• Title/Summary/Keyword: Redox Reaction

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Poly-3,4-dihydroxybenzaldehyde Modified with 3,4-dihydroxybenzoic acid for Improvement of Electrochemical Activities

  • Cha Seong-Keuck
    • Journal of the Korean Electrochemical Society
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    • v.7 no.4
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    • pp.167-172
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    • 2004
  • 3,4-dihydroxybenzaldehyde(3,4-DHB) was oxidatively el electropolymerized on glassy carbon (GC) electrodes to prepare CC/p-3,4-DHB type electrodes, which were subsequently modified with 3,4-dihydroxybenzoic acid(3,4-DHBA) using 0.05M HCI as a catalyst. The esterification reactions were performed between -OH sites on the polymeric film surface of the p-3,4-DHB and the -COOH sites within the 3,4-DHBA molecules in solution. These reactions had a rate constant value of $1.1\times10^{-1}\;s^{-1}$ for the esterification step as obtained from the first-order rate constant in the solution. The electrochemical responses of the GC/p-3,4-DHB-3,4-DHBA electrodes exert an influence upon the buffer solution, its pH and applied potential ranges. The redox process of the electrode was more easily controlled by charge transfer kinetics than that of the CC/p-3,4-DHB. The modified electrodes had redox active sites that were 10 times more active than those present before modification. The electrical admittance of the modified electrodes was also three times higher than that of the unmodified electrodes. After being annealed in ethanol for 20 hrs the electrodes brought about a 3.3 times greater change of water molecules in the redox reaction. The modified electrodes are stable in the potential range of 0.4 to 0.55V.

Electrochemical Properties of Polypyrrole/ Glucose Oxidase Enzyme Electrode (Polypyrrole/Glucose Oxidase 효소전극의 전기화학적 특성)

  • 김현철;구할본
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1999.05a
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    • pp.357-361
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    • 1999
  • GOD electrochemically immobilized in PPy/GOD complex have an effect on redox properties of the complex. In the cyclicvoltammetry, GOD shows the redox reaction at the potential below -0.6Y vs. Ag/AgCI. That leads to new peaks in the cyclicvoltammograms in additional to typical PPy peaks. The pH of electrolyte solution during potential swing decreased to 4.4, and then increased to 10. That suggests the redox of GOD for the cycling. As the concentration of GOD was increased, the anodic wave of the new peaks was strong as much as increased. GOD obstructs the diffusion of electrolyte anion because of its net chain. Insulating property of GOD is cause that it made the faradic impedance of complex large in charge transfer. It suggests that increase of the concentration of GOD be against electrochemical coupling. Therefore, the concentration of GOD and electrochemical coupling should be dealt with each other. The apparent Michaelis-lenten constant ( K\`$_{M}$ ) was determined by 30.7 mmol d $m^{-3}$ fur the PPy/GOD complex. The value is of the same order of magnitude as that for soluble glucose oxidase from Aspergillus Niger.r.

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Development of promotors for fast redox reaction of MgMnO3 oxygen carrier material in chemical looping combustion

  • Hwang, Jong Ha;Lee, Ki-Tae
    • Journal of Ceramic Processing Research
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    • v.19 no.5
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    • pp.372-377
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    • 2018
  • MgO or gadolinium-doped ceria (GDC, $Ce_{0.9}Gd_{0.1}O_{2-{\delta}}$) was added as a promoter to improve the oxygen transfer kinetics of $MgMnO_3$ oxygen carrier material for chemical looping combustion. Neither MgO nor GDC reacted with $MgMnO_3$, even at the high temperature of $1100^{\circ}C$. The average oxygen transfer capacities of $MgMnO_3$, 5 wt% $MgO-MgMnO_3$, and 5 wt% $GDC-MgMnO_3$ were 8.74, 8.35, and 8.13 wt%, respectively. Although the addition of MgO or GDC decreased the oxygen transfer capacity, no further degradation was observed during their use in 5 redox cycles. The addition of GDC significantly improved the conversion rate for the reduction reaction of $MgMnO_3$ compared to the use of MgO due to an increase in the surface adsorption process of $CH_4$ via oxygen vacancies formed on the surface of GDC. On the other hand, the conversion rates for the oxidation reaction followed the order 5 wt% $GDC-MgMnO_3$ > 5 wt% $MgO-MgMnO_3$ >> $MgMnO_3$ due to morphological change. MgO or GDC particles suppressed the grain growth of the reduced $MgMnO_3$ (i.e., (Mg,Mn)O) and increased the specific surface area, thereby increasing the number of active reaction sites.

