• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3118-3122
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• 2010

The water soluble redox polymer, poly(N-vinylimidazole) complexed with Os(4,4'-dichloro-2,2'-bipyridine)$_2Cl]^+$ (PVI-[Os(dCl-bpy)$_2Cl]^+$), was electrodeposited on the surface of a glassy carbon electrode by applying cycles of alternating square wave potentials between 0.2 V (2 s) and 0.7 V (2 s) to the electrode in a solution containing the redox polymer. The coordinating anionic ligand, $Cl^-$ of the osmium complex, became labile in the reduced state of the complex and was substituted by the imidazole of the PVI chain. The ligand substitution reactions resulted in crosslinking between the PVI chains, which made the redox polymer water insoluble and caused it to be deposited on the electrode surface. The deposited film was still electrically conducting and the continuous electrodeposition of the redox polymer was possible. When cycles of square wave potentials were applied to the electrode in a solution of bilirubin oxidase and the redox polymer, the enzyme was co-electrodeposited with the redox polymer, because the enzymes could be bound to the metal complexes through the ligand exchange reactions. The electrode with the film of the PVI-[Os(dCl-bpy)$_2Cl]^+$ redox polymer and the co-electrodeposited bilirubin oxidase was employed for the reduction of $O_2$ and a large increase of the currents was observed due to the electrocatalytic $O_2$ reduction with a half wave potential at 0.42 V vs. Ag/AgCl.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.915-920
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• 2008

In this paper the electrochemical behaviors of hydroquinone ($H_2Q$) were investigated on a carbon paste electrode using room temperature ionic liquid N-butylpyridinium hexafluorophosphate ($BPPF_6$) as binder (ILCPE) and further applied to $H_2Q$ determination. In pH 2.5 phosphate buffer solution (PBS), the electrochemical response of H2Q was greatly improved on the IL-CPE with a pair of well-defined quasi-reversible redox peaks appeared, which was attributed to the electrocatalytic activity of IL-CPE to the $H_2Q$. The redox peak potentials were located at 0.340 V (Epa) and 0.240 V (Epc) (vs. the saturated calomel electrode, SCE), respectively. The formal potential ($E^0$') was calculated as 0.290 V and the peak-to-peak separation (${\Delta}E_p$) was 0.100 V. The electrochemical parameters of $H_2Q$ on the IL-CPE were further calculated by cyclic voltammetry. Under the selected conditions the anodic peak current was linear with $H_2Q$ concentration over the range from $5.0\;{{\times}}\;10^{-6}$ to $5.0\;{\times}\;10^{-3}\;mol\;L^{-1}$ with the detection limit as $2.5\;{\times}\;10^{-6}\;mol\;L^{-1}$ (3$\sigma$ ) by cyclic voltammetry. The proposed method was successful applied to determination of $H_2Q$ content in a synthetic wastewater sample without the interferences of commonly coexisting substances.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1583-1588
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• 2010

A single step fabrication process of carbon nanotube/Prussian Blue (CNT/PB) paste electrodes based on screen printing technology has been studied as an amperometric sensor for the determination of hydrogen peroxide and free chlorine. Compared to the classical carbon paste (CP) electrode, the CNT paste electrode greatly enhanced the response in the presence of hydrogen peroxide due to the electrocatalytic activity of the CNT. Based on the CNT/binder paste, PB was also incorporated into a network of CNT paste and characterized. The best electroanalytical properties of PB-mixed sensors to hydrogen peroxide were obtained with PB ratio of 10 wt % composition, which showed fast response time ($t_{90}{\leq}5$ s; 0.2 - 0.3 mM), low detection limit of 1.0 ${\mu}M$, good linear response in the range from $5.0{\times}10^{-5}$ - $1.0{\times}10^{-3}$ mol $L^{-1}$ ($r^2$ = 0.9998), and high sensitivity of -8.21 ${\mu}AmM^{-1}$. In order to confirm the enhanced electrochemical properties of CNT/PB electrode, the sensor was further applied for the determination of chlorine in water, which exhibited a linear response behavior in the range of 50 - 2000 ppb for chlorine with a slope of 1.10 ${\mu}Appm^{-1}$ ($r^2$ = 9971).

