• Title/Summary/Keyword: redox pair

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$^1H$ NMR Estimation of Multi-Redox potentials of Cytochrome $c_3$ from Desulfovibrio vulgaris Hildenborough

  • 박장수;강신원;최성낙
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.331-336
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    • 1995
  • The macroscopic and microscopic redox potentials of tetrahemoprotein, cytochrome c3 from Desulfovibrio vulgaris(Hildenborough) (DvH) were estimated from 1H NMR and differential pulse polarography(DPP). Five sets of NMR resonances were confirmed by a redox titration. They represent cytochrome c3 molecules in five macroscopic redox states. The electron transfer in cytochrome c3 involves four consecutive one-electron steps. The saturation transfer method was used to determine the chemical shifts of eight heme methyl resonances in five different oxidation states. Thirty two microscopic redox potentials were estimated. The results showed the presence of a strong positive interaction between a pair of particular hemes. Comparing the results with those of Desulfovibrio vulgaris Miyazaki F (DvMF), it was observed that the two proteins resemble each other in overall redox pattern, but there is small difference in the relative redox potentials of four hemes.

Redox Pairs in Redox Flow Batteries (레독스 플로우 전지의 레독스 쌍)

  • Hwang, Byunghyun;Kim, Ketack
    • Journal of the Korean Electrochemical Society
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    • v.16 no.3
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    • pp.99-110
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    • 2013
  • Redox flow batteries are attractive energy-storage devices for renewable energy and peak-power energy control. Even though some prototypes are available already, many new materials are under development for new battery systems. In this reports, redox pairs and theirs properties are explained, by which one can understand issues with redox pairs, such as contaminations, cross-over, ionic selectivity, and solubility. Batteries that have the same redox pairs in both electrode compartments can be operated longer than those with different redox pairs due to the prevention form the cross-contamination. There are undivided redox flow batteries that have no membrane, which is another direction improving cycle life of the batteries.

Study on the hydrogen production using the metal oxide (Cu-ferrite) (금속산화물(Cu-ferrite)를 이용한 수소제조 연구)

  • Park, Chu-Sik;Seo, In-Tai;Kim, Jung-Min;Lee, Sang-Ho;Hwang, Gap-Jin
    • Journal of Hydrogen and New Energy
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    • v.15 no.3
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    • pp.201-207
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    • 2004
  • Redox characteristics of metal oxide for hydrogen production by thermochemical water-splitting were investigated. $CuFe_2O_4$ as a redox pair that had a different molar ratio of Cu and Fe were prepared by co-precipitation method. Hydrogen production consisted of water-splitting step and thermal reduction step was performed below 1200K. Redox characteristics of Cu-ferrites were studied using the thermal gravimetric analysis technique. Also, structure change of Cu-ferrite during thermal reduction was investigated using the high temperature controlled XRD. In results, oxygen release of Cu-ferrite during the thermal reduction was initiated at oxygen site combined with Cu. Consequently, oxygen release amount of Cu-ferrite was increased with increase of Cu molar ratio of Cu-ferrite. It was found that thermal reduction of Cu-ferrite was begun at $875^\circ{C}$. It was confirmed that structure of Cu-ferrite was changed to metal and cation excess metal oxide during the thermal reduction step.

Facile Electrodeposition Technique for the Fabrication of MoP Cathode for Supercapacitor Application

  • Samanta, Prakas;Ghosh, Souvik;Murmu, Naresh Chandra;Lee, Joong Hee;Kuila, Tapas
    • Composites Research
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    • v.34 no.6
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    • pp.345-349
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    • 2021
  • The continued environmental pollution caused by fossil fuel consumption has prompted researchers around the world to develop environmentally friendly energy technologies. Electrochemical energy storage is the significant area of research in this development process, and the research significance of supercapacitors in this field is increasing. Herein, a simple electrodeposition synthetic route was explored to develop the MoP layered cathode material. The layered structure provided a highly ion-accessible surface for smooth and faster ion adsorption/desorption. After Fe was doped into MoP, the morphology of MoP changes and the electrochemical performance was significantly improved. Specific capacitance value of the binder-free FeMoP electrode was found to be 269 F g-1 at 2 A g-1 current density in 6 M aqueous KOH electrolyte. After adding Fe to MoP, an additional redox contribution was observed in the redox conversion from Fe3+ to Fe2+ redox pair, and the charge transfer kinetics of MoP was effectively improved. This research can provide guidance for the development of supercapacitor electrode materials through simple electrodeposition technology.

