• Journal of the Korean Electrochemical Society
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• v.15 no.2
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• pp.83-89
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• 2012

We investigate the electrocatalytic activities for oxygen reduction at nanoporous gold (NPG) surfaces fabricated by selective dissolution of Ag from electrodeposited Ag-Au layers on electrode surfaces. The structure of NPG was controlled by changing the concentration ratios of precursor metal complexes during the electrodeposition of Ag-Au layers and the corresponding surface morphology and surface area was examined. NPG structures with Ag/Au ratio of 2.0 exhibited the highest electrocatalytic activity for oxygen reduction, where the nanoporous structure plays a key role, but the surface area does not affect on the electrocatalytic activity. The mechanism of electroreduction of oxygen was investigated by rotating disk electrode techniques. In acidic media, oxygen was first reduced to hydrogen peroxide followed by further reduction to water through 2-step 4-electron mechanism, whereas the oxygen was reduced directly to water by 4-electron mechanism in basic media.

• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1303-1308
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• 1999

Conducting poly(3,4-ethylenedioxythiophene) (PEDT) films with metalloporphyrins incorporated as the counter ions were prepared by electropolymerization of the monomer in the presence of metal-tetra(sulfonatophenyl) porphyrin anions. Cathodic reduction of oxygen on the resulting conducting polymer films was studied. The overpotential for O2 reduction on electrodes with cobalt-porphyrin complex was significantly smaller in acidic solutions than on gold. In basic solutions, the overpotential at low current densities was close to those on platinum and gold. Polymer electrode with Co-complex yielded higher limiting currents than with Fe-complex, although the Co-complex polymer electrode was a poorer electrocatalyst for O2 reduction in the activation range of potential than the Fe counterpart. From the rotating ring-disk electrode experiments, oxygen reduction was shown to proceed through either a 4-electron pathway or a 2-electron pathway. In contrast to the polypyr-role-based electrodes, the PEDT-based metalloporphyrin electrodes were stable with wider potential windows, including the oxygen reduction potential. Their electrocatalytic properties were maintained at temperatures up to 80℃ in KOH solutions.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.786-790
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• 2004

2-Aminoethanethiol (aet) has been used to make self-assembled monolayer (SAMs) on gold electrodes, which are subsequently modified with 3,4-dihydroxy phenylalanine (dpa). Such modified electrodes having various types of Au/aet-dpa were employed in the electrocatalytic oxidation of NADH. The purpose of this study to characterize the responses of such modified electrodes in terms of the immobilization procedure, pH of the solution and applied potential. The reaction of the surface immobilized dpa with NADH was studied using the rotating disk electrode technique and a value of $2.2{\times}10^4M^{-1}s^{-1}$ was obtained for the second-order rate constant in 0.1 M Tris/$NO_3^-$buffer (pH=8.0). The hydration behavior of the films was characterized by quartz crystal microbalance. When used as a NADH sensor, the Au/aet-dpa electrode exhibited good sensitivity and an excellent correlation (r ${\geq}$ 0.99) for NADH concentration which extended to $3.8{\times}10^{-3}$ M.

• Journal of the Korean Society of Manufacturing Technology Engineers
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• v.21 no.5
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• pp.720-725
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• 2012

Sodium hypochlorite is used worldwide as a water disinfectant and in bleaching agent. Sodium hypochlorite applied to water initially undergoes hydrolysis to form free chlorine consisting of hypochlorous acid(HOCl) and hypochlorite ion($OCl^-$). For free chlorine determination, an electrochemical method is simple due to the electroactivity of free chlorine; it measures current and is free of most reagents. Amperometric free chlorine sensor has been developed with gold (Au)-based electrode. The 3-electrode free chlorine sensor whose working and counter electrodes were Pt exhibited excellent response to HClO at +400mV vs. Ag/AgCl/sat. KCl. In addition, the use of a pH error correction algorithm provided a reliable measurement of residual free chlorine in water sample without any pretreatment in the normal pH range(pH 6~8) of municipal water supply. The free chlorine sensor installed in on-line monitoring system could be used to continually monitor the level of residual free chlorine in real samples.

• Journal of the Korean Electrochemical Society
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• v.3 no.1
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• pp.49-56
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• 2000

In the present we.k, temperature dependence of oxygen diffusivity in the polyvinyl chloride (PVC) film $D_f$ formed on gold electrode was investigated using steady-state rotating disk electrode (RDE) technique and modulated electrohydrodynamic (EHD) impedance technique. Both the diffusion rate defined as the ratio of oxygen diffusivity in the PVC film to the film thickness $D_f/\delta_f$ and the time constant $\delta_f^2/D_f$ for oxygen diffusion through the PVC film were obtained from plot of the limiting current versus disk rotation speed and from filing the EHD impedance spectra experimentally measured to those theoretically calculated on the basis of the diffusion equation for mass transport through the non-conductive and porous film, respectively. By combining measured $D_f/\delta_f$ with $\delta_f^2/D_f$, we determined $\delta_f\;and\;D_f$ at room temperature separately. As temperature increased, it appeared that the $D_f$ value measured for the PVC film-covered gold RDE was enhanced more rapidly than that $D_s$ value in the solution measured for the PVC film-free gold RDE. This means that the pores glowing with increasing temperature act as effective diffusion paths within the film. The present in-situ steady-state and modulated EHD measurements prove to be effective for determining $\delta_f\;and\;D_f$, separately and at the same time the porosity of the PVC film at temperatures below glass temperature $T_g$ of the film.

• Journal of the Korean Electrochemical Society
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• v.10 no.1
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• pp.1-6
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• 2007

Mercaptopropionic acid(mpa) has been used to make self-assembled monolayer(SAMs) on the surface of graphite electrode incorporating gold nano particles, which are subsequently modified with dopamine(dopa). Such modified electrodes haying types of Gr(Au)/mpa-dopa were employed in the electrocatalytic oxidation of NADH. The responses of such modified electrodes were studied in terms of electron transfer kinetics and reaction procedure in the reaction. The reaction of the surface immobilized dopa with NADH was studied using the rotating disk electrode technique and a value of $5.06{\times}10^5M^{-1}s^{-1}$ was obtained for the second-order rate constant in 0.1 M phosphate buffer(pH=7.0), which was a $EC_{cat}$ and kinetic controlled procedure. But, the modified electrodes were diffusion controlled reaction having $4.64{\times}10^{-4}cm^2s^{-1}$ of the coefficient within $10^{-3}s$ after starting the reaction.

• KSBB Journal
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• v.13 no.1
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• pp.52-57
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• 1998

The present work proposes a simple electrochemical method applicable to any immobilization processes of oxidase using a Clark type oxygen electrode as a base transducer. The present work suggests an optimal immobilization technique among three different methods of glucose oxidase(GOD) onto one side of $37[\mu}$mthick blend membranes, composed o 80% of cellulose triacetate and 20% of polycaprolactone, on the basis of the maximum Michaelis-Menten parameter(Vm) determined by either steady state or transient analyses. The electrode system was made of disk type gold cathode(4mm diameter) and Ag/AgCl anode. One side of the blend membrane was in contact with the cathode surface while the other side was immobilized with GOD either in covalent-bond or cross-linked forms, the latter being covered by $25{\mu}$m thick dialysis membrane of cellulose acetate. The resultant current density was on-line monitored by a potentiostat while glucose level was varied from 1 to 20 mM. The present study shows that direct cross-linking of GOD with glutaraldehyde was mostly preferred for fabrication of glucose sensor, on the basis of resultant kinetic parameters from either steady state or transient analyses.