• 한국미생물생명공학회:학술대회논문집
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• 한국미생물생명공학회 2000년도 추계 학술대회
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• pp.181-188
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• 2000

The electrocatalytic reduction of NAD$^{＋}$ using diaphorase was studied. methyl viologen (MV$^{2＋}$) mediator between an electrode and the enzyme. Steady-state currents could be obtained under the conditions of slow scan rate, low MV$^{2＋}$concentration, and high NAD$^{＋}$ concentration as the electrode reaction was converted to an electrochemical-catalytic (EC') reaction. The biomecular rate constant for the reaction of the reduced methyl viologen with the oxidized diaphorase was estimated as 7.5$\times$10$^3$M$^{-1}$ s$^{-1}$ from the slope of the current versus [MV$^{2＋}$] plot. And the optimal concentrations of diaphorase, MV$^{2＋}$ and NAD$^{＋}$ in the mediated electrocatalytic reduction of NAD$^{＋}$ were decided by applying the cyclic voltammetry. The optimal concentrations of the species were obtained by finding the conditions which gave the highest and steady-state current at a gold-amalgam electrode. The highest and steady-state catalytic current was achieved under the conditions of 1.5 U/ml diaphorase, 0.2 mM MV$^{2＋}$, and 4.8 mM NAD$^{＋}$ at the scan rate of 2 mV s$^{-1}$ , suggesting that the rate of the electrocatalytic reation is the higest under the former conditions. The electrochemical procedure under the conditions of 1.5 U/ml diaphorase,0.2 mM MV$^{2＋}$, and 4.8 mM NAD$^{＋}$ was used favorably to drive an enzymatic reduction of pyruvate to D-lactate.

• Bulletin of the Korean Chemical Society
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• 제21권6호
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• pp.571-576
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• 2000

Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.165-166
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• 2004

• Journal of Electrochemical Science and Technology
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• 제4권2호
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• pp.71-80
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• 2013

The study of methyl viologen ($MV^{2+}$) mediated oxygen reduction in electrolytic ethanol media possesses potential application in the electrochemical synthesis of hydrogen peroxide mainly due to the advantages of the much increased solubility of molecular oxygen ($O_2$) and high degree of reversibility of $MV^{2+/{\bullet}+}$ redox couple. The diffusion coefficients of both $MV^{2+}$ and $O_2$ were investigated via electrochemical techniques. For the first time, $MV^{2+}$ mediated $O_2$ reduction in electrolytic ethanol solution has been proved to be feasible on both boron-doped diamond and micro-carbon disc electrodes. The electrocatalytic response is demonstrated to be due to the radical cation, $MV^{{\bullet}+}$. The homogeneous electron transfer step is suggested to be the rate determining step with a rate constant of $(1{\pm}0.1){\times}10^5M^{-1}s^{-1}$. With the aid of a simulation program describing the EC' mechanism, by increasing the concentration ratio of $MV^{2+}$ to $O_2$ electrochemical catalysis can be switched from a partial to a 'total catalysis' regime.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.1996-2002
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• 2007

The redox behavior of a [Ni6(μ3-Se)2(μ4-Se)3(Fe(η 5-C5H4P-Ph2)2)3] (= [Ni-Se-dppf], dppf = 1,1-bis(diphenylphosphino) ferrocene) cluster was studied using platinum (Pt) and glassy carbon electrodes (GCE) in nonaqueous media. The cluster showed electrochemical activity at the potential range between +1.6 and ?1.6 V. In the negative region (0 to ?1.6 V), the cluster exhibited two-step reductions. The first step was one-electron reversible, while the second step was a five-electron quasi-reversible process. On the other hand, in the positive region (0 to +1.6 V), the first step involved one-electron quasi-reversible process. The applicability of the cluster was found towards the electrocatalytic reduction of CO2 and was evaluated by experiments using rotating ring disc electrode (RRDE). RRDE experiments demonstrated that two electrons were involved in the electrocatalytic reduction of CO2 to CO at the Se-Ni-dppf-modified electrode.

