999 resultados para Electrochemical window


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The nucleataon growth model of electrochemical phase formation is analysed for the hnear potential sweep input Apart from deducing diagnostic criteria and method~ of estimating model parameters, the predictions of the nucleation growth model are compared and contrasted with those of a sample adsorption model A dastlnCtlOn is made possible between adsorption and phase transition, which seems useful for understanding the nature of ECPF phenomena, especially underpotentlal deposition (UPD).

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A two-state Ising model has been applied to the two-dimensional condensation of tymine at the mercury-water interface. The model predicts a quadratic dependence of the transition potential on temperature and on the logarithm of the adsorbate concentration. Both predictions have been confirmed experimentally.

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Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

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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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The use of capacitors for electrical energy storage actually predates the invention of the battery. Alessandro Volta is attributed with the invention of the battery in 1800, where he first describes a battery as an assembly of plates of two different materials (such as copper and zinc) placed in an alternating stack and separated by paper soaked in brine or vinegar [1]. Accordingly, this device was referred to as Volta’s pile and formed the basis of subsequent revolutionary research and discoveries on the chemical origin of electricity. Before the advent of Volta’s pile, however, eighteenth century researchers relied on the use of Leyden jars as a source of electrical energy. Built in the mid-1700s at the University of Leyden in Holland, a Leyden jar is an early capacitor consisting of a glass jar coated inside and outside with a thin layer of silver foil [2, 3]. With the outer foil being grounded, the inner foil could be charged with an electrostatic generator, or a source of static electricity, and could produce a strong electrical discharge from a small and comparatively simple device.

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The phenomenological theory of hemispherical growth is generalised to time-dependent nucleation and growth-rates. Special cases, which include models with diffusion-controlled rates, are analysed. Expressions are obtained for small and large time behaviour and peak characteristics of potentiostatic transients, and their use in model parameter estimation is discussed. Two earlier equations are corrected. Numerically calculated transients which are presented exhibit some interesting features such as a maximum preceding the steady state, oscillations and shoulder.

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A general theory is evolved for a class of macrogrowth models which possess two independent growth-rates. Relations connecting growth-rates to growth geometry are established and some new growth forms are shown to result for models with passivation or diffusion-controlled rates. The corresponding potentiostatic responses, their small and large time behaviours and peak characteristics are obtained. Numerical transients are also presented. An empirical equation is derived as a special case and an earlier equation is corrected. An interesting stochastic result pertaining to nucleation events in the successive layers is proved.

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We compare two popular methods for estimating the power spectrum from short data windows, namely the adaptive multivariate autoregressive (AMVAR) method and the multitaper method. By analyzing a simulated signal (embedded in a background Ornstein-Uhlenbeck noise process) we demonstrate that the AMVAR method performs better at detecting short bursts of oscillations compared to the multitaper method. However, both methods are immune to jitter in the temporal location of the signal. We also show that coherence can still be detected in noisy bivariate time series data by the AMVAR method even if the individual power spectra fail to show any peaks. Finally, using data from two monkeys performing a visuomotor pattern discrimination task, we demonstrate that the AMVAR method is better able to determine the termination of the beta oscillations when compared to the multitaper method.

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By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

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Room-temperature zinc ion-conducting molten electrolytes based on acetamide, urea, and zinc perchlorate or zinc triflate have been prepared and characterized by various physicochemical, spectroscopic, and electrochemical techniques. The ternary molten electrolytes are easy to prepare and can be handled under ambient conditions. They show excellent stability, high ionic conductivity, relatively low viscosity, and other favorable physicochemical and electrochemical properties that make them good electrolytes for rechargeable zinc batteries. Specific conductivities of 3.4 and 0.5 mS cm(-1) at 25 degrees C are obtained for zinc-perchlorate-and zinc-triflate-containing melts, respectively. Vibrational spectroscopic data reveal that the free ion concentration is high in the optimized composition. Rechargeable Zn batteries have been assembled using the molten electrolytes, with gamma-MnO2 as the positive electrode and Zn as the negative electrode. They show excellent electrochemical characteristics with high discharge capacities. This study opens up the possibility of using acetamide-based molten electrolytes as alternate electrolytes in rechargeable zinc batteries. (C) 2009 The Electrochemical Society.

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Spectroscopic and electrochemical redox properties of a series of fluorinated porphyrins bearing donor-acceptor groups and their Zn(II) and Cu(II) derivatives are presented. The magnitude of the ring reduction potentials and charge transfer properties derived from spectral data depend on the nature and position of the substituent(s), (nitro/dimethylamino) and the central metal ions.