• 제목/요약/키워드: Electrocatalytic reduction

검색결과 96건 처리시간 0.024초

Amperometric Detection of DNA by Electroreducation of O2 in an Enzyme-Amplified Two-Component Assay

  • Yoon Chang-Jung;Kim Hyug-Han
    • 전기화학회지
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    • 제7권1호
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    • pp.44-48
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    • 2004
  • The two-component type enzyme amplified amperometric DNA assay is described to use an ambient $O_2$ of the substrate of the DNA labeling enzyme. Although the assay detects DNA only at > 0.5M concentration, a concentration $\~10^6$ fold higher than the sandwich-type enzyme amplified amperometric DNA assay, it can be run with an always available substrate. The assay utilizes screen-printed carbon electrodes (SPEs) which were pre-coated by a co-electrodeposited film of an electron conducting redox hydrogel and a 37-base long single-stranded DNA sequence. The DNA in the electron conducting film hybridizes and captures, when present, the 37-base long detection-DNA, which is labeled with bilirubin oxidase (BOD), an enzyme catalyzing the four-electron reduction of $O_2$ to water. Because the redox hydrogel electrically connects the BOD reaction centers to the electrode, completion of the sandwich converts the film from non-electrocatalytic to electrocatalytic for the reduction of $O_2$ to water when the electrode is poised at 200 mV vs. Ag/hgCl. The advantage or the assay over the earlier reported sandwich type enzyme amplified amperometric DNA assay, in which the amplifying enzyme was horseradish peroxidase, is that it utilizes ambient $O_2$ instead of the less stable and naturally unavailable $H_2O_2$.

Fine Structure Effect of PdCo electrocatalyst for Oxygen Reduction Reaction Activity: Based on X-ray Absorption Spectroscopy Studies with Synchrotron Beam

  • Kim, Dae-Suk;Kim, Tae-Jun;Kim, Jun-Hyuk;Zeid, E. F. Abo;Kim, Yong-Tae
    • Journal of Electrochemical Science and Technology
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    • 제1권1호
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    • pp.31-38
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    • 2010
  • In this study, we have demonstrated the fine structure effect of PdCo electrocatalyst on oxygen reduction reaction activity with different alloy composition and heat-treatment time. In order to identify the intrinsic factors for the electrocatalytic activity, various X-ray analyses were used, including inductively coupled plasma-atomic emission spectrometer, transmission electron microscopy, X-ray diffractometer, and X-ray Absorption Spectroscopy technique. In particular, extended X-ray absorption fine structure was employed to extract the structural parameters required for understanding the atomic distribution and alloying extent, and to identify the corresponding simulated structures by using FEFF8 code and IFEFFIT software. The electrocatalytic activity of PdCo alloy nanoparticles for the oxygen reduction reaction was evaluated by using rotating disk electrode technique and correlated to the change in structural parameters. We have found that Pd-rich surface was formed on the Co core with increasing heating time over 5 hours. Such core shell structure of PdCo/C showed that a superior oxygen reduction reaction activity than pure Pd/C or alloy phase of PdCo/C electrocatalysts, because the adsorption energy of adsorbates was apparently reduced by lowering the dband center of the Pd skin due to a combination of the compressive strain effect and ligand effect.

Adsorption of Macrocyclic Cobalt Complex on a Glassy Carbon Electrode for the Electrocatalytic Reduction of $O_2$

  • 강찬
    • Bulletin of the Korean Chemical Society
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    • 제19권7호
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    • pp.754-760
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    • 1998
  • It was found that the adsorption of a cobalt(III) complex with a macrocyclic ligand, C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc), was induced on a glassy carbon electrode by heavily oxidizing the electrode surface. Adsorption properties are discussed. The glassy carbon electrode with the adsorbed complex was employed to see the catalytic activities for the electro-reduction of O2. In the presence of oxygen, reduction of (hmc)Co3+ showed two cathodic waves in cyclic voltammetry. Compared to the edge plane graphite electrode at which two cathodic waves were also observed in a previous study, catalytic reduction of O2 occurred in the potential region of the first wave while it happened in the second wave region with the other electrode. A rotating disk electrode after the same treatment was employed to study the mechanism of the O2 reduction and two-electron reduction of O2 was observed. The difference from the previous results was explained by the different reactivity of the (hmc)CoOOH2+ intermediate, which is produced after the two electron reduction of (hmc)Co3+ in the presence of O2.

Electrocatalysis of Oxygen Reduction by Au Nanoparticles Electrodeposited on Polyoxometalate-Modified Electrode Surfaces

  • Choi, Kyung-Min;Choi, Su-Hee;Kim, Jong-Won
    • 전기화학회지
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    • 제12권1호
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    • pp.75-80
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    • 2009
  • The effect of polyoxometalate monolayers on the electrodeposition of Au nanoparticles (AuNPs) on glassy carbon (GC) surfaces was examined by electrochemical and scanning electron microscope techniques. The presence of $SiMo_{12}O^{4-}_{40}$-layers resulted in average particle sizes of ca. 60 nm, which is larger than AuNPs deposited on bare GC surfaces. AuNPs electrodeposited on $SiMo_{12}O^{4-}_{40}$-modified GC surfaces for 20 s exhibited the best electrocatalytic activity for oxygen reduction. This system exhibited similar or slightly better efficiency for oxygen reduction than a bare Au electrode. Rotating disk electrode experiments were also performed and revealed that the catalytic reduction of oxygen on AuNPs deposited on $SiMo_{12}O^{4-}_{40}$-modified GC electrodes is a two-electron process.

