Sharif Digital Repository

Nickel and nickel-manganese alloy modified graphite electrodes (G/Ni and G/NiMn) prepared by galvanostatic deposition were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (EIS) were employed. In CV studies, in the presence of methanol NiMn alloy modified electrode shows a significantly higher response for methanol oxidation. The peak current of the oxidation of nickel hydroxide increase is followed by a decrease in the corresponding cathodic current in presence of methanol. The anodic peak currents show linear dependency upon the... 

Oxygen reduction on a polycrystalline silver electrode was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The reaction occurred by a two-electron pathway. The steps in the mechanism were observed in the cyclic voltammograms recorded with different scan rates. The intermediates formed in the steps were detected by electrochemical impedance spectroscopy  

The electrocatalytic oxidation of hydrazine was studied over Ni, Cu, Co and Ni-based ternary alloy on graphite electrodes in alkaline solution. The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and the catalytic activity of the modified electrodes were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). It was found that, in the presence of hydrazine, the modified Ni-based ternary alloy electrode (G/NiCuCo) exhibited a good catalytic activity for the oxidation of hydrazine at a reduced overpotential and it has a significant high... 

The electro-oxidation of methanol on nickel and nickel-copper alloy modified glassy carbon electrodes (GC/Ni and GC/NiCu) in a 1 M NaOH solution at different concentrations of methanol was studied by the method of ac-impedance spectroscopy. Two semicircles in the first quadrant of a Nyquist diagram were observed for electro-oxidation of methanol on GC/Ni corresponding to charge transfer resistance and adsorption of intermediates. Electro-oxidation of methanol on GC/NiCu shows negative resistance in impedance plots as signified by semi-circles terminating in the second quadrant. The impedance behavior shows different patterns at different applied anodic potential. The influence of the... 

Nickel and nickel-copper alloy modified glassy carbon electrodes (GC/Ni and GC/NiCu) prepared by galvanostatic deposition were examined for their redox processes and electro-catalytic activities towards the oxidation of glucose in alkaline solutions. The methods of cyclic voltammetry (CV) and chronoamperometry (CA) were employed. The cyclic voltammogram of NiCu alloy demonstrates the formation of β/β crystallographic forms of the nickel oxyhydroxide under prolonged repetitive potential cycling in alkaline solution. It is also observed that the overpotential for O 2 evolution increases for NiCu alloy modified electrode. In CV studies, NiCu alloy modified electrode yields significantly higher... 

Electrochemical deposition of aluminum and manganese from basic and acidic molten AlCl3-NaCl-KCl mixture on an aluminum electrode at 180 °C was studied by the methods of voltammetry, and potential and current transient. The deposition of aluminum was found to proceed via a nucleation/growth mechanism in basic melt, while the deposition of manganese was found to be diffusion controlled in basic melt. The diffusion coefficient of Mn2+ ions in basic melt, as derived by voltammetry was in agreement with the deductions of transient methods. Analysis of the chronoamperograms indicates that the deposition of manganese on Al was controlled by 3D diffusion controlled nucleation and growth. The... 

Electrochemical deposition of aluminum and lead from basic molten AlCl3-NaCl-KCl mixture on an aluminum electrode at 180 °C was studied by the methods of voltammetry, potential and current transient and constant current deposition. The deposition of aluminum was found to proceed via a nucleation/growth mechanism, while the deposition of lead was found to be diffusion controlled. The diffusion coefficient calculated for Pb2+ ions in basic melt by voltammetry was in agreement with the deductions of transient method. The analysis of the chronoamperograms indicates that the deposition process of lead on Al substrates was controlled by 3D diffusion control, nucleation and growth. The processes... 

Nickel and nickel-copper alloy modified glassy carbon electrodes (GC/Ni and GC/NiCu) prepared by galvanostatic deposition were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetery (CV) and chronoamperometry (CA) were employed. The cyclic voltammogram of NiCu alloy demonstrates the formation of β/β crystallographic forms of the nickel oxyhydroxide under prolonged repetitive potential cycling in alkaline solution. In CV studies, in the presence of methanol NiCu alloy modified electrode shows a significantly higher response for methanol oxidation. The peak current of the oxidation of nickel... 

Nickel - copper alloy modified glassy carbon electrodes (GC/NiCu) prepared by galvanostatic deposition were used for the electrocatalytic oxidation of glucose in alkaline solutions. The electro-oxidation of glucose in a 1 M NaOH solution at different concentration of glucose was studied by the method of ac-impedance spectroscopy. The impedance behavior show different patterns, capacitive, and inductive loops and negative resistances, at different applied anodic potential. The influence of the electrode potential on the impedance pattern is studied and a quantitative explanation for the impedance behavior of glucose oxidation is put forward by a proposed mathematical model. At potentials... 

The electrochemical behavior of a tin electrode in citric acid solutions of different concentrations was studied by electrochemical techniques. The E/I curves showed that the anodic behavior of tin exhibits active/passive transition. Passivation is due to the formation of Sn(OH)4 and/or SnO2 film on the electrode surface. Addition of NaCl to citric acid solution, enhances the active dissolution of tin and tends to breakdown the passivity at a certain breakdown potential. Cyclic voltammetry and galvanostatic measurements allow the pitting potential (Epit) and the repassivation potential (Erp) to be determined. Potentiostatic measurements showed that the overall anodic processes can be... 

The mechanism and kinetics of the hydrogen evolution reaction (HER) on tin electrode in 0.1 M H2SO4 solution were studied using the methods of steady-state polarization and electrochemical impedance spectroscopy. The simulation of the data obtained from these two methods, using nonlinear fitting procedure allowed us to determine the rate constants of Volmer, Heyrovsky and Tafel steps associated with the mentioned reaction. The kinetic results indicate that HER mechanism at low negative potentials is a serial combination of Volmer step and parallel Tafel and Heyrovsky steps. At high negative potentials where the hydrogen coverage reaches its limiting value, a Tafel line with the slope of -... 

