4 resultados para REDOX PROCESSES

em Universidad de Alicante


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A simple method was used to synthesize poly(2-aminophenol), poly(2-aminophenol-co-Aniline) and polyaniline nanocomposites with sodium-montmorillonite (Na-M) using in situ intercalative oxidative polymerization. Morphology and thermal properties of the synthesized nanocomposites were examined by transmission electron microscopy (TEM) and thermogravimetric analysis. The thermal analysis shows an improved thermal stability of the nanocomposites in comparison with the pure poly(2-aminophenol). The intercalation of polymers into the clay layers was confirmed by X-ray diffraction studies, TEM images and FTIR spectroscopy. In addition, the room temperature conductivity values of these nanocomposites varied between 8.21 × 10−5 and 6.76 × 10−4 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites, has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerization into Na-M produces electroactive polymers.

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Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

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A novel polymer/TiC nanocomposites “PPA/TiC, poly(PA-co-ANI)/TiC and PANI/TiC” was successfully synthesized by chemical oxidation polymerization at room temperature using p-anisidine and/or aniline monomers and titanium carbide (TiC) in the presence of hydrochloric acid as a dopant with ammonium persulfate as oxidant. These nanocomposites obtained were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and thermogravimetric analysis (TGA). XRD indicated the presence of interactions between polymers and TiC nanoparticle and the TGA revealed that the TiC nanoparticles improve the thermal stability of the polymers. The electrical conductivity of nanocomposites is in the range of 0.079–0.91 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerisation on TiC nanoparticles produces electroactive polymers. These nanocomposite microspheres can potentially used in commercial applications as fillers for antistatic and anticorrosion coatings.

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A novel and selective electrochemical functionalization of a highly reactive superporous zeolite templated carbon (ZTC) with two different aminobenzene acids (2-aminobenzoic and 4-aminobenzoic acid) was achieved. The functionalization was done through potentiodynamic treatment in acid media under oxidative conditions, which were optimized to preserve the unique ZTC structure. Interestingly, it was possible to avoid the electrochemical oxidation of the highly reactive ZTC structure by controlling the potential limit of the potentiodynamic experiment in presence of aminobenzene acids. The electrochemical characterization demonstrated the formation of polymer chains along with covalently bonded functionalities to the ZTC surface. The functionalized ZTCs showed several redox processes, producing a capacitance increase in both basic and acid media. The rate performance showed that the capacitance increase is retained at scan rates as high as 100 mV s−1, indicating that there is a fast charge transfer between the polymer chains formed inside the ZTC porosity or the new surface functionalities and the ZTC itself. The success of the proposed approach was also confirmed by using other characterization techniques, which confirmed the presence of different nitrogen groups in the ZTC surface. This promising method could be used to achieve highly selective functionalization of highly porous carbon materials.