• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.219-228
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• 2007

The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

• Corrosion Science and Technology
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• v.13 no.1
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• pp.28-35
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• 2014

Recently, the fuel oil of diesel engines of marine ships has been increasingly changed to heavy oil of low quality as the oil price is getting higher and higher. Therefore, the spiral gear attached at the motor of the oil purifier which plays an important role to purify the heavy oil is also easy to expose at severe environmental condition due to the purification of the heavy oil in higher temperature. Thus, the material of the spiral gear requires a better mechanical strength, wear and corrosion resistance. In this study, the heat treatment(tempering) with various holding time at temperature of $500^{\circ}C$ was carried out to the alloy of Cu-7Al-2.5Si as centrifugal casting, and the properties of both hardness and corrosion resistance with and without heat treatment were investigated with observation of the microstructure and with electrochemical methods, such as measurement of corrosion potential, cathodic and anodic polarization curves, cyclic voltammogram, and a.c. impedance. in natural seawater solution. The ${\alpha}$, ${\beta}^{\prime}$ and ${\gamma}_2$ phases were observed in the material in spite of no heat treatment due to quenching effect of a spin mold. However, their phases, that is, ${\beta}^{\prime}$ and ${\gamma}_2$ phases decreased gradually with increasing the holding time at a constant temperature of $500^{\circ}C$. The hardness more or less decreased with heat treatment, however its corrosion resistance was improved with the heat treatment. Furthermore, the longer holding time, the better corrosion resistance. In addition, when the holding time was 48hrs, its corrosion current density showed the lowest value. The pattern of corroded surface was nearly similar to that of the pitting corrosion, and this morphology was greatly observed in the case of no heat treatment. It is considered that ${\gamma}_2$ phase at the grain boundary was corroded preferentially as an anode. However, the pattern of general corrosion exhibited increasingly due to decreasing the ${\gamma}_2$ phase with heat treatment. Consequently, it is suggested that the corrosion resistance of Cu-7Al-2.5Si alloy can be improved with the heat treatment as a holding time for 48 hrs at $500^{\circ}C$.

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.695-700
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• 2019

n this study, the evaluation of performance of AORFB using anthraquinone derivative and TEMPO derivative as active materials in neutral supporting electrolyte with various membrane types was performed. Both anthraquinone derivative and TEMPO derivative showed high electron transfer rate (the difference between anodic and cathodic peak potential was 0.068 V) and the cell voltage is 1.17 V. The single cell test of the AORFB using 0.1 M active materials in 1 M KCl solution with using Nafion 212 membrane, which is commercial cation exchange membrane was performed, and the charge efficiency (CE) was 97% and voltage efficiency (VE) was 59%. In addition, the discharge capacity was $0.93Ah{\cdot}L^{-1}$ which is 35% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $4^{th}$ cycle and the capacity loss rate was $0.018Ah{\cdot}L^{-1}/cycle$ during 10 cycles. The single cell tests were performed with using Nafion 117 membrane and SELEMION CSO membrane. However, the results were more not good because of increased resistance because of thicker thickness of membrane and increased cross-over of active materials, respectively.

• Carbon letters
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• v.23
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• pp.38-47
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• 2017

In this study, magnetite ($Fe_3O_4$) nanoparticles were electrochemically synthesized in an aqueous electrolyte at a given potential of -1.3 V for 180 s. Scanning electron microscopy revealed that dendrite-like $Fe_3O_4$ nanoparticles with a mean size of < 80 nm were electrodeposited on a glassy carbon electrode (GCE). The $Fe_3O_4/GCE$ was utilized for sensing chloramphenicol (CAP) by cyclic voltammetry and square wave voltammetry. A reduction peak of CAP at the $Fe_3O_4/GCE$ was observed at 0.62 V, whereas the uncoated GCE exhibited a very small response compared to that of the $Fe_3O_4/GCE$. The electrocatalytic ability of $Fe_3O_4$ was mainly attributed to the formation of Fe(VI) during the anodic scan, and its reduction to Fe(III) on the cathodic scan facilitated the sensing of CAP. The effects of pH and scan rate were measured to determine the optimum conditions at which the $Fe_3O_4/GCE$ exhibited the highest sensitivity with a lower detection limit. The reduction current for CAP was proportional to its concentration under optimized conditions in a range of $0.09-47{\mu}M$ with a correlation coefficient of 0.9919 and a limit of detection of $0.09{\mu}M$ (S/N=3). Moreover, the fabricated sensor exhibited anti-interference ability towards 4-nitrophenol, thiamphenicol, and 4-nitrobenzamide. The developed electrochemical sensor is a cost effective, reliable, and straightforward approach for the electrochemical determination of CAP in real time applications.

• Journal of the Korean Electrochemical Society
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• v.6 no.3
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• pp.169-173
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• 2003

Electrochemical capacitor made with metal oxide electrode uses rapid and reversible protonation/deprotonation of metal oxide material under the aqueous acidic solution, generally. Electrochemical stability window of aqueous electrolyte-type capacitor is narrow compared to that of organic electrolyte-type capacitor. Electrochemical characteristics of electrochemical capacitor made with metal oxide electrode and lithium or ammonium cation based organic electrolyte were evaluated. Electrochemical capacitor based on $RuO_2$ electrode material and 1M $LiPF_6$ in mixed solvents of EC, DEC, and EMC has anodic and cathodic specific capacitance of 145 and $142F/g-RuO_2{\cdot}nH_2O$, respectively, by using cyclic voltammetry with scan rate of 2mV/sec $g-RuO_2$ in potential range of $2.0\~4.2V(Li|Li^+))$.