MnCo2S4/CoS2 Electrode for Ultrahigh Areal Capacitance

  • Pujari, Rahul B.;Lokhande, C.D.;Lee, Dong-Weon
    • Journal of Sensor Science and Technology
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    • v.29 no.4
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    • pp.215-219
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    • 2020
  • MnCo2S4/CoS2 electrode with highly accessible electroactive sites is prepared using the hydrothermal method. The electrode exhibits an areal capacitance of 0.75 Fcm-2 at 6 mAcm-2 in 1 M KOH. The capacitance is further increased to 2.06 Fcm-2 by adding K3Fe(CN)6 and K4Fe(CN)6 (a redox couple) to KOH. This increment is associated with the redox-active properties of cobalt and manganese transition metals, as well as the ion pair of [Fe(CN)6]-3/[Fe(CN)6]-4. The capacitance retention of the MnCo2S4/CoS2 electrode is 87.5% for successive 4000 charge-discharge cycles at 10 mAcm-2 in a composite electrolyte system of KOH and ferri/ferrocyanide. The capacitance enhancement is supported by the lowest equivalent series resistance (0.62 Ωcm-2) of MnCo2S4/CoS2 in the presence of redox additive couple compared with the bare KOH electrolyte.

Preparation and Characterization of $Pd/CeO_2/Ta/Si$ model catalysts

  • 김도희;우성일
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.145-145
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    • 2000
  • M-CeO2 (M : noble metal) catalysts have been widely studied as three-way catalysts and methanol synthesis catalysts. Ceria is thought to play a number of roles in these catalysts. The Ce(IV)/Ce(III) redox pair may store/release gases under oxidizing/reducing conditions, extending the operational window. Additionally, metal-ceria interactions lead to several effects, including the dispersion of the active components and promoting the activation of molecules such as CO or NO. Pd is a promising component to current TWC formulations and behaves particularly well when compared with Pt and Rh-based catalysts for low-temperature oxidation of Co and hydrocarbon. However the effect of Pd-ceria interactions on the physicochemical properties of Pd and the redox properties of Ce is not elucidated yet. In order to know exactly about the metal-ceria interactions, the model study are expecting to give a better environment, resulting in the wide use of the surface science tools. The substrate was Si(100) wafer, on which Ta metal was sputtered as a thickness of 100nm. The CeO2 thin film of 30nm was deposited by using the magnetron sputtering. Spin coating and magnetron sputtering methods were used to make the Pd thin film layer. The prepared sample was investigated by in-situ XPS, AES, SEM and AFM analysis.

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A Study on the Electronic Properties and Redox Reaction of Europium(Ⅲ) Complexes in Aprotic Solvent (반 양성자성 용매속에서 Europium(Ⅲ) 착물에 대한 전자적 성질과 산화 · 환원 반응에 관한 연구)

  • Choe, Chil Nam;Son, Hyo Youl;Kim, Se Bong
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.65-71
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    • 1996
  • The chemical behaviour of the Eu(Ⅲ) complexes with organic ligands(tris[3-(trifluoromethylhydroxymethylene-camphorato)]) and tris[3-heptafluoropropylhydroxymethylene-camphorato)] has been investigated by the UV/vis-spectrophotometric, magnetic, and electrochemcial methods. The two or three energy absorption bands are observed by the spectra of these complexes. The magnitude of crystal field splitting energy, the spin pair energy and strength were obtained from the spectra of the complexes. These complexes are found to be delocalization, low-spin state, and strong bonding strenth of electron configuration. The magnetic dipolemoment are found to be diamagnetic. The redox reaction processes of complexes were investigated by cyclic voltammetry in aprotic solvent. The redox reaction processes of complexes are turned out to be single or double reaction with respect to one electron diffusion current.

