ELECTROCATALYTIC OXIDATION OF REDUCED NICOTINAMIDE COENZYMES AT ORGANIC DYE-MODIFIED ELECTRODES

Chemically modified electrodes (CMEs) were prepared by adsorbing different dyes, including methylene blue (MB), toluidine blue (TB) and brilliant cresyl blue (BCB), onto glassy carbon electrodes (GCE) with anodic pretreatment. The electrochemical reactions of adsorbed dyes are fairly reversible at low coverages. The CMEs are more stable in acid solutions than in alkaline ones, which is mainly due to decomposition of the dyes in the latter media. They exhibit an excellent catalytic ability for the oxidation of nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between the coenzyme and the adsorbed mediator has been demonstrated using a rotating disk electrode. The charge transfer complex decomposition is a slow step in the overall electrode reaction process. Some kinetic parameters are estimated. Dependence of the electrocatalytic activity of the CMEs on the solution pH is discussed.

ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON ELECTRODES IN ACETONITRILE

The anodic oxidation kinetics of hydrazine on glassy carbon electrodes in acetonitrile were examined by cyclic voltammetry, a rotating ring-disc electrode technique and chronoamperometry. The experimental results of the rotating ring-disc electrode prove that hydrazine is oxidized to HN=NH, which cannot be oxidized further in acetonitrile. Hydrazine molecules are adsorbed on the electrode surface. One-third of the adsorbed hydrazine molecules are oxidized to HN=NH and the other two thirds act as proton acceptors. A possible mechanism of hydrazine oxidation is proposed.

ELECTROCHEMICAL CATALYSIS AT AN ULTRAMICROELECTRODE MODIFIED WITH REDOX SPECIES

General equations of the electrocatalytic reaction at an ultramicroelectrode modified with redox species have been described according to the Andrieux Saveant model. The electrocatalytic kinetic process has been discussed for the whole set of cases, ie (R), (R + S), (SR) (SR + E), (E), (R + E), (ER), (S), (ER + S) and (S + E) limiting situations. The effect of gamma on the catalytic steady state current shows that the higher the value of gamma, the lower the catalytic current. The kinetic process shifts rapidly from R to E with increasing values of gamma. It is favorable for catalysis only when gamma is very low. Therefore, the redox species modified ultramicroelectrode with thin film is utilized for electrocatalysis, and the larger the radius of ultramicroelectrode, the higher the catalytic efficiency.

THE ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON ELECTRODE

The anodic oxidation kinetics of hydrazine (N2H4) on glassy carbon (GC) electrode was examined by cyclic voltammetry, rotating disk and ring-disc electrode techniques. The possible mechanisms of N2H4 oxidation in both aqueous and nonaqueous solutions are proposed.

ELECTROCHEMICAL-BEHAVIOR OF YTTRIUM ION IN LICL-KCL-NACL EUTECTIC MELT

The electrochemical reduction of yttrium ion on a molybdenum electrode in a LiCl-KCl-NaCl eutectic melt at 723 K was found to be almost reversible and to proceed by a one-step three electron reaction. The diffusion coefficient D of the Y(III) ion was measured to be (3.3 +/- 0.4) x 10(-6) cm2 s-1 by cyclic voltammetry, (5.0 +/- 0.9) x 10(-6) cm2 s-1 by the rotating disk electrode method, and (7.1 +/- 0.7) x 10(-6) cm2 s-1 by chronopotentiometry. The D values obtained by the latter two methods are in fairly good agreement with each other. The rather low D value obtained by cyclic voltammetry might be attributed to the fact that yttrium metal can dissolve slightly in the chloride melt. The standard potential of Y(III)/Y(0) couple was determined to be (-3.174 +/- 0.006) V (vs. Cl2/Cl-) by open-circuit potentiometry, (-3.15 +/- 0.02) V (vs. Cl2/Cl-) by the rotating disk electrode method and (-3.16 +/- 0.02) V (vs. Cl2/Cl) by chronopotentiometry. These three values are in good agreement with each other. Several types of Ni-Y intermetallic compounds were found to be formed on a nickel electrode.

INTERPRETATION OF THE PHOTOREDUCTION CURRENT RESPONSE ON POLYANILINE MODIFIED ELECTRODE

The photoreduction current response on a polyaniline modified electrode is interpreted as photo-assisted reduction of oxygen dissolved in the electrolyte solution but not due to the excited species PAn* and PAn* dagger. The effect of light is just the same as that of the electrode rotating or of stirring of the electrolyte which accelerates the oxygen dissolved in the electrolyte solution to react with leucoemeraldine (reduced polyaniline). The potentiostat is set to reduce the oxidized polyaniline at constant potential, thus producing a reduction current.

ELECTROCATALYTIC OXIDATION OF ASCORBIC ACID AT POLYANILINE FILM MODIFIED GLASSY CARBON ELECTRODES

A conducting polyaniline (PAn) film modified glassy carbon (GC) electrode was prepared by electrochemical polymerization. The electrochemical behavior of ascorbic acid (AH(2)) in aqueous solution at this PAn modified electrode was studied in detail. The experimental results show that PAn film modified electrode has good electrocatalytic activity on the oxidation of ascorbic acid in aqueous solution over a wide range of pH value, among which pH 4 is the optimum condition. The oxidation process of ascorbic acid at PAn film electrode can be regarded as an EC catalytic mechanism. The kinetic process of the catalytic reaction was investigated by rotating disk electrode (RDE) coated with PAn films. The rate constant of the catalytic reaction was evaluated. The catalytic peak currents are proportional to the concentrations tions of ascorbic acid in the range of 5 x 10(-2)-1 x 10(-6) mol . L-1. The PAn film elec trodes give very stable responce for the oxidation of ascorbic acid. The present investigation shows the posibility of using PAn film modified electrode for the determination of ascorbic acid.

ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON MODIFIED BY MACROCYCLIC TRANSITION-METAL COMPLEXES .1. COBALT PROTOPORPHYRIN DIMETHYL ESTER MODIFIED ELECTRODE

The electrocatalytic oxidation of hydrazine (N2H4) on a glassy carbon electrode (GC) modified by monolayer and polymer films of cobalt protoporphyrin dimethyl ester (CoPP) has been studied. Both the monolayer and polymer films of CoPP are very active to the anodic oxidation of N2H4. The activity of CoPP for the anodic oxidation of N2H4 is dependent on the pH of the solution, and the thickness of polymerized CoPP film. The oxidation kinetics were examined by methods of cyclic voltammetry, rotating disc electrodes and steady-state polarization measurement.

THE ELECTROCATALYTIC OXIDATION OF ASCORBIC-ACID ON PRUSSIAN BLUE FILM MODIFIED ELECTRODES

The kinetics of prussian blue (PB) film itself during the redox process and of the catalytic oxidation of ascorbic acid (AH_2) on it have been studied in detail. The charge transfer diffusion coefficient D_(ct) in PB film is determined as 2.62×10~(-10)cm~2·s~(-1), using potential-step chronoamperometry, chronocoulometry and constant-current chronopotentialmetry, respectively. The rate constant of the cross-exchange reaction between AH_2 in solution and the active centers in PB film is measured in rotating d...

Numerical simulation of principal tidal constituents in the South China Sea, Gulf of Tonkin and Gulf of Thailand

The principal tidal constituents M-2, S-2, K-1 and O-1 in the South China Sea, Gulf of Tonkin and Gulf of Thailand are simulated simultaneously using the numerical scheme of Kwok et al. (1995 Proceedings of the 1st Asian Computational Fluid Dynamics Conference, pp. 16-19). The average differences between the computed and observed harmonic constants are mostly within 5 cm and 10 degrees for amplitudes and phase-lags, respectively. The simulated tidal regimes in the present model are believed to be more accurate than the previous numerical results. Our studies confirm that a clockwise rotating M-2 amphidromic system lies in the southeast of the Gulf of Thailand and an S-2 amphidromic system at the near-shore area of the northeast South China Sea. The linear tidal energy equation developed by Garrett (1975 Deep-Sea Research 22, 23-35) is generalized to the nonlinear case. Based on the numerical results, the energy budgets in the South China Sea and its subareas, namely the Taiwan Strait, the Gulf of Tonkin, the Gulf of Thailand and the remaining area are investigated. The tidal motion in the Taiwan Strait is maintained mainly by the energy fluxes from the East China Sea for both semidiurnal and diurnal species and partially from the Luzon Strait for semidiurnal species. For the other parts of the South China Sea, the tidal motion is mainly maintained by the energy fluxes through the Luzon Strait. The energy inputs from the tide-generating force are negative for semidiurnal species and positive for diurnal species. (C) 1999 Elsevier Science Ltd. All rights reserved.

Effective properties of graded elliptical cylindrical composites

The effective property has been investigated theoretically in graded elliptical cylindrical composite's consisting of inhomogeneous graded elliptical cylinders and an isotropic matrix under external uniform electric field. As a theoretical model, the dielectric gradient profile in the elliptical cylinder is modeled by a power-law function of short semi-axis variable parameter (xi(2) - 1) in the elliptical cylindrical coordinates, namely epsilon(i)(xi) = c(k) (xi(2) - 1)(k), where c(k) and k are the parameters, and xi is the long semi-axis space variable in an elliptical cylindrical inclusion region. In the dilute limit, the local analytical potentials in inclusion and matrix regions are derived exactly by means of the hyper-geometric function, and the formulas are given for estimating the effective dielectric responses under the external lfield along (x) over cap- and (y) over cap -directions, respectively. Furthermore, we have demonstrated that our effective response formulas can be reduced to the well-known results of homogeneous isotropic elliptical cylindrical composites if we take the limit k -> 0 in graded elliptical cylindrical composites. (c) 2006 Elsevier B.V. All rights reserved.

Light energy conversion into H-2 by Anabaena variabilis mutant PK84 dense cultures exposed to nitrogen limitations

Concentrated cultures (25-86 mg Chl a l(-1)) of Anabaena variabilis PK84 were incubated under 99% Ar+1% CO2 atmosphere in the photobioreactor made of coaxial cylinders. Under illumination equal to 353 mu E m(-2) s(-1) they produced hydrogen with the rate more than 20 ml l(-1) h(-1) for several days. The efficiency of light energy conversion into H-2 was approx. 1% and did not depend significantly on initial Chl a concentration. H-2/O-2 ratio reached 41.5% of theoretical value for water photolysis. Data indicate that dense cultures might be used for outdoor systems under direct sun light. Supra-optimal temperatures 36 degrees C were not harmful for cultures even for 2 days period. Short-term incubation of cultures under 36 degrees C even increased H2 production rate and efficiency of light energy bioconversion by 1.25 times. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

The electrochemical reduction reaction of dissolved oxygen on Q235 carbon steel in alkaline solution containing chloride ions

Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.

对螺钉无轴向压力的高精度自动螺丝刀的设计

区别于现有的电动、气动螺丝刀工具,该螺丝刀系统在驱动螺丝时,能对螺钉头实现无轴向压力的调节。刀头在旋转的同时随螺钉轴向进给,转速与进给量匹配,保证刀头与螺钉不脱节。该系统调整精度高,刀头转动精度可达0.72°,其应用于断路器类低压电气产品的自动调试,对确保产品质量、提高生产效率具有积极意义。