Adsorption of cadmium ions on thiol or sulfonic-functionalized poly(dimethylsiloxane) networks.

Thiol or sulfonic-functionalized poly(dimethylsiloxane) elastomeric networks were prepared from 3-mercaptopropyltrimethoxysilane or the oxidized silane. The characterization of these materials using infrared spectroscopy (IR) and (13)C/(29)Si nuclear magnetic resonance (NMR) suggested that the materials were functionalized with the aforementioned groups and that the networks are composed of linear segments of PDMS crosslinked by nodes of silsesquioxanes, which contain T(3) and/or T(2) type silicon. The thermogravimetric analysis of the polymeric networks revealed that they exhibit good thermal stability. The adsorption capacities for cadmium ions in ethanolic solutions were 0.33 and 0.89 mmol g(-1) for the thiol- and sulfonic-functionalized PDMS networks, respectively. In water solution the material with thiol group do not adsorbed Cd (II), however, the network with sulfonic group adsorbed 0.70 mmol g(-1). In ethanol, the linearization of the adsorption isotherms revealed that the Langmuir model describes the interaction between the adsorbate-adsorbent, in water, the Freundlich adsorption model described the metal adsorption for the sulfonic-functionalized PDMS.

n-Propylpyridinium chloride-modified poly(dimethylsiloxane) elastomeric networks: preparation, characterization, and study of metal chloride adsorption from ethanol solutions.

An n-propylpyridinium chloride-modified PDMS elastomeric network, PDMS/Py(+)Cl(-), was prepared from linear PDMS chains containing Si(CH(3))(2)OH end-groups cross-linked by 3-chloropropyltrimethoxysilane and posterior reaction with pyridine. PDMS/Py(+)Cl(-) material was structurally characterized by infrared spectroscopy (IR) and solid state (13)C and (29)Si NMR. Thermogravimetric analysis of the product showed good thermal stability, with the initial temperature of weight loss at 450 K. The ion-exchange capacity of the PDMS/Py(+)Cl(-) was 0.65 mmol g(-1). Metal halides, MCl(z) [M=Fe(3+), Cu(2+), and Co(2+)], were adsorbed by the modified solid from ethanol solutions as neutral species by forming the surface anionic complexes MCl(z+n)(n-). The nature of the anionic complex structure was proposed by UV-vis diffuse reflectance spectra. The species adsorbed were FeCl(-)(4), CuCl(2-)(4), and CoCl(2-)(4). The specific sorption capacities and the heterogeneous stability constants of the immobilized metal complexes were determined with the aid of computational procedures. The trend in affinities of PDMS/Py(+)Cl(-) for the metal halides were found to be FeCl(3)>CuCl(2) approximately CoCl(2).

Al2O3-coated 3-N-propylpyridinium chloride silsesquioxane polymer film: preparation and electrochemical property study of adsorbed cobalt tetrasulfophthalocyanine.

Porous Al2O3 presenting a specific surface area of SBET = 105 m2 g(-1) was coated with 3-N-propylpyridinium chloride silsesquioxane polymer. The ion exchange capacity of this polymer grafted onto an Al2O3 surface, resulting in a material designated as AlSiPy(+)Cl-, was 1.09 mmol g(-1). Furthermore, a cobalt(II) tetrasulfophthalocyanine anionic complex was immobilized on the chemically modified surface by an ion exchange reaction with a yield of 40 micromol g(-1) (the surface density of the electroactive species is 3.80 x 10(-11) mol cm(-2)). The electrochemical properties of the material obtained, AlSiPy/CoTsPc, were tested for the catalytic oxidation of oxalic acid at 0.77 V vs SCE in 1.0 mol l(-1) KCl solution. Furthermore, a chronoamperometric technique was used with the electrode to test its potential use as a sensor for oxalic acid. The electrode response to oxalic acid concentrations between 1.0 and 3.5 mmol l(-1) was linear with an estimated detection limit of 0.5 mmol l(-1). The charge transfer resistance of the material, measured using the electrochemical impedance spectroscopy technique, was 43 Omega cm2.