920 resultados para Anodic Oxidation
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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(Photo)electrochemical experiments on pyrite electrodes in acetic acid-acetate buffer (pH = 4.5) are conducted to clarify the main oxidation reactions and the nature of the products. Electrochemical reactions in the -0.40 to 1.25 V (SHE) potential range are studied, and the production of iron (III) polysulfide from anodically formed iron oxides and polysulfides is discussed. Charges experimentally obtained are considered for the estimation of the most likely stoichiometry of the metallic polysulfide. The photoselectivity of the pyrite corrosion process indicates that the oxidation reactions of Fe2+ and S-2(2-) an not consecutive. The changes in stoichiometry and/or annihilation of crystalline structure defects are responsible for the observed photosensitivity of pyrite. A description of light effects on the interfacial behaviour and stability of pyrite is presented in terms of conduction and valence band energies, and thermodynamic potentials. (C) 2001 Elsevier Science B.V. All rights reserved.
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Cyclic voltammograms and capacitance measurements are presented to characterize the mineral response at relatively moderate environmental conditions, pH 4.5 and T = 25degreesC. The experiments involve examining the rates of oxidation and the surface morphology of arsenopyrite, which is oxidized abiotically. The semiconducting properties of the mineral have been investigated in attempt to gain additional information of FeAsS dissolution behavior in acidic solutions at potentials close to the open circuit potential of the mineral. A mechanistic pathway for the anodic dissolution of arsenopyrite in open circuit conditions is also suggested. At high overpotentials, anodic reactions produce mainly sulfate and arsenate ions and may be described as hole limited. The reduction of orpiment-like compounds at potentials more negative than the open circuit potential is discussed.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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The electrocatalytic oxidation of 1-propanol was investigated on platinum electrodes modified by submonolayers of Pb and Sn in acid media. An increase of oxidation rates observed for both Pb and Sn, and the influence of theta values was investigated. The values of the apparent activation energy evaluated from the Arrhenius plots concerning the electrochemical oxidation of 1-propanol on modified platinzed platinum electrodes, reveal a significant decrease in the presence of upd Sn and Ph adatoms. A decrease from 56 to 26 U mol(-1) in the presence of Sn. and from 78 to 25 U mol(-1) for Ph adatoms are some illustrative values which reflect the promoting effect of the upd adatoms.
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This study aimed to evaluate the sensitiveness of the information obtained for the residual lignin from Eucalyptus grandis kraft pulps analyzed through the nitrobenzene oxidation, copper oxide (CuO) reduction and acidolysis techniques. The chips were cooked, resulting pulps of kappa number 14,5 and 16,9, respectively. Both lignins' pulps were evaluated through three methods (nitrobenzene oxidation, copper oxide oxidation and acidolysis). Then, they were subjected to an oxygen delignification stage. The 16,9 kappa number pulp resulted in higher levels of non-condensed lignin structures by the acidolysis method, higher syringyl/vanillin ratios (S/V) by the nitrobenzene and copper oxide methods and better performance in the oxygen delignification stage. The different methods allowed to differ the residual lignin pulps with kappa number 14,5 and 16,9, and the nitrobenzene oxidation method showed the highest sensitiveness in this study results.
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Silver nanoparticles (Ag) were deposited on multi-walled carbon nanotube by eletroless. The hybrid Ag/MWCNT was used in the modification of glassy carbon electrode (GC) surface. The electrochemical characterization confirmed the presence of Ag in the nanocomposite has been showed that the synthesis was successful. The GC electrode modified with Ag/MWCNT film was evaluated for electro-oxidation of benzene. The electrochemical behavior presented an improvement on the catalytic surface in relation to non-modified GC electrode. The anodic peak current increased the magnitude in three times when compared with the CG electrode modified only with MWCNT
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The oxidation of ethanol (EtOH) at Pt(111) electrodes is dominated by the 4e path leading to acetic acid. The inclusion of surface defects such as those present on stepped surfaces leads to an increase of the reactivity towards the most desirable 12e path leading to CO2 as final product. This path is also favored when the methyl group is more oxidized, as in the case of ethylene glycol (EG) that spontaneously decomposes to CO on Pt(111) electrodes, thus showing a more effective breaking of the C-C bond. Some trends in reactivity can be envisaged when other derivative molecules are compared at well-ordered electrodes. This strategy was used in the past, but the improvement in the electrode pretreatment and the overall information available on the subject suggest that relevant information is still missing.
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A novel nanostructured composite, azide copper octa (3-aminopropyl)octasilsesquioxane (ASCA) was incorporated into a graphite paste electrode and the electrochemical studies were conducted with cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E ) = 0.30 V and an irreversible process at 1.1 V (vs Ag/AgCl; NaCl 1.0 mol L-1 ; v = 20 mV s-1 ). The redox couple with (E ) = 0.30V presents an electrocatalytic response for determination of ascorbic acid. The modified electrode gives a linear range from 1.010-4 – 1.010-3 mol L-1 (r = 0.998) for the determination of ascorbic acid with detection limit of 6.910-5 mol L-1 and standard deviation of 2.3% for n = 3 . The amperometric sensitivity was 122.1 mA/mol L-1 for ascorbic acid. The application this electrode was tested and ascorbic acid in three commercial pharmaceutical product (Cebion, Cewin and Redoxon) have been determined.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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The electrooxidation of hydroxylamine, NH2OH, in 0.1 M phosphate buffer (PB, pH = 7) on Pt-, and Pd-modified Au electrodes prepared by galvanic displacement of underpotential deposited Cu, was investigated by electrochemical techniques and three and in situ vibrational probes, substrate-induced surface enhanced Raman scattering, SI-SERS, surface enhanced infrared absorption, SEIRAS, and Fourier transform infrared reflection-absorption, IRAS, spectroscopies. Analyses of the results obtained made it possible to identify at low overpotentials, solution phase (sol) and adsorbed (ads) nitric oxide, NO, as well as solution phase nitrous oxide, N2O. As the potential was increased, the peak(s) ascribed to NO(ads) gained in intensity and new features associated with NO2−(ads) and NO2−(sol) were clearly discerned. Further excursion toward higher potentials yielded an additional peak assigned to NO2(ads). This behavior is analogous to that found for bare Au electrodes in a potential region in which the metal is at least partially oxidized under otherwise the same experimental conditions.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Specimens of aluminum-based composites reinforced by silicon carbide nanoparticles (Al/SiCnp) produced by powder metallurgy (PM) were anodized under voltage control in tartaric-sulfuric acid (TSA). In this work, the influence of the amount of SiCnp on the film growth during anodizing was investigated. The current density versus time response and the morphology of the porous alumina film formed at the composite surface are compared to those concerning a commercial aluminum alloy (AA1050) anodized under the same conditions. The processing method of the aluminum alloys influences the efficiency of the anodizing process, leading to a lower thicknesses for the unreinforced Al-PM alloy regarding the AA1050. The current density versus time response is strongly dependent on the amount of SiCnp. The current peaks and the steady-state current density recorded at each voltage step increases with the SiCnp volume fraction due to the oxidation of the SiCnp. The formation mechanism of the anodic film on Al/SiCnp composites is different from that occurring in AA1050, partly due the heterogeneous distribution of the reinforcement particles in the metallic matrix, but also to the entrapment of SiCnp in the anodic film.