• Korean Journal of Materials Research
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• v.25 no.3
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• pp.113-118
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• 2015

To improve the methanol electro-oxidation in direct methanol fuel cells(DMFCs), Pt electrocatalysts embedded on porous carbon nanofibers(CNFs) were synthesized by electrospinning followed by a reduction method. To fabricate the porous CNFs, we prepared three types of porous CNFs using three different amount of a styrene-co-acrylonitrile(SAN) polymer: 0.2 wt%, 0.5 wt%, and 1 wt%, respectively. A SAN polymer, which provides vacant spaces in porous CNFs, was decomposed and burn out during the carbonization. The structure and morphology of the samples were examined using field emission scanning electron microscopy and transmission electron microscopy and their surface area were measured using the Brunauer-Emmett-Teller(BET). The crystallinities and chemical compositions of the samples were examined using X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical properties on the methanol electro-oxidation were characterized using cyclic voltammetry and chronoamperometry. Pt electrocatalysts embedded on porous CNFs containing 0.5 wt% SAN polymer exhibited the improved methanol oxidation and electrocatalytic stability compared to Pt/conventional CNFs and commercial Pt/C(40 wt% Pt on Vulcan carbon, E-TEK).

• Environmental Engineering Research
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• v.23 no.4
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• pp.345-353
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• 2018

This paper summarizes results of research on the electrochemical (EC) degradation of disinfection by-products (DBPs) and iodine-containing contrast media (ICMs), with the focus on EC reductive dehalogenation. The efficiency of EC dehalogenation of DBPs increases with the number of halogen atoms in an individual DBP species. EC reductive cleavage of bromine from parent DBPs is faster than that of chlorine. EC data and quantum chemical modeling indicate that the EC reduction of iodine-containing DBPs (I-DBPs) is characterized by the formation of active iodine that reacts with the organic substrate. The occurrence of ICMs has attracted attention due to their association with the generation of I-DBPs. Indirect EC oxidation of ICMs using anodes that produce reactive oxygen species can result in a complete degradation of these compounds yet I-DBPs are formed in the process. Reductive EC deiodination of ICMs is rapid and its overall rate is diffusion-controlled yet I-DBPs are also produced in this reaction. Further progress in practically feasible EC methods to remove DBPs, ICMs and other trace-level organic contaminants requires the development of novel electrocatalytic materials, elimination of mass transfer limitations via innovative design of 3D electrodes and EC reactors, and further progress in the understanding of intrinsic mechanisms of EC reactions of DBPs and TrOC at EC interfaces.

• Journal of the Korean Chemical Society
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• v.67 no.5
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• pp.339-347
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• 2023

In this study, a nanocomposite of multi-walled carbon nanotubes@poly(p-phenylenediamine)-Prussian blue (MWCNTs@PpPD-PB) was synthesized and employed for the electrochemical detection of hydrogen peroxide (H₂O₂). A straightforward approach was utilized to prepare an electrochemical H₂O₂ sensor using a MWCNTs@PpPD-PB modified glassy carbon electrode, and its electrochemical behavior was investigated through techniques such as electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The modified electrode displayed a favorable electrocatalytic response towards the reduction of H₂O₂ in an acidic solution. The developed sensor exhibited linearity in the concentration range of 0.005 mM to 2.225 mM for H₂O₂, with high sensitivity (583.6 ㎂ mM^-1cm^-2) and a low detection limit (0.95 ㎛, S/N = 3) at an applied potential of +0.15 V (vs. Ag/AgCl). Additionally, the sensor demonstrated excellent selectivity, reproducibility, and stability. Moreover, successful detection of H₂O₂ was achieved in real samples.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.672-678
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• 2006

A new approach to fabricate an enzyme electrode was described based on the immobilization of horseradish peroxidase (HRP) on dithiobis-N-succinimidyl propionate (DTSP) self-assembled monolayer (SAM) formed on gold-nanoparticles (Au-NPs) which were electrochemically deposited onto glassy carbon electrode (GCE) surface. The overall surface area and average size of Au-NPs could be controlled by varying deposition time and were examined by Field Emission-Scanning Electron Microscope (FE-SEM). The $O_2$ reduction capability of the surface demonstrated that Au-NPs were thermodynamically stable enough to stay on GCE surface. The immobilized HRP electrode based on Au-NPs/GCE presented faster, more stable and sensitive amperometric response in the reduction of hydrogen peroxide than a HRP immobilized on DTSP/gold plate electrode not containing Au-NPs. The effects of operating potential, mediator concentration, and pH of buffer electrolyte solution on the performance of the HRP biosensor were investigated. In the optimized experimental conditions, the HRP immobilized GCE incorporating smaller-sized Au-NPs showed higher electrocatalytic activity due to the high surface area to volume ratio of Au-NPs in the biosensor. The HRP electrode showed a linear response to $H_2O_2$ in the concentration range of 1.4 $\mu$M-3.1 mM. The apparent Michaelis-Menten constant ($K _M\; ^{app}$) determined for the immobilized HRP electrodes showed a trend to be decreased by decreasing size of Au-NPs electrodeposited onto GCE.

