Adsorption of Copper (II) Ions on a Montmorillonite Clay and its Application as Heterogeneous Catalyst for Knoevenagel Condensation Reaction

Journal of Chemical Health Risks

مقاله 6، دوره 12، شماره 3، آذر 2022، صفحه 379-396   

نوع مقاله: Original Article

شناسه دیجیتال (DOI): 10.22034/jchr.2021.1913071.1209

نویسندگان

Hanane Essebaai^{* 1}؛ zakaria Benzekri²؛ Houda Serrar²؛ Ahmed Lebkiri³؛ Said Boukhris²؛ Said Marzak³؛ ElHousseine Rifi³

¹Laboratory of Organic Synthesis and Extraction Processes, Department of Chemistry, Faculty of Sciences, Ibn Tofail University, Kénitra, Morocco

²Laboratory of Organic, Organometallic and Theoretical Chemistry, Faculty of Science, Ibn Tofaïl University, Kenitra, Morocco

³Laboratory of Organic Synthesis and Extraction Processes, Department of Chemistry, Faculty of Sciences, Ibn Tofail University, Kénitra, Morocco.

چکیده

In the present study, a simplest and most effective method was applied to removal of Cu²⁺ ions from an aqueous solution using Montmorillonite clay, nontoxic and abundantly available as an adsorbent. The used adsorbent was characterized using X-ray diffraction (XRD), the X-ray fluorescence spectrometry, Fourier Transform Infrared Spectroscopy (FT-IR) and scanning electron microscope (SEM) coupled with EDX analysis. Adsorption experiments were conducted under various conditions,.i.e., contact time , initial concentration,  pH of Cu(II) ions solution, adsorbent mass, and particle size . The results proved that the adsorption of Cu(II) ions by Montmorillonite clay was favorable at pH=5.5 with an extraction yield of 85% after 30 min contact. The equilibrium isotherm data were analyzed using the Langmuir and Freundlich equations. In all cases, the adsorption process fitted the second-order kinetics well, and the isotherm equation due to Freundlich showed good fits with the experimental data. In order to value our Cu-Montmorillonite clay (Cu-MC) support, we thought of applying it as recyclable heterogeneous catalyst for the condensation of Knoevenagel. The model reaction was carried out at room temperature, using a quantity of 0.5 mg of catalyst and a volume of  2ml of ethanol, the reaction yield was excellent (87%). The recyclable solid catalyst was effective for five successive cycles, indicating that this clay is a potentially eco-friendly heterogeneous catalyst.In the present study, a simplest and most effective method was applied to removal of Cu²⁺ ions from an aqueous solution using Montmorillonite clay, nontoxic and abundantly available as an adsorbent. The used adsorbent was characterized using X-ray diffraction (XRD), the X-ray fluorescence spectrometry, Fourier Transform Infrared Spectroscopy (FT-IR) and scanning electron microscope (SEM) coupled with EDX analysis. Adsorption experiments were conducted under various conditions,.i.e., contact time , initial concentration,  pH of Cu(II) ions solution, adsorbent mass, and particle size . The results proved that the adsorption of Cu(II) ions by Montmorillonite clay was favorable at pH=5.5 with an extraction yield of 85% after 30 min contact. The equilibrium isotherm data were analyzed using the Langmuir and Freundlich equations. In all cases, the adsorption process fitted the second-order kinetics well, and the isotherm equation due to Freundlich showed good fits with the experimental data. In order to value our Cu-Montmorillonite clay (Cu-MC) support, we thought of applying it as recyclable heterogeneous catalyst for the condensation of Knoevenagel. The model reaction was carried out at room temperature, using a quantity of 0.5 mg of catalyst and a volume of  2ml of ethanol, the reaction yield was excellent (87%). The recyclable solid catalyst was effective for five successive cycles, indicating that this clay is a potentially eco-friendly heterogeneous catalyst.

کلیدواژه‌ها

Natural clay؛ Copper؛ Linear method؛ Non-linear method؛ Montmorillonite؛ kinetic model؛ heterogeneous catalyst؛ Knoevenagel reaction

مراجع

1. Tizaoui K., Benguella B., Makhoukhi B., 2019. Selective Adsorption of Heavy Metals (Co²⁺, Ni²⁺, and Cr³⁺) from Aqueous Solutions onto Natural Marne Clay. Desalination Water Treat. 142, 252–259.