Poly(3,4-ethylenedioxythiophene) Electrodes Doped with Anionic Metalloporphyrins

  • 송의환;여인형;백운기
    • Bulletin of the Korean Chemical Society
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    • 제20권11호
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    • pp.1303-1308
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    • 1999
  • Conducting poly(3,4-ethylenedioxythiophene) (PEDT) films with metalloporphyrins incorporated as the counter ions were prepared by electropolymerization of the monomer in the presence of metal-tetra(sulfonatophenyl) porphyrin anions. Cathodic reduction of oxygen on the resulting conducting polymer films was studied. The overpotential for O2 reduction on electrodes with cobalt-porphyrin complex was significantly smaller in acidic solutions than on gold. In basic solutions, the overpotential at low current densities was close to those on platinum and gold. Polymer electrode with Co-complex yielded higher limiting currents than with Fe-complex, although the Co-complex polymer electrode was a poorer electrocatalyst for O2 reduction in the activation range of potential than the Fe counterpart. From the rotating ring-disk electrode experiments, oxygen reduction was shown to proceed through either a 4-electron pathway or a 2-electron pathway. In contrast to the polypyr-role-based electrodes, the PEDT-based metalloporphyrin electrodes were stable with wider potential windows, including the oxygen reduction potential. Their electrocatalytic properties were maintained at temperatures up to 80℃ in KOH solutions.

Pt-Ru@TiO2-H 나노구조체촉매의 합성 및 전기화학적 특성평가 (Electrocatalytic activity of the bimetallic Pt-Ru catalysts doped TiO2-hollow sphere nanocomposites)

  • 이인호;권해두;최성호
    • 분석과학
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    • 제26권1호
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    • pp.42-50
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    • 2013
  • 이 논문은 센서 및 연료전지에 사용할 수 있는 $Pt-Ru@TiO_2-H$ 나노구조체촉매의 제조 및 전기화학적 촉매의 특성에 대한 것이다. 이 $Pt-Ru@TiO_2-H$ 나노구조체촉매는 주형제인 폴리스틸렌볼(PSB)을 제조하고, 이 주형제의 표면에 졸-겔 반응을 통해 $TiO_2$를 코팅한 후, $Pt^{4+}$$Ru^{3+}$의 환원에 의해 제조하였다. 제조된, $Pt-Ru@TiO_2-H$ 나노구조체촉매는 전자투과현미경(TEM), X-선 회절(XRD)와 원소분석에 의해 특성평가 하였고, $Pt-Ru@TiO_2-H$의 전기화학적 촉매특성은 에탄올, 메탄올, 도파민, 아스크로브 산, 프로말린과 글루코오즈의 산화-환원 능력에 의해 평가 하였다. 이 $Pt-Ru@TiO_2-H$ 나노구조체촉매는 바이오분자에 대해 전기화학적촉매 특성을 나타내어, 연료전지 전극 또는 비효소바이오센서에 사용 될 것으로 기대된다.

Electropolymerization Mechanism for Poly(o-phenylenediamine) (PPD) and Its Electrocatalytic Behavior for $O_2$ Reduction

  • 장동훈;유용섭;오승모
    • Bulletin of the Korean Chemical Society
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    • 제16권5호
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    • pp.392-397
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    • 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.

Electrocatalytic Reduction of Dioxygen at Glassy Carbon Electrodes with Irreversible Self-assembly of N-hexadecyl-N'-methyl Viologen

  • Lee, Chi-Woo;Jang, Jai-Man
    • Bulletin of the Korean Chemical Society
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    • 제15권7호
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    • pp.563-567
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    • 1994
  • The electroreduction of dioxygen at glassy carbon electrodes with irreversible self-assembly of N-hexadecyl-N'-methyl viologen $(C_{16}VC_1)$ proceeds at potentials more positive than those where the reduction occurs at bare electrodes. The electrocatalyzed reduction takes place at potentials well ahead of those where the catalyst is reduced in the absence of dioxygen and the limiting currents observed at rotating disk electrodes did not deviate from the thoretical Levich line up to 6400 rpm, indicating that the electrocatalysis is extremely rapid. The rate constant for the heterogeneous reaction between $C_{16}V^+C_1$ immobilized on the electrode surface and $O_2$ in solution was estimated to be ca. $10^8\;M^{-1}s^{-1}$. The half-wave potential of dioxygen reduction was independent of solution pH.

Electrocatalytic Reduction of Thionyl Chloride by Schiff Base Metal(II) Complexes (1)

  • 신미숙;김우성;조기형;최용국
    • Bulletin of the Korean Chemical Society
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    • 제16권3호
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    • pp.205-210
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    • 1995
  • Catalytic effects of various Schiff base metal(II) complexes on the reduction of thionyl chloride at glassy carbon electrode are evaluated by determining the kinetic parameters from cyclic voltammetry technique. The charge transfer process is affected strongly by the concentration of catalysts during the reduction of thionyl chloride. The catalytic effects are shown by both a shift of the reduction potential for thionyl chloride toward more positive direction and an increase in peak current. The diffusion coefficient value, Do, of the 8.17 ${\times}$ 10-9 $cm^2/s$ was observed at the bare glassy carbon electrode, whereas larger values (0.9-1.09 ${\times}$ 10-8 $cm^2/s$) were observed at the catalyst supported glassy carbon electrode. Significant improvements in the cell performance have been noted in terms of both exchange rate constants and current densities at glassy carbon electrode.