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.298-305
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• 2016

The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex $[CuLbpy]ClO_4$ (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with $E_{1/2}=-0.2V$ vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

• Journal of the Korean Ceramic Society
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• v.56 no.5
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• pp.497-505
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• 2019

Lanthanum-based transition metal cations containing perovskites have emerged as potential catalysts for the intermediate-temperature (600-800℃) oxygen reduction reaction (ORR). Here, we report a facile acetylacetone-assisted combustion route for the synthesis of nanostructured La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF6428) cathodes for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The as-prepared powder was analyzed by thermogravimetry analysis-differential scanning calorimetry. The powder calcined at 800℃ was characterized by X-ray diffraction, scanning electrode microscopy, energy dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller surface area measurements. It was found that the porosity of the air electrode significantly increased by utilizing the nanostructured LSCF6428 instead of commercial powder. The performance of a single cell fabricated with the nanostructured LSCF6428 cathode increased by 112%, from 0.4 to 0.85 W cm^-2, at 700℃. Electrochemical impedance spectroscopy showed a considerable reduction in the area-specific resistance and activation energy from 133.5 to 61.5 kJ/mol, resulting in enhanced electrocatalytic activity toward ORR and overall cell performance.

• Transactions of the Korean hydrogen and new energy society
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• v.25 no.1
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• pp.1-10
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• 2014

Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance and to increase the duration of the membrane. In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) and the organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted phophomolybdic acid(Cs-MoPA) with cross-linking agent contents of 0.01mL. In conclusion, CL-SPEEK/$Cs_{(2.5)}$-MoPA/ceria(1%) membrane showed the optimum results such as 0.1095S/cm of proton conductivity at $80^{\circ}C$, 2.906meq./g-dry-membrane of ion exchange capacity and mechanical characteristics, and 49.73MPa of tensile strength which were better than Nafion 117 membrane.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.5
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• pp.450-457
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• 2018

To design the practical core-shell electrocatalysts, combination of core and shell materials is important to meet catalytic activity and durability target. In general, Pd is considered as a good core material due to its best activity caused by strain/ligand effect. Preparing Pd nanoparticles can be a starting point in fabricating core-shell type electrocatalysts, much simplified Pd preparing process is suggested by using carbon monoxide (CO) as a reducing agent and/or capping agent. The solvent composition and reaction temperature can control to nanosheet, tetrahedron, and sphere without using additional stabilizer. Among them, Pd nanosheet which has mainly (111) plane showed about 3 times higher electrocatalytic activity for oxygen reduction reaction (ORR) to the spherical Pd nanoparticles. The enhanced ORR activity of Pd nanosheets can be attributed to the exposure of Pd (111) surface and the high electrochemical surface area. Therefore, we demonstrated that the shape of Pd nanomaterials is easily controlled via a facile reduction method using CO, and (111) plane-oriented Pd nanosheets can be a promising ORR catalysts and core material for polymer electrolyte fuel cells (PEFCs).

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.697-700
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• 2008

The underpotential deposited Bi on Pt($Bi_{upd}/Pt$) anode for formic acid fuel cells (FAFCs) was developed using multi-layered preparation method for better electrocatalytic utilization of Pt. The electron probe microanalysis (EPMA) result indicated that $Bi_{upd}$ remains through the catalyst layer during stability test. In performance test, the multilayered $Bi_{upd}$ on Pt black showed superior performance by approximately 200 mV at current density of $150mA/cm^2$ compared with PtRu black anode catalyst. Based on preparation condition of $Bi_{upd}/Pt$ black, carbon supported $Bi_{upd}/Pt/C$ electrode was prepared and it showed enhanced performance and stability.

• Journal of the Korean Chemical Society
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• v.41 no.8
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• pp.385-391
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• 1997

Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.582-588
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• 2009

Direct electron transfer of hemoglobin (Hb) in the chitosan (CTS) and $TiO_2$ nanoparticles (nano-$TiO_2$) composite films was achieved by using a room temperature ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate ($BMIMPF_6$) modified carbon paste electrode (CILE) as the basal electrode. UV-Vis and FT-IR spectroscopy indicated that Hb in the film retained the native structure. Electrochemical investigation indicated that a pair of well-defined quasi-reversible redox peaks of Hb heme Fe(III)/Fe(II) was obtained with the formal potential located at -0.340 V (νs. SCE) in pH 7.0 phosphate buffer solution (PBS). The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n) and the standard electron transfer rate constant ($k_s$) were got as 0.422, 0.93 and 0.117 $s^{-1}$, respectively. The fabricated CTS/nano-$TiO_2$/Hb/CILE showed good electrocatalytic ability to the reduction of trichloroacetic acid (TCA) and hydrogen peroxide ($H_2O_2$), which exhibited a potential application in fabricating a new kind of third generation biosensor.