925 resultados para Oxygen reduction reaction mechanism
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.
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The rate constants for reduction of the flavoenzyme, l-lactate oxidase, and a mutant (in which alanine 95 is replaced by glycine), by a series of para-substituted mandelates, in both the 2-1H- and 2-2H- forms, have been measured by rapid reaction spectrophotometry. In all cases, significant isotope effects (1H/2H = 3–7) on the rate constants of flavin reduction were found, indicating that flavin reduction is a direct measure of α-C-H bond breakage. The rate constants show only a small influence of the electronic characteristics of the substituents, but show a good correlation when combined with some substituent volume parameters. A surprisingly good correlation is found with the molecular mass of the substrate. The results are compatible with any mechanism in which there is little development of charge in the transition state. This could be a transfer of hydride to the flavin N(5) position or a synchronous mechanism in which the α-C-H is formally abstracted as a H+ while the resulting charge is simultaneously neutralized by another event.
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This work aims to understand the influence of TiO2 surface structure in Au/TiO2 catalysts on CO oxidation. Au nanoparticles (3 wt%) in the range of 4 to 8 nm were loaded onto four kinds of TiO2 surfaces, which had different surface structures and were synthesized by calcining hydrogen titanate nanotubes at various temperatures and in different atmospheres. The Au catalyst supported on anatase nanorods exhibited the highest activity in CO oxidation at 30 °C among all the five Au/TiO2 catalysts including the reference catalyst of Au/TiO2-P25. X-ray photoelectron spectroscopy (XPS) and infrared emission spectra (IES) results indicate that the anatase nanorods have the most active surface on which water molecules can be strongly adsorbed and OH groups can be formed readily. Theoretical calculation indicates that the surface OH can facilitate the O2 adsorption on the anatase surface. Such active surface features are conducive to the O2 activation and CO oxidation
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The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.
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Catalytic activities of some transition metal-phthalocyanine complexes towards electroreduction of molecular oxygen are examined on Nafion®-bound and bare porous carbon electrodes in 2.5 M H2SO4 electrolyte. It is found that these metal complexes exhibit better catalytic activities towards oxygen reduction with the Nafion®-bound electrodes.
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Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cnbalt-phosphate (Co-Pi) catalyst: Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and It centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water.
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Iridium nanoparticles-anchored reduced graphene oxide (Ir-RGO) was prepared by simultaneous reduction of graphene oxide and Ir3+ ions and its catalytic activity for oxygen electrode in Li-O-2 cells was demonstrated. Ir particles with an average size of 3.9 nm were uniformly distributed on RGO sheets. The oxygen reduction reaction (ORR) was studied on an Ir-RGO catalyst in non-aqueous electrolytes using cyclic voltammetry and rotating disk electrode techniques. Li-O-2 cells with Ir-RGO as a bifunctional oxygen electrode catalyst were subjected to charge-discharge cycling at several current densities. A discharge capacity of 9529 mA h g(-1) (11.36 mA h cm(-2)) was obtained initially at a current density of 0.5 mA cm(-2) (393 mA g(-1)). A decrease in capacity was observed on increasing the current density. Although there was a decrease in capacity on repeated discharge-charge cycling initially, a stable capacity was observed for about 30 cycles. The results suggest that Ir-RGO is a useful catalyst for rechargeable Li-O-2 cells.
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It was based on the comparisons of the variance properties of fragment multiplicities FM's and nuclear stoppings R's for the neutron-halo colliding system with those of FZ's and R's for the proton-halo colliding system with the increases of beam energy in more detail, the closely correlations between the reaction mechanism and the inner structures of halo-nuclei is found. From above comparisons it is found that the variance properties of fragment multiplicities and nuclear stopping with the increases of beam energy are quite different for the neutron-halo and proton-halo colliding systems, such as the effects of loosely bound neutron-halo structure on the fragment multiplicities and nuclear stopping are obviously larger than those for the proton-halo colliding system. This is due to that the structures of halo-neutron nucleus Li-11 is more loosely than that of the proton-halo nucleus Al-23 in this paper. In this case, the fragment multiplicity and nuclear stopping of halo nuclei may be used as a possible probe for studying the reaction mechanism and the correlation between the reaction mechanism and the inner structure of halo-nuclei.
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Combined with polymer wrapping and layer-by-layer techniques, a noncovalent functionalization method is developed to disperse Pt nanocubes (NCs) onto carbon nanotubes (CNTs). By adjusting the relative ratio of Pt NCs to CNTs, nanotubes with different Pt NC loadings are produced. The composites exhibit excellent electrocatalytic activity towards oxygen reduction.