• 한국수소및신에너지학회논문집
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• 제26권4호
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• pp.324-330
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• 2015

The electrolyte flow rates of vanadium redox flow battery play very important role in terms of ion transfer to electrolyte, kinetics and pump efficiency in system. In this paper a vanadium redox flow battery single cell was tested to suggest the optimization criteria of electrolyte flow rates on the efficiencies. The compared electrolyte circulation flow rates in this experimental work were 15, 30 and 45 mL/min. The charge/discharge characteristics of the flow rate of 30 mL/min was the best out of all flow rates in terms of charging and discharging time. The current efficiencies, voltage efficiencies and energy efficiencies at the flow rate of 30 mL/min were the best. The IR losses obtained at thd current density of $40mA/cm^2$, at the flow rates of 15, 30 and 45 mL/min were 0.085 V, 0.042 V and 0.115 V, respectively. The charge efficiencies at the current density of $40mA/cm^2$ were 96.42%, 96.45% and 96.29% for the electrolyte flow rates of 15, 30 and 45 mL/min, respectively. The voltge efficiencies at the current density of $40mA/cm^2$ were 77.34%, 80.62% and 76.10% for the electrolyte flow rates of 15, 30 and 45 mL/min, respectively. Finally, the energy efficiencies at the current density of $40mA/cm^2$ were 74.57%, 77.76% and 73.27% for the electrolyte flow rates of 15, 30 and 45 mL/min, respectively. The optimum flow rates of electrolytes were 20 mL/min in most of operating variables of vanadium redox flow battery.

• 대한화학회지
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• 제33권3호
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• pp.309-314
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• 1989

산 용액내에서 cis-$[Co(en)_2(N_3)_2]^+$와 Fe(II)간의 산화-환원 반응속도를 UV/vis-분광광도계로 측정하였다. 여기서 촉매 $H^+$가 관여한 반응속도상수와 각 반응물의 반응차수 그리고 활성화파라메타를 구하여 이들 자료를 바탕으로 타당한 반응메카니즘을 제안하였다. 본 연구의 실험결과를 보면, Co(III)와 Fe(II) 그리고 $H^+$에 대해서 각각 1차로 총괄반응이 3차 반응이다. 이때 반응속도상수 $K_H^+$는 $3.27{\times}10^{-2}l^2{\cdot}mol^{-2}{\cdot}sec^{-1}$이였다. 그리고 활성화에너지 $E_a$는 14.8Kcal/mol, 활성화엔탈피 ${\Delta}H^{\neq}$는 14.2Kcal/mol, 활성화엔트로피 ${\Delta}S^{\neq}$는 -16.7e.u.였다. 이러한 실험적 사실을 바탕으로, 본 반응계에서 $H^+$가 촉매로 작용하여 내부권(inner-sphere) 메카니즘으로 산화-환원반응이 진행되는 타당한 반응메카니즘을 제안하였다.

• Bulletin of the Korean Chemical Society
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• 제16권9호
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• pp.819-823
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• 1995

Thin films of two kinds of Prussian Blue (PB)-modified, using iron(Ⅲ) complex instead of conventional FeCl3, were prepared on a gold substrate and these films were able to be electrochemically reduced in potassium nitrate solution. In case of PB-modified films prepared from Fe(Ⅲ)-ethylenediamine-N,N'-diacetic acid (FeEN3+)/K3Fe(CN)6 solution, the mid-peak potential was 0.156 V in 0.1 M KNO3 and it was found that potassium ion migrates into or out of the film during the electrolysis. These films were shown to be electrochromic. These films exhibited smaller peak separation than those formed from Fe(Ⅲ)-tartaric acid (FeTA3+)/K3Fe(CN)6 system. The diffusion coefficient of Fe(CN)63-/4- redox couple, evaluated using the fabricated Au rotating disc electrode(rde) previously reported, was in good agreement with the existing data. Two experimental procedures, including the voltammetry at relatively low scan rates and the rde study, have been used in order to characterize the electrode kinetics. The electrode kinetics of some redox couples (FeEN2+-FeEN3+ and FeTA2+-FeTA3+) on both PB-modified thin films and bare Au electrode were studied using a Au rde. In all cases the rate constants of electron transfer obtained with the PB-modified film electrodes were only slightly less than those obtained for the same reaction on bare Au disc electrodes. The conductivities, as determined from the slopes of the i-V curves for a ca. 1 mm sample for dried PB-modified potassium-rich and deficient bulk samples pressed between graphite electrodes, were 6.21 × 10-7 and 2.03 × 10-7(Ω·cm)-1, respectively.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3539-3543
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• 2012

Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in $HClO_4$ medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both $[CAB]_o$, and $[substrate]_o$, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

• Journal of Electrochemical Science and Technology
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• 제10권2호
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• pp.185-195
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• 2019

The large surface area and the high electrical conductivity of graphene (GP) allow it to act as an "electron wire" between the redox center of biomolecules and an electrode surface. The faster electron transfer kinetics and excellent catalytic activity of GP facilitate the accurate and selective electrochemical detection of biomolecules. This mini-review provides an overview of the recent developments and progress of GP, functionalized or doped GP, and GP-composites based sensors for the selective and interference-free detection of dopamine (DA). The electrochemical principles and future perspective and challenges of DA sensors were also discussed based on GP.

• 센서학회지
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• 제30권2호
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• pp.71-75
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• 2021

Recently, transition-metal-based hydroxide materials have attracted significant attention in various electrochemical applications owing to their low cost, high stability, and versatility in composition and morphology. Among these applications, transition-metal-based hydroxides have exhibited significant potential in supercapacitors owing to their multiple redox states that can considerably enhance the supercapacitance performance. In this study, nanostructured Ni-Mn double hydroxide is directly grown on a conductive substrate using an electrodeposition method. Ni-Mn double hydroxide exhibits excellent electrochemical charge-storage properties in a 1 M KOH electrolyte, such as a specific capacitance of 1364 Fg-1 at a current density of 1 mAcm-2 and a capacitance retention of 94% over 3000 charge-discharge cycles at a current density of 10 mAcm-2. The present work demonstrates a scalable, time-saving, and cost-effective approach for the preparation of Ni-Mn double hydroxide with potential application in high-charge-storage kinetics, which can also be extended for other transition-metal-based double hydroxides.

• Journal of Ceramic Processing Research
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• 제19권5호
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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.

• 대한화학회지
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• 제31권2호
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• pp.178-183
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• 1987

$VO_2^+$와 $[Mo_3O_4(H_2O)_9]^{4+}$의 산화반응에 대한 속도론을 $25^{\circ}C$에서 분광광도법으로 연구하였다. 과량의 $VO_2^+$에서 $[Mo_3O_4(H_2O)_9]^{4+}$의 산화반응은 $Mo^{IV}_3+6V^V{\rightleftarrows}3Mo^{IV}+6V^IV}$이다. 반응에 대한 관찰된 속도상수, $k_{obs}$는 수소이온과 $VO^{2+}$에 의존한다. $[Mo_3O_4(H_2O)_9]^{4+}$와 $VO_2^+$의 산화-환원반응에 대한 상세한 메카니즘이 제시되며 이에 대하여 논의된다.

• 대한화학회지
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• 제30권6호
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• pp.532-537
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• 1986

$VO_2^+$와 $[Mo_2O_4(H_2O)_6]^{2+}$의 반응에 대한 속도론은 25$^{\circ}$C에서 분광광도법으로 연구하였다. $[Mo_2O_4(H_2O)_6]^{2+}$이 산화반응의 화학양론은$ Mo_2^V + 2V^V {\rightleftharpoons} 2Mo^{VI} + 2V^{IV}$이다. 관찰된 유사일차속도상수, $k_{obs}$는 수소이온과 $ VO^{2+}$에 의존한다. $[Mo_2O_4(H_2O)_6]^{2+}$와 $VO^{2+}$의 산화-환원반응에 대한 메카니즘이 제시되며 이에 대하여 논의된다.

• Bulletin of the Korean Chemical Society
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• 제9권5호
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.