Synthesis and Metal Ion Uptake Studies of Silica Gel-Immobilized Schiff Base Derivatives and Catalytic Behaviors of their Cu(II) Complexes

Document Type: Research Article


1 Altınözü Vocational School, Mustafa Kemal University, Hatay, TURKEY

2 Department of Chemistry, Faculty of Arts and Sciences, Mustafa Kemal University, Hatay, Turkey


New silica supported Schiff base ligands were prepared by the condensation reaction of 4,6-diacetylresorcinol with silica-gel derivatives, which modified with 3-aminopropyltriethoxysilane and N-(2-aminoethyl) -3-aminopropyltrimethoxysilane. Metal ion uptake capacities of these compounds were studied towards of selected transition metal (Cd(II), Cu(II), Co(II), Mn(II), Pb(II) and Ni(II)) cations in an aqueous medium. In addition, Cu(II) complexes of these ligands were prepared by using heterogeneous reaction conditions. The synthesized compounds were characterized by using elemental analysis, FT-IR, DR-UV-vis., CP/MAS 13C-NMR, AAS, XRD and TGA techniques. Moreover, the morphological and chemical properties of these compounds were investigated by using a scanning electron microscope (SEM) coupled to an energy-dispersive X-ray spectrometer (EDX). The catalytic performances of the Cu(II) complexes were investigated on H2O2 decomposition. These complexes displayed good catalytic activities towards the decomposition of H2O2 as heterogeneous catalysts.


Main Subjects

[1] Silva O.G., Filho E.C.S., Fonseca M.G., Arakaki L.N.H., Airoldi C.J., Hydroxyapatite Organofunctionalized with Silylating Agents to Heavy Cation Removal, Colloid Interf. Sci., 302:485-491 (2006).
[2] Silva O.G., Filho E.C.S., Fonseca M.G., Arakaki L.N.H., Silylated Calcium Phosphates and their New Behavior for Copper Retention from Aqueous Solution, Esticide 2,4-Dichlorophenoxyacetic Acid on a Silica Gel Surface, Colloid Surface A., 301(1-3): 376-381 (2007).
[5] Prado A.G.S., Airoldi C.J., Immobilization of the Pesticide 2,4-Dichlorophenoxyacetic Acid on a Silica Gel Surface, Pest Manag. Sci., 56(5):419-424 (2000).
[6] Quintanilla D.P., Sanches A., Hierro I., Fajardo M., Sierra I.J., Preparation, Characterization, and Zn2+ Adsorption Behavior of Chemically Modified MCM-41 with 5-Mercapto-1-methyltetrazole, Colloid Interf. Sci., 313(2): 551-562 (2007).
[8] Ganesan V., Functionalized Silica Materials for Electrocatalysis, J. Chem. Sci., 127(2): 307-313 (2015).
[13] Padilha P.M., Gomes L.A.M., Padilha C.C.F., Moreira J.C., Dias N.L.F., Determination of Metal Ions in Natural Waters by Flame-AAS after Preconcentration on a 5-Amino-1,3,4-Thiadiazole-2-Thiol Modified Silica Gel, Anal. Lett., 32: 1807-1820 (1999).
[14] Gübbük I.H., Güp R., Ersöz M., Synthesis, Characterization, And Sorption Properties of Silica Gel-Immobilized Schiff Base Derivative, J. Colloid. Interf. Sci., 320(2):376-382 (2008).
[15] You Z.L., Zhu H.L., Syntheses, Crystal Structures, and Antibacterial Activities of Four Schiff Base Complexes of Copper and ZincZ. Anorg. Allg. Chem., 630:2754-2760 (2004).
[16] Gölcü A., Tümer M., Demirelli H., Wheatley R.A., Cd(II) And Cu(II) Complexes of Polydentate Schiff Base Ligands: Synthesis, Characterization, Properties and Biological Activity, Inorg. Chim. Acta., 358(6):1785-1797 (2005).
[19] Gao J., Martell A.E., Reibenspies J.H., Novel Dicopper(II) Catalase-Like Model Complexes: Synthesis, Crystal Structure, Properties and Kinetic Studies, Inorg. Chim. Acta., 346:32-42 (2003).
[21] Lane B.S., Burgess K., Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide, Chem. Rev., 103: 2457-2473 (2003).
[22] Vasconcellos-Dias M., Nunes C.D., Vaz P.D., Ferreira P., Calhorda M.J., Pyridine Carboxylate Complexes of MoII as Active Catalysts in Homogeneous and Heterogeneous Polymerization, Eur. J. Inorg. Chem., 2007(18):2917-2925 (2007).
[24] Bhunia S., Jana S., Saha D., Dutta B., Koner S., Catalytic Olefin Epoxidation Over Cobalt(II)-Containing Mesoporous Silica by Molecular Oxygen in Dimethylformamide Medium, Cat. Sci. Tec.,
4: 1820-1828 (2014).
[27] Marshall M.A, Mottola H.A., Synthesis of Silica-Immobilized 8-Quinolinol with (Aminophenyl) Trimethoxysilane, Anal. Chem., 55(13): 2089-2093 (1983).
[28] Durak D., Delikanli A., Demetgül C., Kani I., Serin S., Crystal Structure of an Unsymmetrical Schiff Base, Immobilization of its Cobalt and Manganese Complexes on a Silica Support, and Catalytic Studies, Transit. Metal. Chem., 38(2): 199-206 (2013).
[31] Ebraheem K.A.K., Mubarak M.S., Al-Gharabli S.I., Synthesis and Chelation Properties of some new Mannich Condensation Polymers Containing a Salicylaldoxime Group,J. Macromol. Sci.-Pure and Appl. Chem., A39(3):217-229 (2002).
[32] Deletioğlu D., Yalçınkaya S., Demetgül C., Timur M., Serin S., Electropolymerization of CuII-(N,N′-bis(3-methoxysalicylidene)-2-aminobenzylamine) on Platinum Electrode: Application to the Electrocatalytic Reduction of Hydrogen Peroxide, Mater. Chem. Phys., 128(3):500-506 (2011).
[34] Shimizu I., Yoshino A., Okabayashi H., Nishio E., O'Connor C.J., Kinetics of Interaction of 3-Aminopropyltriethoxysilane on Asilica Gel Surface Using Elemental Analysis and Diffuse Reflectanceinfrared Fourier Transform Spectra, Chem. Soc. Faraday T., 93: 1971-1979 (1997). 
[35] Etienne M., Lebeau B., Walcarius A., Organically-Modified Mesoporous Silica Spheres with MCM-41 ArchitectureNew J. Chem., 26: 384-386 (2002).
[36] Kim S.H., Han O.H., Kim J.K., Lee K.H., Multinuclear Solid-State NMR Investigation of Nanoporous Silica Prepared by Sol-gel Polymerization Using Sodium Silicate, B. Korean Chem. Soc., 32:3644-3649 (2011).