Electrocatalytic activity of electrodeposited nanocrystalline CoNiFe alloy in hydrogen evolution reaction (HER) was studied in 1 M NaOH solution. The steady-state polarization measurement and electrochemical impedance spectroscopy were used to determine the Tafel slope, the exchange current density and the activation energy. The simulation of the data obtained from these two methods, using a nonlinear fitting procedure, allowed us to determine the surface coverage and the rate constants associated with the mentioned reaction. The ac-impedance spectra measured at various overpotentials in the HER region exhibited three semicircles in the complex plane plots. The high-frequency semicircle was... 

Aluminum electrocrystallization is studied by means of electrochemical impedance spectroscopy (EIS). A model based on random birth and deterministic growth of monolayers is proposed, in which the edges are assumed to follow a propagation law. The high frequency impedance data show charge transfer reaction of AlCl4- reduction while the low frequency features signifies the growth mode of deposits. The inductive response observed in the course of polycrystalline deposition reflects the activation of electrode area while a capacitive loop appears in regular growth. Parameters of impedance model in this system can be calculated from the fitting of experimental data to the Faradaic impedance... 

Hydrogen evolution and electrosorption on/in TiHg alloy have been investigated in acidic solution using cyclic voltammetry, open circuit potential transient, steady-state polarization, chronopotentiometry and electrochemical impedance measurements. Comparison has been made with pure Ti. Cyclic voltammetry and open circuit potential measurements show that hydrogen absorption into the electrode material occurs during proton discharge. The steady-state polarization curves in the course of positive and negative potential scans illustrate that the formation of absorbed hydrogen slightly improves the electrocatalytic properties of the electrode. The hydrogen diffusion coefficient into the bulk of... 

Electrochemical deposition of aluminum from basic and acidic molten NaCl-KCl-AlCl3 mixture on a graphite electrode at 140 °C was studied by voltammetry, chronopotentiometry and constant current deposition. The deposition of aluminum was found to proceed via a nucleation/growth mechanism in basic melt, while it was found to be diffusion controlled in acidic melt. The diffusion coefficient calculated for Al2Cl- 7 ions in acidic melt by voltammetry was in agreement with the deductions of voltammetry. The morphology of the aluminum deposits was examined using a metallographic microscope and by SEM. It was shown that, depending on the current density (c.d.) and AlCl3 concentration (acidic or... 

The electro-catalytic oxidation of methanol on a Ni-Cu alloy (NCA) with atomic ratio of 60/40 having previously undergone 50 potential sweep cycles in the range 0-600 mV vs. (Ag/AgCl) in 1 m NaOH was studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS). The electro-oxidation was observed as large anodic peaks both in the anodic and early stages of the cathodic direction of potential sweep around 420 mV vs. (Ag/AgCl). The electro-catalytic surface was at least an order of magnitude superior to a pure nickel electrode for methanol oxidation. The diffusion coefficient and apparent rate constant of methanol oxidation were found to be 2.16 × 10-4 cm2 s-1 and... 

Electrodeposition of aluminum onto graphite from a molten electrolyte containing AlCl3-NaCl-KCl was studied by the method of chronoamperometery. In the early stage of the deposition and at low cathodic potentials two-dimensional (2D) nucleation and growth proceeding through instantaneous and a multitude of progressive steps followed the initial double layer charging. The processes are manifested as peaks on a decaying chronoamperogram. Non-linear fitting methods were applied to obtain the kinetic parameters in the light of Bewick, Fleischmann and Thirsk (BFT) theory. Under more cathodic potentials, transition from 2D to three-dimensional (3D) processes have been observed as manifested in the... 

Platinum microparticles electrodeposited at a glassy carbon surface (Pt/GC) and within a poly-ortho-aminophenol film formed on a GC substrate (Pt/PoAP/GC) have been used for investigating their catalytic activity towards hydrogen evolution reaction and methanol oxidation by cyclic voltammetry, impedance spectroscopy and chronoamperometry. The effect of the deposition time (t dep) of the Pt particles dispersed into GC and PoAP electrodes and of the acid anions (SO42-, ClO4- on the hydrogen adsorption/desorption peaks and hydrogen evolution reaction has been studied. It has been shown that the main cause of immediate blocking of the PoAP-SO42- pores with platinum microparticles is its smaller... 

The electro-oxidation of methanol on copper in alkaline solutions has been studied by the methods of cyclic voltammetry, quasi-steady state polarization and chronoamperometry. It has been found that in the course of an anodic potential sweep the electro-oxidation of methanol follows the formation of CuIII and is catalysed by this species through a mediated electron transfer mechanism. The reaction also continues in the early stages of the reversed cycle until it is stopped by the prohibitively negative potentials. The process is diffusion controlled and the current-time responses follow Cottrellian behavior. The rate constants, turnover frequency, anodic transfer coefficient and the apparent... 

The processes of adsorption and absorption of H atoms on silver electrode in alkaline media has been studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The potential range in the CV studies has been between -0.1 and -1.6 V /Ag-AgCl. In the first cycle, two cathodic and three anodic peaks have been observed. The H atom electrosorption current peak at ca. -0.6 V/Ag-AgCl, which appears at second cycle, is assigned to hydrogen absorption states. Nyquist plots consist of two overlapping semi-circles of variable diameters depending on the extent of the cathodic dc-potential offset. Hydrogen absorption occurs simultaneously with the hydrogen evolution reaction...