• 한국석유지질학회:학술대회논문집
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• 대한자원환경지질학회/한국석유지질학회/한국암석학회 2000년도 추계공동학술발표회 초록집
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• pp.45-45
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• 2000

• Journal of Electrochemical Science and Technology
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• 제11권3호
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• pp.220-237
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• 2020

Modern electrochemical energy devices involve generation and reduction of fuel gases through electrochemical reactions of water splitting, alcohol oxidation, oxygen reduction, etc. Initially, these processes were executed in the presence of noble metal-based catalyst that showed low overpotential and high current density. However, its high cost, unavailability, corrosion and related toxicity limited its application. The search for alternative with high stability, durability, and efficiency led scientists towards carbon nanoparticles supported catalysts which has high surface area, good electrical conductivity, tunable morphology, low cost, ease of synthesis and stability. Carbon nanoparticles are classified into two groups based on morphology, one and zero dimensional particles. Carbon nanoparticles at zero dimension, denoted as carbon dots, are less used carbon support compared to other forms. However, recently carbon dots with improved electronic properties have become popular as catalyst as well as catalyst support. This review focused on the recent advances in electrocatalytic activities of carbon dots. The mechanisms of common electrocatalytic reactions and the role of the catalysts are also discussed. The review also proposed future developments and other research directions to overcome current limitations.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3835-3839
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• 2013

A new synthesis route for Pt nanoparticles by direct electrochemical reduction of a solid-state Pt ion precursor ($K_2PtCl_6$) is demonstrated. Solid $K_2PtCl_6$-supported polyethyleneimine (PEI) coatings on the surface of glassy carbon electrode were prepared by simple mixing of solid $K_2PtCl_6$ into a 1.0% PEI solution. The potential cycling or a constant potential in a PBS (pH 7.4) medium were applied to reduce the solid $K_2PtCl_6$ precursor. The reduction of Pt(IV) began at around -0.2 V and the reduction potential was ca. -0.4 V. A steady state current was achieved after 10 potential cycling scans, indicating that continuous formation of Pt nanoparticles by electrochemical reduction occurred for up to 10 cycles. After applying the reduction potential of -0.6 V for 300 s, Pt nanoparticles with diameters ranging from $0.02-0.5{\mu}m$ were observed, with an even distribution over the entire glassy carbon electrode surface. Characteristics of the Pt nanoparticles, including their performance in electrochemical reduction of $H_2O_2$ are examined. A distinct reduction peak observed at about -0.20 V was due to the electrocatalytic reduction of $H_2O_2$ by Pt nanoparticles. From the calibration plot, the linear range for $H_2O_2$ detection was 0.1-2.0 mM and the detection limit for $H_2O_2$ was found to be 0.05 mM.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.459-462
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• 2006

Formic acid recently attracted attention as an alternative fuel for direct liquid fuel cells(DLFCs) due to its high theoretical open circuit voltage(1.45V). In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the deposition of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled Pt layer were formed on the surface of carbon-supported Au nanoparticles. The Au-Pt[x] showed the higher electrocatalytic activity than those of the particle-alloys and commercial one (Johnson-Matthey) for the reaction of formic acid oxidation when the mass-specific currents were compared. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• Journal of Electrochemical Science and Technology
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• 제6권3호
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• pp.106-110
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• 2015

This study investigates Cu(II) complexes of cyclam, propylene cross-bridged cyclam (PCB-cyclam), and propylene cross-bridged cyclam diacetate (PCB-TE2A) as homogeneous electrocatalysts for CO₂ reduction in comparison with Ni(II)-cyclam. It is found that Cu(II)-cyclam can catalyze CO₂ reduction at the potential close to its thermodynamic value (0.75 V vs. Ag/AgCl) in tris-HCl buffer (pH 8.45) on a glassy carbon electrode. Cu(II)-cyclam, however, suffers from severe demetalation due to the insufficient stability of Cu(I)-cyclam. Cu(II)-PCB-cyclam and Cu(II)-PCB-TE2A are revealed to exhibit much less demetalation behavior, but poor CO₂ reduction activities as well. The inferior electrocatalytic ability of Cu(II)-PCB-cyclam is ascribed to its redox potential that is too high for CO₂ reduction, and that of Cu(II)-PCB-TE2A to the steric hindrance preventing facile contact with CO₂ molecules. This study suggests that in addition to the redox potential and chemical stability, the stereochemical aspect has to be considered in designing efficient electrocatalysts for CO₂ reduction.