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Received 13 April 2004; received in revised form 2 July 2004; accepted 7 July 2004
Available online 24 July 2004
Abstract
The complexation agent 2[-bis-(pyridylmethyl) aminomethyl]-4-methyl-6-formyl-phenol (HL) was immobilized in chitosan in order to
obtain a new adsorbent material to be employed in studies on adsorption and pre-concentration of Cu(II). The chitosan modified by the
complexation agent was characterized by infrared spectroscopy, DSC and TGA. The studies were conducted as a function of the pH of the
medium and the mechanism of Cu(II) adsorption in the solid phase was analyzed utilizing several kinetic models. The parameters for
the adsorption of Cu(II) ions by chitosan–HL were determined with a Langmuir isotherm, the maximum saturation capacity of the monolayer
being 109.4 mg of Cu(II) per gram of polymer. Electron paramagnetic resonance spectroscopy revealed that CuII ions coordinate to the donor
atoms of the HL ligand anchored to the surface of the polymer forming a stable chelate complex in the solid state.
q 2004 Elsevier Ltd. All rights reserved.
Chitin, a component of the exoskeleton of crustaceans temperature range of 25–500 8C, with a heating rate of
such as crabs, lobsters, shrimps, etc. is a biomass used in the 10 8C minK1, under a nitrogen atmosphere.
synthesis of chitosan [10]. This biopolymer has excellent Electron paramagnetic resonance (EPR) spectra were
properties for the adsorption of transition metals, principally recorded at X-band on a Bruker ESP300E spectrometer at
due to the presence of amino groups in the polymer matrix. room and liquid N2 temperatures.
However, its capacity to adsorb is dependent on the degree
of deacetylation, the nature of the metal ion and the pH of
the solution [4,5,11–13]. The presence of a high percentage 2.3. Chitosan–HL synthesis
of reactive primary amino groups distributed in the polymer
matrix, offers innumerous chemical modifications, such as The chitosan was dispersed in methanol in a ratio of
the immobilization of complexation agents. The modifi- 1.5 mol of HL ligand per mol of glucosamine and the system
cation of the polymer surface through the introduction of was maintained under agitation for 16 h and in reflux for
new complexation groups may result in the formation of 18 h. The desired product was obtained after the reaction
different chelates, so increasing its adsorption capacity and had an intense yellow color. The chitosan–HL was initially
selectivity toward metal ions in solution [9,14–16]. washed with methanol to remove the excess ligand,
The aim of this study was to prepare a new adsorbent followed by distilled water and then dried in a vacuum.
material, covalently immobilizing in the chitosan, via the Fig. 1 shows the structure of the Schiff base formed by the
Schiff’s base reaction, the complexation agent 2[-bis- chitosan and the HL ligand as an intermediate stage in the
(pyridylmethyl) aminomethyl]-4-methyl-6-formyl-phenol synthesis of the adsorbent used in this study. To increase
(HL), and to study the adsorption of Cu(II) ions in an the resistance of the adsorbent to acid solutions, the
aqueous medium. chitosan–HL was cross-linked with a 2.5% glutaraldehyde
solution for 24 h at room temperature [20,21]. The cross-
linked material was filtered and thoroughly washed with
2. Experimental distilled water. After reticulation, the imine groups were
reduced with a solution of sodium borohydride [22].
2.1. Materials
2.4. Adsorption experiments
The chitosan with a 90% degree of deacetylation was
obtained from Purifarma (Brazil). The 2[-bis-(pyridyl-
All batch experiments were carried out in a thermostated
methyl) aminomethyl]-4-methyl-6-formyl-phenol (HL)
bath at 25 8C, with a shaking of 200 rpm.
ligand was prepared through the reaction of 2-chloro-
The study of the pH dependency of the adsorption of
methyl-4-methyl-6-(formyl)phenol with bis-(2-pyridyl-
Cu(II) by chitosan–HL was carried out utilizing buffer
methyl)amine [17,18].
solutions: KCl/HCl (pHZ3), acetic acid/sodium acetate
A 1000 mg lK1 copper (II) stock solution was prepared
(pHZ4, 5 and 6), tris(hydroxymethyl) aminomethane
by dissolving the appropriate quantity of copper sulphate
(pHZ8) and ammonia/ammonium chloride (pHZ9 and
analytical grade and standardized with a standard solution of
0.01 mol lK1 EDTA [19]. Working standard solutions of the 10). Aliquots (50.0 ml) of the 100 mg lK1 Cu(II) solutions
Cu(II) metal ion were prepared through the dilution of the buffered at different pH values, were placed in contact
1000 mg lK1 stock solution with distilled water. with 100 mg samples of chitosan–HL for a period of
All other reagents utilized were of analytical grade. 2 h. The quantity of Cu(II) adsorbed was obtained from
the difference between the initial and the final
2.2. Instrumentation concentration of metal in solution and the mass of
adsorbent used.
An atomic absorption spectrophotometer, (FAAS) Spec- The adsorption kinetics were determined in a closed flask
tra AA 50 Varian, equipped with a flame atomizer and a containing 100 mg of chitosan–HL and 100.0 ml of Cu(II)
metal hollow cathode lamp, was used for the copper solution buffered at pH 5.5. After pre-determined time
determination. periods, 200 ml aliquots were removed and the concen-
The batch adsorption experiments were carried out in a tration of copper ions in solution was measured.
thermostated Lab-Line Shaker Bath with controlled In the adsorption equilibrium experiments, 100 mg
agitation. samples of chitosan–HL and 50.0 ml of solutions buffered
Infrared spectra were obtained from KBr pellets, using a at pH 5.5 containing several concentrations of Cu(II) were
spectrophotometer with Fourier Transform System, 2000 used. The system was maintained under shaking at 25 8C
FT-IR-Perkin Elmer. until adsorption equilibrium was reached. Aliquots (200 ml)
DSC and TG analyses were carried out with a DSC-50 were removed and diluted in volumetric flasks and the metal
Shimadzu and a TG-50 Shimadzu, respectively. In the case concentration was determined by atomic absorption spec-
of the DSC, the scanning was carried out within a trophotometry (FAAS) at 324.8 nm.
K.C. Justi et al. / Polymer 45 (2004) 6285–6290 6287
4. Conclusions
Fig. 7. X-band EPR spectrum for chitosan–HL with CuII in the solid state. (—) Experimental spectrum and (.) simulated spectrum using the Winepr SimFonia
Program. The Hamiltonian parameters are gsZ2.26, gtZ2.076, AsZ175!10K4 cmK1 and AtZ20 cmK1.
Finally, this new material shows significant capacity for [10] Kumar MNVR. React Funct Polym 2000;46:1–27.
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