Synthesis and Characterization of Bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato)nickel(II), nickel(III) and of Related Dialkyl Nickel(III) Dithiolene Complexes

  • 김영진;최성낙;오영희
    • Bulletin of the Korean Chemical Society
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    • v.18 no.9
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    • pp.1022-1028
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    • 1997
  • The reaction between Ni(Ⅱ) and sodium salt of 5,6-dihydro-1,4-dithiin-2,3-dithiolate (DDDT2-) in the presence of oxygen results in the formation of Ni(Ⅲ) species, Ni(DDDT)2-, which is isolated as tetraalkylammonium salt. The same reaction performed in the absence of oxygen yields dianionic Ni(Ⅱ) species, Ni(DDDT)22-, which is also isolated as the tetraethylammonium salt. The bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato) nickelate (Ⅱ) dianion, Ni(DDDT)22-, reacts with methyl iodide to yield unusually stable bis(methylthio)dithiolene complex, Ni(CH3)2C8H8S8. All the isolated dithiolato-nickel(Ⅱ) and nickel(Ⅲ) complexes are characterized by 1H NMR, UV/Vis, IR and mass spectroscopic methods. The internal redox reaction of the nickel(Ⅱ)-dithiolate has been studied by spectro-electrochemical method and the results were compared with those of other metal-dithiolenes. The alkylated nickel(dithiolene) complex presumably undergoes cis-trans isomerization reaction in solution, judging from the experimental results of variable-temperature 1H NMR measurements.

Kinetic Studies on the Reaction of Iron (Ⅲ) with D-penicillamine in Acidic Solution$^1$

  • Hyun-Jae Park;Yung-Hee Oh Kim;Jung-Ae Shim;Sung-Nak Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.444-449
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    • 1993
  • Anaerobic oxidation of D-penicillamine by Fe(III) in acidic solution has been studied kinetically by the use of stopped-flow system. The reaction is biphasic with a rapid complexation of 1: 1 complex, $Fepen^+$ (pen= D-penicillamine dianion) which is then internally reduced to Fe(II) and disulfide. Rates of both the complexation and the redox process are pH dependent and also are affected by the presence of chloride ion. Different from the reaction of Cu(II) with D-penicillamine, partially oxidized mixed-valence complex is not formed even transiently in this reaction.

Application of Porous Carbon Catalyst Activating Reaction of Positive Electrode in Vanadium Redox Flow Battery (바나듐 레독스 흐름전지의 양극반응 활성화를 위한 다공성 탄소 촉매의 적용)

  • Jeong, Sanghyun;Chun, Seung-Kyu;Lee, Jinwoo;Kwon, Yongchai
    • Journal of Energy Engineering
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    • v.23 no.3
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    • pp.150-156
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    • 2014
  • In this study, we implemented a research for improving performance of redox flow battery (RFB) via enhancing reaction rate of vanadium reaction ($[VO]^{2+}/[VO_2]^+$) that was a rate determining step. For doing that, porous catalyst, CMK3 was employed and its perfoamance was compared with that of Vulcan(XC-72) and commercial Pt/C (Johnson-Matthey Pt 20wt.%). Cyclic voltammetry (CV) was used for inspecting reactivity, while its structural feature was measured by TEM and BET&BJH. Also, Charge-discharge trend was evaluated by single cell tests. As result, CMK3 showed 6 times better catalytic activity and twice better reversibility than Vulcan(XC-72), while it showed larger surface area than Vulcan XR due to its porous structure. Furthermore, CMK3 indicated 85% of reactivity and reversibility of commercial Pt/C despite its Pt-less situation. In single cell tests, when RFB adopted CMK3 as catalyst for positive electrode, its charge-discharge curve result was better than that adopted commercial Pt/C.

