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

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

• Bulletin of the Korean Chemical Society
• /
• 제31권5호
• /
• pp.1182-1186
• /
• 2010

A novel poly(safranine)-modified electrode has been constructed for the determination of 4-nitrophenol (4-NP) in natural water sample. The electrochemical behavior of poly(safranine) film electrode and its electrocatalytic activity toward 4-NP were studied in detail by cyclic voltammetry (CV) and adsorptive linear stripping voltammetry (LSV). All experimental parameters were optimized and LSV was proposed for its determination. In optimal working conditions, the reduction current of 4-NP at this poly(safranine)-modified electrode exhibited a good linear relationship with 4-NP concentration in the range of $8.0{\times}10^{-8}$ to $4.0{\times}10^{-5}mol\;L^{-1}$. The detection limit was $3.0{\times}10^{-8}mol\;L^{-1}$. The high sensitivity and selectivity of the sensor were demonstrated by its practical application for the determination of trace amounts of 4-NP in natural water and fruit samples.

• Bulletin of the Korean Chemical Society
• /
• 제16권5호
• /
• pp.392-397
• /
• 1995

o-Phenylenediamine (o-PD) was electropolymerized on glassy carbon electrodes under a potential cycling condition. The resulting polymer films mediated electrons for the reduction of molecular oxygen at pH=1.0. It was found from the RDE, RRDE, and cyclic voltammetry experiments that the modified electrodes reduce oxygen to hydrogen peroxide at about 300 mV lower potential than the bare glassy carbon electrode. The polymer film consisted of more than two components. Among those, only one component was active in oxygen reduction, which was formed mainly in the earlier stage of the electropolymerization. 2,3-Diaminophenazine, a cyclic dimer of o-PD, was also active in the oxygen reduction reaction, from which it was suggested that the active polymeric component has a structural unit similar to the cyclic dimer. Finally, the electropolymerization mechanism for the formation of the active and inactive components has been proposed.

• Journal of Electrochemical Science and Technology
• /
• 제7권4호
• /
• pp.277-285
• /
• 2016

There is a growing demand for simple, cost-effective, and accurate analytical tools to determine the concentrations of biological and environmental compounds. In this study, a stable electroactive thin film of cobalt hexacyanoferrate (Cohcf) was prepared as an in situ chemical precipitant using electrostatic adsorption of $Co^{2+}$ on a silicate sol-gel matrix (SSG)-modified indium tin oxide electrode pre-adsorbed with $[Fe(CN)_6]^{3-}$ ions. The modified electrode was characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical techniques. Electrocatalytic oxidation of hydrazine on the modified electrode was studied. An electrochemical sensor for hydrazine was constructed on the SSG-Cohcf-modified electrode. The oxidation peak currents showed a linear relationship with the hydrazine concentration. This study provides insight into the in situ growth and stability behavior of Cohcf nanostructures and has implications for the design and development of advanced electrode materials for fuel cells and sensor applications.

• 대한화학회지
• /
• 제67권5호
• /
• pp.339-347
• /
• 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.

• 한국재료학회지
• /
• 제19권5호
• /
• pp.233-239
• /
• 2009

The electrocatalytic behavior of the PtCo catalyst supported on the multi-walled carbon nanotubes (MWNTs) has been evaluated and compared with commercial Pt/C catalyst in a polymer electrolyte membrane fuel cell(PEMFC). A PtCo/MWNTs electrocatalyst with a Pt:Co atomic ratio of 79:21 was synthesized and applied to a cathode of PEMFC. The structure and morphology of the synthesized PtCo/MWNTs electrocatalysts were characterized by X-ray diffraction and transmission electron microscopy. As a result of the X-ray studies, the crystal structure of a PtCo particle was determined to be a face-centered cubic(FCC) that was the same as the platinum structure. The particle size of PtCo in PtCo/MWNTs and Pt in Pt/C were 2.0 nm and 2.7 nm, respectively, which were calculated by Scherrer's formula from X-ray diffraction data. As a result we concluded that the specific surface activity of PtCo/MWNTs is superior to Pt/C's activity because of its smaller particle size. From the electrochemical impedance measurement, the membrane electrode assembly(MEA) fabricated with PtCo/MWNTs showed smaller anodic and cathodic activation losses than the MEA with Pt/C, although ohmic loss was the same as Pt/C. Finally, from the evaluation of cyclic voltammetry(CV), the unit cell using PtCo/MWNTs as the cathode electrocatalyst showed slightly higher fuel cell performance than the cell with a commercial Pt/C electrocatalyst.

• Bulletin of the Korean Chemical Society
• /
• 제31권6호
• /
• pp.1583-1588
• /
• 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
• /
• 제7권4호
• /
• pp.298-305
• /
• 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 Microbiology and Biotechnology
• /
• 제22권10호
• /
• pp.1406-1411
• /
• 2012

5,5'-Dithiobis(2-nitrobenzoic acid) (DTNB) was selected as an electron transfer mediator and was covalently immobilized onto high porosity carbon cloth to employ as a working electrode in an electrochemical $NAD^+$-regeneration process, which was coupled to an enzymatic reaction. The voltammetric behavior of DTNB attached to carbon cloth resembled that of DTNB in buffered aqueous solution, and the electrocatalytic anodic current grew continuously upon addition of NADH at different concentrations, indicating that DTNB is immobilized to carbon cloth effectively and the immobilized DTNB is active as a soluble one. The bioelectrocatalytic $NAD^+$ regeneration was coupled to the conversion of L-glutamate into ${\alpha}$-ketoglutarate by L-glutamate dehydrogenase within the same microreactor. The conversion at 3 mM monosodium glutamate was very rapid, up to 12 h, to result in 90%, and then slow up to 24 h, showing 94%, followed by slight decrease. Low conversion was shown when substrate concentration exceeding 4 mM was tested, suggesting that L-glutamate dehydrogenase is inhibited by ${\alpha}$-ketoglutarate. However, our electrochemical $NAD^+$ regeneration procedure looks advantageous over the enzymatic procedure using NADH oxidase, from the viewpoint of reaction time to completion.