Sharif Digital Repository

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... 

Cathodically deposited Ag 2Se, to form a 1-μm-thick film, characterized by energy dispersive X-ray analysis and scanning electron microscopy, showed high electro-catalytic activity for l-ascorbic acid oxidation in alkaline solution. The onset of the process was about 80 mV cathodic of that previously observed on Ag under the same conditions and far superior over glassy carbon and Pt. The values of the exchange current density, standard heterogeneous rate constant, and transfer coefficient of the reaction were 1. 65 × 10 -4 A cm -2, 4. 35 × 10 -7 cm s -1, and 0. 60, respectively. Diffusion coefficient of l-ascorbate di-anion was also measured and was around 7. 00 × 10 -6 cm 2 s -1  

Complexes of Ni II-(N,N′-bis(2-hydroxy, 3-methoxy benzaldehyde)-1,2-propandiimine) can be electro-polymerized onto GC electrode in an alkaline solution to give an electro-active film strongly adhered on the electrode surface. In alkaline solution, this poly-(Ni II{sal-1,2-pn(3-OMe) 2})/GC film shows the typical voltammetric response of a surface-immobilized redox couple, as can be anticipated for the Ni 2+/Ni 3+ transitions into the film. In addition, the film exhibits a potent and persistent electro-catalytic activity towards the oxidation of 1- and 2-propanol. In CV studies, in the presence of these alcohols, poly-(Ni II{sal-1,2-pn(3-OMe) 2})/GC electrode shows a new oxidation peak for the... 

Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A... 

Electro-oxidation of methanol on Ni in NaOH solutions with the alkali concentration in the range of 0.05-0.5 M and in the presence of 0.5 M Na 2SO4 supporting electrolyte is studied. All the mentioned species compete for adsorption on Ni and OH- is essential for the electro-oxidation process. The electro-oxidation seems to proceed through the electro-chemical reactions of adsorbed methanol and hydroxide species and the removal of the resulting intermediate by adsorbed hydroxyl groups. The mechanism is consistent with the cyclic voltammetry and impedance spectroscopy results and can semi-quantitatively account for the appearance of capacitive, inductive and negative resistance loops as well... 

Electrochemical oxidation of l-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10-5 cm2 s-1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm-2 and 4 mF cm-2 as well as the adsorption and decomposition resistances (rates). © 2009 Elsevier B.V. All... 

L-Ascorbate anion electro-oxidation on a silver electrode in hydroxide solution in the absence and presence of sodium polysulfide of concentrations from 1 × 10 -5 to 4.5 × 10 -4 mol/L was studied using cyclic voltammetry and electrochemical impedance spectroscopy. Both hydroxide and polysulfide ions inhibited L-ascorbate ion oxidation, with the poisoning effect of polysulfide ion being more pronounced in the potential range of -0.3 to -0.2 V/SCE. The time constants for L-ascorbate ion oxidation in the absence and presence of polysulfide were, 10 -3 to 1 × 10 -2 s and 1 × 10 -4 to 1 × 10 -2 s, respectively depending on the potential used for the impedance analysis. Based on the cyclic... 

The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution (0.1 mol/L). The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and 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 methanol, the modified Ni-based ternary alloy electrode (G/NiCuCo) exhibited a significantly higher response for methanol oxidation compared to the other samples. The anodic peak... 

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... 

In this work, a nanocomposite containing manganese dioxide (MnO2) modified reduced graphene oxide (rGO) supported bimetallic palladium-nickel (Pd-Ni) catalyst is prepared by electrodeposition method. The nanocomposite modifier film is prepared by forming a thin layer of graphene oxide (GO) via drop-casting of GO nanosheet dispersion on glassy carbon electrode (GCE), followed by electrochemical reduction of the film to provide rGO/GCE. Then, a two-step potential procedure is applied to deposit MnO2 nanoparticles on rGO/GCE. At the optimum deposition conditions, MnO2 nanoparticles with a thickness of 30-50 nm homogeneously covered the rGO surface (MnO2/rGO/GCE). Finally, the bimetallic Pd-Ni... 

A carbon-paste electrode (CPE) modified with iron(II) phthalocyanine was used for the sensitive voltammetric determination of epinephrine (EN). The electrochemical response characteristics of the modified electrode toward EN, ascorbic acid (AA) and uric acid (UA) were investigated by cyclic and differential pulse voltammetry (CV and DPV). The results show an efficient catalytic activity of the electrode for the electro-oxidation of EN, which leads to improvement of reversibility of the electrode response and lowering its overpotential by more than 100 mV. The effect of pH and potential sweep rate on the mechanism of the electrode process was investigated. The modified electrode exhibits an... 

Over the last few years, substantial efforts have been made to develop earth-abundant bi-functional catalysts for urea oxidation and energy-saving electrolytic hydrogen production due to their low cost and the potential to replace traditional noble-metal-based catalysts. Nevertheless, finding a straightforward and effective route to prepare efficient catalysts with unique structural features and optimal supports still is a big challenge. Among the various candidates, metal-organic framework (MOF)-derived materials show great advantages as new kinds of active non-precious catalysts. On the other hand, the controllable integration of MOFs and carbon-based nanomaterials leads to further... 

The preparation and electrochemical performance of the carbon nanotube-paste electrode modified with salophen complexes of cobalt(III) perchlorate, with various substituents on the salophen ligand, as well as their electrocatalytic activity toward the oxidation of N-acetylcysteine (NAC) is investigated. Several Schiff base complexes containing various nucleophilic and electrophilic functional groups were prepared, and their electrochemical characteristics for the electro-oxidation of NAC were evaluated using cyclic and differential pulse voltammetry (CV and DPV). The results revealed, the modified electrodes show an efficient and selective electrocatalytic activity toward the anodic...