2 .Calagui M.J.C., Senoro D.B., Kan C.C., Salvacion J.W., Futalan C.M., Wan M.W., 2014. Adsorption of Indium (III) Ions from Aqueous Solution Using Chitosan-Coated Bentonite Beads. J Hazard Mater.277, 120–126.

3. Bouna L., Ait El Fakir A., Abdeljalil B., Draoui K., Villain S., Guinneton F., 2020. Physico-Chemical Characterization of Clays from Assa-Zag for Valorization in Cationic Dye Methylene Blue Adsorption. Mater. Today Proc. 22, 22-27.

4. Alshameri A., He H., Zhu J., Xi Y., Zhu R., Ma L., Tao Q., 2018. Adsorption of Ammonium by Different Natural Clay Minerals: Characterization, Kinetics and Adsorption Isotherms. Appl Clay Sci. 159, 83–93.

5. Ouaddari H., Beqqour D., Bennazha J., El Amrani I.E., Albizane A., Solhy A., Varma R.S., Natural Moroccan Clays: Comparative Study of Their Application as Recyclable Catalysts in Knoevenagel Condensation. Sustain Chem Pharm. 10, 1–8.

6. Lamberth C., Godineau E., Smejkal T., Trah S., 2012. ChemInform Abstract: A New Knoevenagel-Type Synthesis of Fully Substituted γ-Hydroxybutenolides. Tetrahedron Lett. 53, 4117–4120.

7.Heydari R., Tahamipour B., 2011. Highly Regioselective Synthesis of Dicyano-8a,10,11-Trihydropyrrolo[1,2-a][1,10]Phenanthrolines via a Domino-Knoevenagel-Cyclization. Chin Chem Lett. 22(11), 1281–1284.

8. Tietze L.F., Rackelmann N., 2004. Domino Reactions in the Synthesis of Heterocyclic Natural Products and Analogs. Pure Appl Chem. 76(11), 1967–1983.

9. Vijender M., Kishore P., Satyanarayana B., 2008. Zirconium Tetrachloride-SiO₂ Catalyzed Knoevenagel Condensation: A Simple and Efficient Protocol for the Synthesis of Substituted Electrophilic Alkenes. Arkivoc. 13, 122–128.

10. Alandis N.M., Mekhamer W., Aldayel O., Hefne J.A.A., Alam M., 2019. Adsorptive

Applications of Montmorillonite Clay for the Removal of Ag(I) and Cu(II) from Aqueous Medium. J Chem. 1-7.

11.Rosati O., Lanari D., Scavo R., Persia D., Marmottini F., Nocchetti M., Curini M., Piermatti O., 2018. Zirconium Potassium Phosphate Methyl and/or Phenyl Phosphonates as Heterogeneous Catalysts for Knoevenagel Condensation under Solvent Free Conditions. Microporous Mesoporous Mater. 268, 251–259.

12. Çi̇Men O., Koç Ş., Sari A., 2013. Rare earth element (REE) geochemistry and genesis of oil shales around Daghacilair  village, Goynuk-Bolu, TurkeyURKEY. Oil Shale. 30 (3), 419.

13. Gionis V., Kacandes G.H., Kastritis I.D., 2006. Chryssikos G.D., On the Structure of Palygorskite by Mid-and near-Infrared Spectroscopy. Am Mineral. 91(7), 1125–1133.

14. Suarez M., Garcia-Romero E.,2006. FTIR Spectroscopic Study of Palygorskite: Influence of the Composition of the Octahedral Sheet. Appl Clay Sci. 31 (1–2), 154–163.

15. Blanco C., González F., Pesquera C., Benito I., Mendioroz S., Pajares  J.A., 1989. Differences between One Aluminic Palygorskite and Another Magnesic by Infrared Spectroscopy. Spectrosc Lett. 22(6), 659–673.

16. Yan W.,  Liu D., Tan D., Yuan P., Chen M., 2012. FTIR Spectroscopy Study of the Structure Changes of Palygorskite under Heating. Spectrochim. Acta A Mol Biomol Spectrosc. 97, 1052–1057.

17. Jiang M., Jin X., Lu X.Q., Chen Z., 2010. Adsorption of Pb (II), Cd (II), Ni (II) and Cu (II) onto Natural Kaolinite Clay. Desalination . 252 (1–3), 33–39.

