Mesoporous silica functionalized with diethylenetriamine moieties for metal removal and thermodynamics of cation-basic center interactions

The inorganic-organic hybrid material was synthesized by co-condensation of tetraethylorthosilicate and the organosilane N-[3-(trimethoxysilyl)propyl)diethylenetriamine. Spectroscopic analysis of the hybrid material by FTIR showed bands at 2937 and 2839 cm(-1) related to nu(C-H); Si-29 NMR spectrum gave signals at -108, -99, -68 and -59 ppm, Q(4), Q(3), T-4 and T-2 species related to the silica backbone structure. The well-defined peaks obtained in the C-13 NMR spectrum in the 10-58 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous silica. Particle morphology evaluated by a scanning electron microscopic (SEM) study showed the formation of spherical particles in the nanometer range. The X-ray diffraction pattern showed a peak at a 2H of 2.3 degrees, demonstrating the rnesoporous characteristic of the synthesized material. Adsorption evaluated by batch equilibrium processes gave the maximum adsorption of 2.2 and 2.8 mmol g(-1) for copper and nickel, respectively. From these values a stoichiometry of 2:1 for cation/ligand was established, considering the amount of 1.2 mmol of pendant groups per gram of the hybrid material. Thermodynamic parameters related to the adsorption of metal ions, evaluated using the calorimetric titration technique presented a negative Gibbs free energy value, in agreement with the spontaneity of cation removal on the basic center in the mesoporous silica at the solid/liquid interface. (C) 2008 Elsevier B.V. All rights reserved.