• 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.

• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.581-584
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• 2020

The effect of a chemical pretreatment on the surface carbon was investigated using a scanning electron microscope (SEM) and electrochemical methods. Primitive carbon has a reducing power likely due to incompletely oxidized functional groups on the surface. We aim to control this reducing power by chemical treatment and apply for the spontaneous deposition of nanoparticles (NPs). Highly ordered pyrolytic graphite (HOPG) was initially treated with a reducing agent, NaBH4 or an oxidizing agent, KMnO₄, for 5 min. Subsequently, the pretreated carbon was immersed in a platinum (Pt) precursor. Unexpectedly, SEM images showed that the reducing agent increased spontaneous PtNPs deposition while the oxidizing agent decreased Pt loading more as compared to that of using bare carbon. However, the amount of Pt on the carbon obviously decreased by NaBH₄ treatment for 50 min. Secondly, spontaneous reduction on pretreated glassy carbon (GC) was investigated using the catalytic hydrogen evolution reaction (HER). GC electrode treated with NaBH4 for a short and long time showed small (onset potential: -640 mV vs. MSE) and large overpotential for the HER, respectively. Although the mechanism is unclear, the electrochemistry results correspond to the optical data. As a proof-of-concept, these results demonstrate that chemical treatments can be used to design the shapes and amounts of deposited catalytic metal on carbon by controlling the surface state.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.475-481
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• 2013

By using ionic liquid 1-hexylpyridinium hexafluorophosphate ($HPPF_6$) based carbon ionic liquid electrode (CILE) as the substrate electrode, a $CoMoO_4$ nanorods and myoglobin (Mb) composite was casted on the surface of CILE with chitosan (CTS) as the film forming material to obtain the modified electrode (CTS/$CoMoO_4$-Mb/CILE). Spectroscopic results indicated that Mb retained its native structures without any conformational changes after mixed with $CoMoO_4$ nanorods and CTS. Electrochemical behaviors of Mb on the electrode were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks from the heme Fe(III)/Fe(II) redox center of Mb appeared, which indicated that direct electron transfer between Mb and CILE was realized. Electrochemical parameters such as the electron transfer number (n), charge transfer coefficient (${\alpha}$) and electron transfer rate constant ($k_s$) were estimated by cyclic voltammetry with the results as 1.09, 0.53 and 1.16 $s^{-1}$, respectively. The Mb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid in the concentration range from 0.1 to 32.0 mmol $L^{-1}$ with the detection limit as 0.036 mmol $L^{-1}$ ($3{\sigma}$), and the reduction of $H_2O_2$ in the concentration range from 0.12 to 397.0 ${\mu}mol\;L^{-1}$ with the detection limit as 0.0426 ${\mu}mol\;L^{-1}$ ($3{\sigma}$).

• 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.

• Analytical Science and Technology
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• v.11 no.6
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• pp.460-468
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• 1998

Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.1
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• pp.18-25
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• 2008

The membrane electrode assembly(MEA) was prepared by a nonequilibrium impregnation- reduction (I-R) method. Nafion 117 and covalently cross-linked sulfonated polyetherether with tungsto- phosphoric acid (CL-SPEEK/TPA30) prepared by our laboratory, were chosen as polymer electrolyte membrane(PEM). $Pt(NH_3)_4Cl_2$, $RuCl_3$ and reducing agent $(NaBH_4)$ were used as electrocatalytic materials. Electrochemical activity surface area(ESA) and specific surface area(SSA) of Pt cathodic electrode with Nafion 117 were $22.48m^2/g$ and $23.50m^2/g$ respectively under the condition of 0.8 M $NaBH_4$. But Pt electrode prepared by CL-SPEEK/TPA30 membrane exhibited higher ESA $23.46m^2/g$ than that of Nafion 117. In case of Pt-Ru anodic electrode, the higher concentration of Ru was, the lower potential of oxygen reduction and region of hydrogen desorption was, and Pt-Ru electrode using 10 mM $RuCl_3$ showed best properties of SSA $34.09m^2/g$ with Nafion 117. In water electrolysis performance, the cell voltage of Pt/PEM/Pt-Ru MEA with Nafion 117 showed cell property of 1.75 V at $1A/cm^2$ and $80{\circ}C$. On the same condition, the cell voltage with CL-SPEEK/TPA30 was the best of 1.73 V at $1A/cm^2$.