18. Essebaai H., Ismi I., Lebkiri A., Marzak S., 2019. Kinetic and Thermodynamic Study of Adsorption of Copper (II) Ion on Moroccan Clay. Mediterr J Chem. 9 (2), 102–115.

19. Van Tran T.,  Nguyen D.T.C., Le H.T., Tu T.T., Le N.D., Lim K.T., Bach L.G., Nguyen T.D., 2019. MIL-53 (Fe)-Directed Synthesis of Hierarchically Mesoporous Carbon and Its Utilization for Ciprofloxacin Antibiotic Remediation. J Environ Chem Eng. 7(1), 102881.

20. Nartowska E., 2019. The Effects of Potentially Toxic Metals (Copper and Zinc) on Selected Physical and Physico-Chemical Properties of Bentonites. Heliyon . 5(10), e02563.

21. Ndzana G.M., Huang L., Zhang Z., Zhu J., Liu F., Bhattacharyya R., 2019. The Transformation of Clay Minerals in the Particle Size Fractions of Two Soils from Different Latitude in China. Catena . 175, 317–328.

22. Lagergren S.,1899. Zur Theorie der sogenannten Adsorption gelöster Stoffe. Physik Ch. 32, 174–75.

23. Ho Y.S., McKay G., 1999. Pseudo-Second Order Model for Sorption Processes. Process Biochem. 34(5), 451–465.

24. Fu J., Xin Q.,  Wu X.,  Chen Z., Yan Y., Liu S., Wang M., Xu Q., 2016. Selective Adsorption and Separation of Organic Dyes from Aqueous Solution on Polydopamine Microspheres. J Colloid Interface Sci. 461, 292–304.

25. Mahmoodi N.M., 2015. Surface Modification of Magnetic Nanoparticle and Dye Removal from Ternary Systems. J Ind Eng Chem. 27, 251–259.

26. Bentahar  S., Dbik  A., El Khomri M., El Messaoudi N., Lacherai A., 2017. Adsorption of Methylene Blue, Crystal Violet and Congo Red from Binary and Ternary Systems with Natural Clay: Kinetic, Isotherm, and Thermodynamic. J Environ Chem Eng. 5 (6), 5921–5932.

27. Weber W.J., Morris J.C.,1963. Kinetics of Adsorption on Carbon from Solution. J Sanit Eng Div. 89(2), 31–60.

28. Chowdhury S., Misra  R., Kushwaha P., Das P., 2011. Optimum Sorption Isotherm by Linear and Nonlinear Methods for Safranin onto Alkali-Treated Rice Husk. Bioremediation J. 15(2), 77–89.

29. Benderdouche N., Bestani B., Hamzaoui M., 2018. The Use of Linear and Nonlinear Methods for Adsorption Isotherm Optimization of Basic Green 4-Dye onto Sawdust-Based Activated Carbon. J Mater Env Sci. 9, 1110–1118.

30. Jeppu G.P., Clement T.P., 2012. A Modified Langmuir-Freundlich Isotherm Model for Simulating PH-Dependent Adsorption Effects. J Contam Hydrol. 129, 46–53.

31. Chen X., 2015. Modeling of Experimental Adsorption Isotherm Data. Information. 6(1), 14–22.

32. Kapoor A., Yang R.T., 1989 Correlation of Equilibrium Adsorption Data of Condensible Vapours on Porous Adsorbents. Gas Sep. Purif. 3(4), 187–192.

33. Kausar A., Naeem K., Hussain T.,  Bhatti H.N.,  Jubeen F., Nazir A., Iqbal M., 2019. Preparation and Characterization of Chitosan/Clay Composite for Direct Rose FRN Dye Removal from Aqueous Media: Comparison of Linear and Non-Linear Regression Methods. J Mater Res Technol. 8(1), 1161–1174.

34. Amrhar O., Nassali H., Elyoubi M.S., 2015. Application of Nonlinear Regression Analysis to Select the Optimum Absorption Isotherm for Methylene Blue Adsorption onto Natural Illitic Clay. Bull Société R Sci Liège. 84, 116–130.

35. Vasanth Kumar K.,,Sivanesan S., 2005. Comparison of linear and non-linear method in   estimating  the sorption isotherm parameters for safranin onto activated carbon. Journal of Hazardous Materials B123, 288–292.