• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.868-873
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• 2019

In this study, the evaluation of performance of AORFB using methyl viologen and TEMPOL as organic active materials in neutral supporting electrolyte (NaCl) with various membrane types was performed. Using methyl viologen and TEMPOL as active materials in neutral electrolyte solution, the cell voltage is 1.37V which is relatively high value for AORFB. Two types of membranes were examined for performance comparison. First, when using Nafion 117 membrane which is commercial cation exchange membrane, only the charge process occurred in the first cycle and the single cell couldn't work because of its high resistance. However, when using Fumasep anion exchange membrane (FAA-3-50) instead of Nafion 117 membrane, the result was obtained as the totally different charge-discharge graphs. When current density was $40mA{\cdot}cm^{-2}$ and cut off voltage range was from 0.55 V to 1.7 V, the charge efficiency (CE) was 97% and voltage efficiency (VE) was 78%. In addition, the discharge capacity was $1.44Ah{\cdot}L^{-1}$ which was 54% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $10^{th}$ cycle and the capacity loss rate was $0.0015Ah{\cdot}L^{-1}$ per cycle during 50 cycles. Through cyclic voltammetry test, it seems that this difference in the performance between the full cell using Nafion 117 membrane and Fumasep anion exchange membrane came from increasing resistance due to chemical reaction between membrane and active material, not the capacity loss due to cross-over of active material through membrane.

• Korean Chemical Engineering Research
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• v.60 no.4
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• pp.588-593
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• 2022

Terephthalaldehyde (TPA) is introduced as a cross liker to enhance electron transfer of hemin-based cathodic catalyst consisting of polyethyleneimine (PEI), carbon nanotube (CNT) for hydrogen peroxide reduction reaction (HPRR). In the cyclic voltammetry (CV) test with 10 mM H₂O₂ in phosphate buffer solution (pH 7.4), the current density for HPRR of the suggested catalyst (CNT/PEI/hemin/PEI/TPA) shows 0.2813 mA cm^-2 (at 0.2 V vs. Ag/AgCl), which is 2.43 and 1.87 times of non-cross-linked (CNT/PEI/hemin/PEI) and conventional cross liker (glutaraldehyde, GA) used catalyst (CNT/PEI/hemin/PEI/GA), respectively. In the case of onset potential for HPRR, that of CNT/PEI/hemin/PEI/TPA is observed at 0.544 V, while those of CNT/PEI/hemin/PEI and CNT/PEI/hemin/PEI/GA are 0.511 and 0.471 V, respectively. These results indicate that TPA plays a role in facilitating electron transfer between the electrodes and substrates due to the π-conjugated cross-linking bonds, whereas conventional GA cross-linker increases the overpotential by interrupting electron and mass transfer. Electrochemical impedance spectroscopy (EIS) results also display the same tendency. The charge transfer resistance (R_ct) of CNT/PEI/hemin/PEI/TPA decreases about 6.2% from that of CNT/PEI/hemin/PEI, while CNT/PEI/hemin/PEI/GA shows the highest R_ct. The polarization curve using each catalyst also supports the superiority of TPA cross liker. The maximum power density of CNT/PEI/hemin/PEI/TPA (36.34±1.41 μWcm^-2) is significantly higher than those of CNT/PEI/hemin/PEI (27.87±0.95 μWcm^-2) and CNT/PEI/hemin/PEI/GA (25.57±1.32 μWcm^-2), demonstrating again that the cathode using TPA has the best performance in HPRR.