• Bulletin of the Korean Chemical Society
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• v.19 no.8
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• pp.825-830
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• 1998

The electrocatalytic reduction of dioxygen by Co(TTFP)(Y)2 {Y=H2O or HO-} is investigated by cyclic voltammetry, spectroelectrochemistry, hydrodynamic voltammetry at a glassy carbon electrode in dioxygen-saturated aqueous solutions. Electrocatalytic reduction of dioxygen by CoⅡ(TTFP)(Y)2 establishes a pathway of 2e- reduction to form hydrogen peroxide, and then the generated hydrogen peroxide is reduced to water by CoⅠ(TTFP)(Y)2 at more negative potential. CoⅡ(TTFP)(Y)2 may bind dioxygen to produce the adduct complex [CoⅡ-O2 or CoⅢ-O2] which exhibits a Soret band at 411 nm and Q band at 531 nm.

• Analytical Science and Technology
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• v.8 no.4
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• pp.617-622
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• 1995

Electrocatalytic reduction of dioxygen has been investigated by cyclic voltammetry at glassy carbon electrode modified with new Co(II)-Schiff base complexes in aqueous solutions of various pH. The reduction potentials of dioxygen at chemically adsorbed electrodes show the dependence of pH between pH 4 and 14. The catalytic effect is large and the reaction occurs via two or four electron transfer in various pH solution.

• Bulletin of the Korean Chemical Society
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• v.20 no.9
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• pp.1056-1060
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• 1999

New water soluble and highly electron deficient cobalt(II) tetrakis-(1,2,5,6-tertrafluoro-4-NN'N"-trimethyla-nilinium)-β-octabromoporphyrin [Co II (Br8TTFP)(Y)2] was synthesized and used for the electrocatalytic reduction of dioxygen. The first reduction of synthesized [Co II (Br8TTFP)(Y)2] involves one electron process to give metal centered [Co I (Br8TTFP)(Y)2]. The reduction of potential [E1/2 = -0.32 V] of [Co II (Br8TTFP)(Y)2] shifts positively 370 mV compared with that of [Co II (TTFP)(Y)2] due to the substituted bromide to β-pyrrole positions. The electrochemically reduced [Co I (Br8TTFP)(Y)2] binds dioxygen and catalytically reduces it to HOOH by 2e - transfer. Cyclic and hydrodynamic voltammetry at a glassy carbon electrode in dioxygen-saturated aqueous solutions are used to study the electrocatalytic pathway.

• Bulletin of the Korean Chemical Society
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• v.15 no.7
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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.

• Journal of the Korean Chemical Society
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• v.37 no.4
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• pp.462-469
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• 1993

The electrocatalytic reduction of dioxygen is investigated by cyclic voltammetry and chronoamperometry at glassy carbon electrode and carbon microelectrode coated with a variety of cobalt phenylporphyrins. The n value obtained at carbon microelectrode is slightly different from that determined at glassy carbon electrode. Dioxygen reduction catalyzed by the monormeric porphyrin Co(II)-TPP mainly occurs through the $2e^-$ reduction pathway resulting in the formation of hydrogen peroxide, electrocatalytic process carries out $4e^-$ reduction pathway of dioxygen to $H_2O$ at the electrodes coated with bis-cobalt phenylporphyrins. The electrocatalytic reduction of dioxygen is irreversible and diffusion controlled.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.449-451
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• 1992

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.170-171
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• 1990

• Journal of the Korean Electrochemical Society
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• v.9 no.3
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• pp.113-117
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• 2006

The electrochemical properties of the redox mediator, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) ($ABTS^{2-}$) were studied using cyclic voltammetry. The measured potentials (${E^o}'$ vs SCE) of the two redox couples of ABTS are 0.45 V for $ABTS^{2-}/ABTS^{\cdot-}$ and 0.87 V for $ABTS^{\cdot-}/ABTS^0$. The rate constant for heterogeneous electron transfer and the diffusion coefficients for $ABTS^{2-}$ are $5x10^{-3}cm\;s^{-1}$ and $3.1x10^{-6}cm^2\;s^{-1}$, respectively. Our interest in $ABTS^{2-}$ stems from the fact that this molecule functions as a substrate to the copper oxidase, laccase, by providing the reducing equivalents necessary for the biocatalyzed reduction of dioxygen to water. Consequently, when laccase is tethered to an electrode surface or dissolved in solution, $ABTS^{2-}$ can be used to quantify enzyme activity electrochemically.

• Analytical Science and Technology
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• v.11 no.6
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• pp.460-468
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• 1998

Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.195-200
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• 1993

The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.