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Investigation of Direct and Mediated Electron Transfer of Laccase-Based Biocathode

  • Jamshidinia, Zhila;Mashayekhimazar, Fariba;Ahmadi, Masomeh;Molaeirad, Ahmad;Alijanianzadeh, Mahdi;Janfaza, Sajad
    • Journal of Electrochemical Science and Technology
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    • v.8 no.2
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    • pp.87-95
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    • 2017
  • Enzymatic fuel cells are promising low cost, compact and flexible energy resources. The basis of enzymatic fuel cells is transfer of electron from enzyme to the electrode surface and vice versa. Electron transfer is done either by direct or mediated electron transfer (DET/MET), each one having its own advantages and disadvantages. In this study, the DET and MET of laccase-based biocathodes are compared with each other. The DET of laccase enzyme has been studied using two methods; assemble of needle-like carbon nanotubes (CNTs) on the electrode, and CNTs/Nafion polymer. MET of laccase enzyme also is done by use of ceramic electrode containing, ABTS (2,2'-azino-bis [3-ethylbenzthiazoline-6-sulphonic acid]) /sol-gel. Cyclic voltammetric results of DET showed a pair of well-defined redox peaks at $200{\mu}A$ and $170{\mu}A$ in a solution containing 5and $10{\mu}M$ o-dianisidine as a substrate for needle-like assembled CNTs and CNTs-Nafion composite respectively. In MET method using sol-gel/ABTS, the maximum redox peak was $14{\mu}A$ in the presence of 15 M solution o-dianisidine as substrate. The cyclic voltammetric results showed that laccase immobilization on needle-like assembled CNTs or CNTs-Nafion is more efficient than the sol-gel/ABTS electrode. Therefore, the expressed methods can be used to fabricate biocathode of biofuel cells or laccase based biosensors.

Electrochemical Behaviors of Hydroquinone on a Carbon Paste Electrode with Ionic Liquid as Binder

  • Sun, Wei;Jiang, Qiang;Yang, Maoxia;Jiao, Kui
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.915-920
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    • 2008
  • In this paper the electrochemical behaviors of hydroquinone ($H_2Q$) were investigated on a carbon paste electrode using room temperature ionic liquid N-butylpyridinium hexafluorophosphate ($BPPF_6$) as binder (ILCPE) and further applied to $H_2Q$ determination. In pH 2.5 phosphate buffer solution (PBS), the electrochemical response of H2Q was greatly improved on the IL-CPE with a pair of well-defined quasi-reversible redox peaks appeared, which was attributed to the electrocatalytic activity of IL-CPE to the $H_2Q$. The redox peak potentials were located at 0.340 V (Epa) and 0.240 V (Epc) (vs. the saturated calomel electrode, SCE), respectively. The formal potential ($E^0$') was calculated as 0.290 V and the peak-to-peak separation (${\Delta}E_p$) was 0.100 V. The electrochemical parameters of $H_2Q$ on the IL-CPE were further calculated by cyclic voltammetry. Under the selected conditions the anodic peak current was linear with $H_2Q$ concentration over the range from $5.0\;{{\times}}\;10^{-6}$ to $5.0\;{\times}\;10^{-3}\;mol\;L^{-1}$ with the detection limit as $2.5\;{\times}\;10^{-6}\;mol\;L^{-1}$ (3$\sigma$ ) by cyclic voltammetry. The proposed method was successful applied to determination of $H_2Q$ content in a synthetic wastewater sample without the interferences of commonly coexisting substances.

Direct Electrochemistry and Electrocatalysis of Myoglobin with CoMoO4 Nanorods Modified Carbon Ionic Liquid Electrode

  • Zhao, Zengying;Cao, Lili;Hu, Anhui;Zhang, Weili;Ju, Xiaomei;Zhang, Yuanyuan;Sun, Wei
    • 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 ${\mu}mol\;L^{-1}$ ($3{\sigma}$).