49 resultados para OXIDATION REACTION
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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In situ solid state oxidation reaction for an alternative La1-xSrxMnO3 (x = 0, 0.1, 0.2 and 0.3) formation is reported. Samples have been obtained by using strontium peroxide, lanthanum and manganese (III) oxide reagents. Strontium peroxide has induced the oxidation of Mn+3 to Mn+4. Lanthanum strontium-doped manganite was obtained without secondary phase formation. La0.825Sr0.175MnO3 showed two structural transitions. The first from 88 to 373 K and the second at 1073 K. which are explained by Jahn-Teller effect at low temperature and cation displacement at high temperature. (C) 2001 Elsevier B.V. B.V. All rights reserved.
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An experimentally based kinetic and mechanistic study of the hydrogen oxidation reaction (HOR) on platinum and platinum ordered intermetallic materials in acid medium is presented. RDE kinetic data were re-evaluated and complemented by Tafel plots obtained from chronoamperometric measurements. Among the materials evaluated, PtSb and PtSn exhibited markedly improved kinetic current densities and exchange current densities, compared to Pt in the same experimental conditions. It is proposed that the intermetallic phase enhanced the adsorptive characteristic of the surface sites and, as a consequence, improved the kinetics of the adsorption steps (Tafel or Heyrovsky) of the mechanism involved. (c) 2006 Published by Elsevier B.V.
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This describes an experimental evaluation of the electrocatalytic activity of the hydrogen oxidation reaction on electrodes of platinum and the ordered intermetallic phases PtSb and PtSn, on which CO has previously been deposited. The experiments were carried out in perchloric acid solution and the analysis based on steady-state polarization curves and Tafel plots derived from chronoamperometric data. Both intermetallics, PtSb and PtSn, performed better than Pt towards the HOR, when their surface was deliberately covered with CO. It is suggested that the intermetallic surfaces have a lower affinity for CO molecules, causing a lower CO coverage on these surfaces, and/or a weaker surface-CO interaction, compared to Pt under the same conditions. (C) 2007 Elsevier B.V. All rights reserved.
Kinetics and mechanism of the induced redox reaction of [Ni(cyclam)](2+) promoted by SO5 center dot-
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Oxidation of [Ni(cyclam)](2+), cyclam = 1,4,8,11-tetraazacyclotetradecane, accelerated by sulfur dioxide, was studied spectrophotometrically by following the formation of [Ni(cyclam)](3+) under the conditions: [Ni(cyclam)](2+) = 6.0 x 10(-3) M; initial [Ni(cyclam)](3+) = 8.0 x 10(-6) M; [cyclam] = 6.0 x 10(-3) M; [SO2] = (1.0-5.0) x 10(-4) M and 1.0 M perchloric acid in oxygen saturated solutions at 25.0 degrees C and ionic strength = 1.0 M. The oxidation reaction exhibits autocatalytic behavior in which the induction period depends on the initial Ni(III) concentration. A kinetic study of the reduction of Ni(III) by SO2 under anaerobic conditions, and the oxidation of Ni(II), showed that the rate-determining step involves reduction of Ni(III) by SO2 to produce the SO3.- radical, which rapidly reacts with dissolved oxygen to produce SO5.- and rapidly oxidizes Ni(II). The results clearly show a redox cycling process which depends on the balance of SO2 and oxygen concentrations in solution.
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Possible molecular mechanisms of the gas-phase ion/molecule reaction of VO2+ in its lowest singlet and triplet states ((1)A(1)/(3)A '') with propyne have been investigated theoretically by density functional theory (DFT) methods. The geometries, energetic values, and bonding features of all stationary and intersystem crossing points involved in the five different reaction pathways (paths 1-5), in both high-spin (triplet) and low-spin (singlet) surfaces, are reported and analyzed. The oxidation reaction starts by a hydrogen transfer from propyne molecule to the vanadyl complex, followed by oxygen migration to the hydrocarbon moiety. A hydride transfer process to the vanadium atom opens four different reaction courses, paths 1-4, while path 5 arises from a hydrogen transfer process to the hydroxyl group. Five crossing points between high- and low-spin states are found: one of them takes place before the first branching point, while the others occur along path 1. Four different exit channels are found: elimination of hydrogen molecule to yield propynaldehyde and VO+ ((1)Sigma/(3)Sigma); formation of propynaldehyde and the moiety V-(OH2)(+); and two elimination processes of water molecule to yield cationic products, Prod-fc(+) and Prod-dc(+) where the vanadium atom adopts a four- and di-coordinate structure, respectively.
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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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To assess the response of common sulfide minerals to oxidizing conditions, a methodology to immobilize mechanically solid particles on carbon surfaces (voltammetry of microparticles, VMP) was employed, to define the influence of the pyrrhotite content in pyrite-pyrrhotite mixtures. The influence of the galvanic interactions and local pH on the oxidation reaction of pyrite was also investigated. With this purpose, artificial two-mineral electrodes were constructed, ranging in weight from 20 to 80% pyrrhotite. The resulting cyclic voltammograms were analyzed and relative quantities of oxidation products were evaluated. The goal of this work was to define the boundary conditions, in terms of pyrrhotite content in the mixture, that determine the SO42-/S ratio obtained and to describe some parameters which influence this ratio: local pH and galvanic interactions. (C) 2003 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH 2, PtO 2, SnO 2 and IrO 2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded. © 2012 Sociedade Brasileira de Química.
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Pós-graduação em Engenharia e Ciência de Alimentos - IBILCE
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Pós-graduação em Química - IQ