y. (2008). Kinetics and Isotherm Studies on Methylene Blue Adsorption onto Ground Palm Kernel Coat. Turkish Journal of Engineering & Environmental Sciences, 32(5).

Raji, Z., Karim, A., Karam, A., & Khalloufi, S. (2023). Adsorption of heavy metals: mechanisms, kinetics, and applications of various adsorbents in wastewater remediation—a review. Paper presented at the Waste.

Rathore, E., & Biswas, K. (2018). Selective and ppb level removal of Hg (ii) from water: synergistic role of graphene oxide and SnS 2. Journal of Materials Chemistry A, 6(27), 13142-13152.

Sadeek, S. A., Negm, N. A., Hefni, H. H., & Wahab, M. M. A. (2015). Metal adsorption by agricultural biosorbents: adsorption isotherm, kinetic and biosorbents chemical structures. International journal of biological macromolecules, 81, 400-409.

Shalaby, A., Nihtianova, D., Markov, P., Staneva, A., Iordanova, R., & Dimitriev, Y. (2015). Structural analysis of reduced graphene oxide by transmission electron microscopy. Bulgarian Chemical Communications, 47(1), 291-295.

Shek, T.-H., Ma, A., Lee, V. K., & McKay, G. (2009). Kinetics of zinc ions removal from effluents using ion exchange resin. Chemical Engineering Journal, 146(1), 63-70.

Tan, P., Bi, Q., Hu, Y., Fang, Z., Chen, Y., & Cheng, J. (2017). Effect of the degree of oxidation and defects of graphene oxide on adsorption of Cu2+ from aqueous solution. Applied Surface Science, 423, 1141-1151.

Tan, P., Sun, J., Hu, Y., Fang, Z., Bi, Q., Chen, Y., & Cheng, J. (2015). Adsorption of Cu2+, Cd2+ and Ni2+ from aqueous single metal solutions on graphene oxide membranes. Journal of hazardous materials, 297, 251-260.

Türkmen, D., Bakhshpour, M., Akgönüllü, S., Aşır, S., & Denizli, A. (2022). Heavy metal ions removal from wastewater using cryogels: a review. Front Sustain. In.

Wang, H., Hu, X., Guo, Y., Qiu, C., Long, S., Hao, D., . . . Liu, Y. (2018). Removal of copper ions by few‐layered graphene oxide nanosheets from aqueous solutions: external influences and adsorption mechanisms. Journal of Chemical Technology & Biotechnology, 93(8), 2447-2455.

White, R. L., White, C. M., Turgut, H., Massoud, A., & Tian, Z. R. (2018). Comparative studies on copper adsorption by graphene oxide and functionalized graphene oxide nanoparticles. Journal of the Taiwan Institute of Chemical Engineers, 85, 18-28.

Wu, C.-H., Kuo, C.-Y., & Guan, S.-S. (2016). Adsorption of heavy metals from aqueous solutions by waste coffee residues: kinetics, equilibrium, and thermodynamics. Desalination and Water Treatment, 57(11), 5056-5064.

Wu, W., Yang, Y., Zhou, H., Ye, T., Huang, Z., Liu, R., & Kuang, Y. (2013). Highly efficient removal of Cu (II) from aqueous solution by using graphene oxide. Water, Air, & Soil Pollution, 224(1), 1372.

Xue, B., Zhu, J., Liu, N., & Li, Y. (2015). Facile functionalization of graphene oxide with ethylenediamine as a solid base catalyst for Knoevenagel condensation reaction. Catalysis Communications, 64, 105-109. doi:10.1016/j.catcom.2015.02.003

Yi, I.-G., Kang, J.-K., Kim, J.-H., Lee, S.-C., Sim, E.-H., Park, J.-A., & Kim, S.-B. (2017). Adsorption characteristics of graphene oxide in the removal of Cu (II) from aqueous solutions. Desalination and Water Treatment, 72, 308-317.