Electrodeposition of Conducting Polymers on Copper in Nonaqueous Media by Corrosion Inhibition

  • Lee, Seonha;Lee, Hochun
    • Journal of Electrochemical Science and Technology
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    • v.3 no.2
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    • pp.85-89
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    • 2012
  • This study demonstrates the direct anodic electrodeposition of polypyrrole (PPy), poly(3,4-ethyl-enedioxythiophene) (PEDOT), and polythiophene (PTh) on Cu electrodes by employing a corrosion inhibitor, succinonitrile (SN). SN was found to suppress anodic Cu dissolution beyond the oxidation potential of the polymer monomers. It is also revealed that the Cu surface passivated by SN is still adequately conductive to allow the redox reaction of 1,4-difluoro-2,5-dimethoxybenzene (FMB) and the oxidation of the polymer monomers. Through both cyclic voltammetry and galvanostatic techniques, PPy, PEDOT, and PTh films were successfully synthesized on Cu electrodes in the presence of SN, and the redox behaviors of the films were evaluated.

Redox Potential of a Soybean Ferric Leghemoglobin Reductase

  • Kim, Hyun-Mi
    • BMB Reports
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    • v.31 no.5
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    • pp.444-452
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    • 1998
  • The visible spectra of soybean ferric leghemoglobin reductase exhibited a charge transfer band at 530 nm under aerobic condition. Spectra of the oxidized enzyme show a flavin peak at 454 nm and the enzyme has three redox states associated with the active site of the enzyme. The enzyme has an active disulfide bridge and two-electron transfer may dominate in the ferric state of leghemoglobin reduction. The midpoint potentials of the enzyme were determined by spectrotitration to be -0.294 V for disulfide/dithiol and -0.318 V for FAD/$FADH_2$. Since the midpoint potentials for $NAD^+$/NADH and the ferrous/ferric states of leghemoglobin are -0.32 V and +0.22 V, respectively, it is proposed that two electrons are transferred sequentially from NADH to FAD, to the disulfide group, and then to the ferric state of leghemoglobin in the enzyme reaction.

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Electrochemical Approach in Plasma Display Panel Glass Melts doped with Sulfate and Sulfide II. Square Wave Voltammetry

  • Kim, Ki-Dong
    • Journal of the Korean Ceramic Society
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    • v.45 no.7
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    • pp.375-379
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    • 2008
  • Redox behavior was observed in alkali alkaline earth silicate PDP (Plasma Display Panel) glass melts doped with sulfate and sulfide by square wave voltammetry (SWV). According to voltammograms produced at a temperature range of 1100 to $1400^{\circ}C$ and frequency range of 5 to 1000 Hz, both melts showed the same behavior in which there is one reduction peak at low frequency but another peak at an increase of frequency. Based on the frequency dependence of the peak current, self diffusivity of $S^{4+}$ was determined. Based on the temperature dependence of the peak potential, standard enthalpy (${\Delta}H^0$) and standard entropy (${\Delta}S^0$) for the reduction of $S^{4+}$ to $S^0$ were calculated.

The Synthesis of New Leuco Squarylium Dyes

  • Park, Soo-Youl;Jun, Kun;Shin, Seung-Rim;Shin, Jong-Il
    • Textile Coloration and Finishing
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    • v.19 no.5
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    • pp.24-29
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    • 2007
  • It is well known that certain classes of dye are reducible to stable colorless leuco compounds, which can be oxidized in air back to the colored species. We now reported that bis(4-dialkylaminophenyl)squaraine dyes are readily reduced in solution by borohydride to give alkali soluble leuco compound, which exists in the 3-hydroxy 2,4-bis(4-dialkylaminophenyl)cyclobuten-one. New alkylamine leuco compounds were synthesized by the reaction of leuco chloro-squaraine with alkylamine derivatives. The leuco compounds are easily isolated and can be air oxidized back to the squaraine dyes. These dyes have many technical application. e.g. in xerography, solar cell, optical recording material, redox indicators, and enzyme assays.