• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.11-25
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• 2009

Fuel cells are expected to be one of the major clean new energy sources in the near future. However, the slow kinetics of electrocatalytic hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR), and the high loading of Pt for the anode and cathode material are the urgent issues to be addressed since they determine the efficiency and the cost of this energy source. In this review paper, a new approach was developed for designing electrocatalysts for the HOR and ORR in fuel cells. It was found that the electronic properties of Pt could be fine-tuned by the electronic and geometric effects introduced by the substrate alloy metal and the lateral effects of the neighboring metal atoms. The role of substrate was found reflected in a volcano plot for the HOR and ORR as a function of their calculated d-band centers. This paper demonstrated a viable way to designing the electrocatalysts which could successfully alleviate two issue facing the commercializing of the fuel cell-the cost of electrocatalysts and their efficiency.

• Journal of Hydrogen and New Energy
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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).

• Clean Technology
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• v.23 no.3
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• pp.308-313
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• 2017

In this study, we investigated the electrocatalytic effects of the N and O co-doping of Graphite Felt (GF) electrode for the vanadium redox flow battery (VRFB) at the cathode and the anode reaction, respectively. The electrodes were prepared by chemical vapor deposition (CVD) with $NH_3-O_2$ at 773 K, and its effects were compared with an electrode prepared by an O doping treatment. The surface morphology and chemical composition of the electrodes were characterized by scanning electron microscopy (SEM) and photoelectron spectroscopy (XPS). The electrocatalytic properties of these electrodes were characterized in a VRFB single cell comparing the efficiencies and performance of the electrodes at the cathode, anode, and single cell level. The results exhibited about 2% higher voltage and energy efficiencies on the N-O-GF than the O-GF electrode. It was found that the N and O co-doping was particularly effective in the enhancement of the reduction-oxidation reaction at the anode.

• 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.

• 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.

• Korean Journal of Materials Research
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• v.19 no.12
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• pp.667-673
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• 2009

The electrocatalytic characteristics of oxygen reduction reaction of the $PtxM_{(1-x)}$ (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The $Pt_xM_{(1-x)}$/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the $Pt_xM_{(1-x)}$ particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and $Pt_xM_{(1-x)}$/MWNTs catalysts are seen as FCC, and synthesized $Pt_xM_{(1-x)}$ crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, $Pt_{0.77}Co_{0.23}$/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or $Pt_xM_{(1-x)}$/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and $Pt_xM_{(1-x)}$ (M = Co, Cu, Ni) catalysts, the $Pt_{0.77}Co_{0.23}$/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.

• Korean Chemical Engineering Research
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• v.60 no.1
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• pp.151-158
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• 2022

Iron and nitrogen coordinated carbon catalyst (Fe-N-C) is the most promising non-precious metal catalyst (NPMC) studied to alternate the Pt-group oxygen reduction reaction (ORR) catalyst. In this work, Fe/N/C type catalysts are prepared by four different nitrogen precursors; N, N, N', N'-tetramethylethylenediamine (TMEDA), 1,2-ethylenediamine (EDA), m-dicyanobenzene (DCB), dicyandiamide (DCDA) which can chelate a transition metal; In addition, the catalysts conducted the pyrolysis process at four different temperatures of 700, 800, 900, 1000 ℃ to investigate the ORR activities depend on pyrolysis temperature and to find an appropriate temperature. The characterizations of catalysts were investigated by scanning electron microscope-energy dispersive X-ray spectrometer (SEM-EDS), X-ray diffraction (XRD), and element analysis (EA). The electrocatalytic activity was measured by ORR polarization, also the electron transfer number was calculated from the slope of the K-L plot. The FeNC-EDA-800 which were prepared at pyrolysis temperature of 800 ℃ with EDA showed better ORR activity than the other catalysts.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2363-2368
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• 2007

A glassy carbon electrode (GCE) modified with phytic acid (PA) and single-walled carbon nanotubes (SWNTs) were investigated by voltammetric methods in buffer solution. The PA-SWNTs/GCE-modified electrode demonstrated substantial enhancements in electrochemical sensitivity and selectivity towards dopamine (DA) in the presence of L-ascorbic acid (AA). The PA-SWNTs films promoted the electron transfer reaction of DA, while the PA film, acting as a negatively charged linker, combined with the positively charged DA to induced DA accumulation in the film at pH under 7.4. However, the PA film restrained the electrochemical response of the negatively charged AA due to the electrostatic repulsion. The anodic peak potentials of DA and AA could be separated by electrochemical techniques, and the interferences from AA were effectively eliminated in the DA determination. Linear calibration plots were obtained in the DA concentration range of 0.1-10 μM and the detection limit of the DA oxidation current was determined to be 0.06 μM at a signal-to-noise ratio of 3. The results indicated that the modified electrode is used to determine DA without interference from AA.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.229-232
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• 2007

An amperometric immunosensor for the determination of rabbit IgG is proposed. The immunoassay utilizes a screen-printed carbon electrode on which osmium redox polymer is electrodeposited. This immunoassay detects 0.1 ng/ml of rabbit IgG, which is ${\sim}10^2$ fold higher than the most sensitive enzyme amplified amperometric immunoassay. The assay utilizes a screen-printed carbon electrode which was pre-coated by a co-electrodeposited film of an electron conducting redox hydrogel and a rabbit IgG. The rabbit IgG in the electron conducting film conjugates captures, when present, the anti-rabbit IgG. The captured anti-rabbit-IgG is labeled with horseradish peroxidase (HRP) which catalyzes the two-electron reduction of $H_2O_2$ to water. Because the redox hydrogel electrically connects HRP reaction centers to the electrode, completion of the sandwich converts the film from non-electrocatalytic to electro-catalytic for the reduction of $H_2O_2$ to $H_2O$ when the electrode is poised at 200 mV vs. Ag/AgCl.