• Journal of Electrochemical Science and Technology
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• 제9권1호
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• pp.20-27
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• 2018

We describe a redox-enhanced electric double-layer capacitor (EDLC) that turns the electrolyte in a conventional EDLC into an integral, active component for charge storage-charge is stored both through faradaic reactions with soluble redox-active molecules in the electrolyte, and through the double-layer capacitance in a porous carbon electrode. The mixed-redox electrolyte, composed of vanadium and iodides, was employed to achieve high power density. The electrochemical reaction in a supercapacitor with vanadium and iodide was studied to estimate the charge capacity and energy density of the redox supercapacitor. A redox supercapacitor with a mixed electrolyte composed of 0.75 M NaI and 0.5 M $VOSO_4$ was fabricated and studied. When charged to a potential of 1 V, faradaic charging processes were observed, in addition to the capacitive processes that increased the energy storage capabilities of the supercapacitor. The redox supercapacitor achieved a specific capacity of 13.44 mAh/g and an energy density of 3.81 Wh/kg in a simple Swagelok cell. A control EDLC with 1 M $H_2SO_4$ yielded 7.43 mAh/g and 2.85 Wh/kg. However, the relatively fast self-discharge in the redox-EDLC may be due to the shuttling of the redox couple between the polarized carbon electrodes.

• 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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2006년도 영호남 합동 학술대회 및 춘계학술대회 논문집 센서 박막 기술교육
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• pp.63-64
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• 2006

본 연구에서는 광에너지를 화학적인 에너지로 변환할 때, 디바이스의 전하전달 매개를 위한 electron transfer mediator로서 널리 이용되는 Viologen이 자기조립화된 수정진동자률 전기화학법의 하나인 순환전압전류법(Cyclic Voltammetry)을 이용하여 산화 환원 반응 (redox reaction) 특성과 주사속도와 피크전류와의 상관관계를 분석하였다. 먼저 수정진동자를 친수 처리한 후, 메탄올 용액과 아세토니트릴 용액을 섞은 용매에 Viologen 분자를 자기조립 (self-assembly)하여, 전해질 용액의 농도 변화에 따른 산화 환원반응 특성과 피크전류의 값을 측정하였다 주사 속도를 2 배씩 증가하여 피크전류와의 상관관계를 조사한 결과, 선형적인 증가를 보였으며, 이를 통해 가역적인 반응(reversible reaction)이 일어났음을 확인할 수 있었다. 또한, 산화 환원 반응과 동시에 측정된 수정진동자의 공진 주파수(resonant frequency) 변화로부터 전하이동(charge transfer) 특성에 의해 반응에 참가한 이온의 질량을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제17권1호
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• pp.21-30
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• 2006

[ $M/Fe_2O_3$ ] (M=Rh, Ce and Zr) mixed oxides were prepared using urea method to develop a medium for chemical hydrogen storage by their redox cycles. And their redox behaviors by repeated cycles were studied using temperature programmed reaction(TPR) technique. Additives such as Rh, Ce and Zr were added to iron oxides in order to lower the reaction temperature for reduction by hydrogen and re-oxidation by water-splitting. From the results, concentration of urea used as a precipitant had little effect on particle size and reduction property of iron oxide. TPR patterns of iron oxide consisted of two reduction peaks due to the course of $Fe_2O_3\;{\rightarrow}\;Fe_3O_4\;{\rightarrow}\;Fe$. The results of repeated redox tests showed that Rh added to iron oxide have an effect on lowering the re-oxidation temperature by water-splitting. Meanwhile, Ce and Zr additives played an important role in prevention of deactivation by repeated cycles. Finally, Fe-oxide(Rh, Ce, Zr) sample added with Rh, Ce and Zr showed the lowest re-oxidation temperature by water-splitting and maintained high $H_2$ recovery in spite of the repeated redox cycles. Consequently, it is expected that Fe-oxide(Rh, Ce, Zr) sample can be a feasible medium for chemical hydrogen storage using redox cycle of iron oxide.

• 한국세라믹학회지
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• 제33권9호
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• pp.1045-1049
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• 1996

Pressureless-sintered polycrystalline alumina and carbon steel were joined with Ag-33.5Cu-1.5Ti (wt%) brazing alloy. SEM observation revealed that two reaction layers with different thicknesses were continuously formed between the alumina and the brazing alloy. A thick layer formed on the brazing alloy side was identified as Ti3(Cu0.93Al0.07)3O phase with diamond cubic structure. Another thin layer adjacent to the alumina was revealed as $\delta$-TiO phase of which the crystal structure was HCP with a lattice parameter of a0=0.419 nm and c0=0.284 nm. It was confirmed using XPS analysis that $\delta$-TiO was formed directly by a redox reaction of alumina with titanium ir, molten brazing alloy.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.303-306
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• 1990

Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

• 전기화학회지
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• 제5권4호
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• pp.189-191
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• 2002

Reversible trans-cis isomerization of meta-bipyridylazobenzene coordinated to cobalt was achieved by a combination of photoirradiation with a single UV light source and a Co(II)/Co(III) redox reaction. The trans/cis conversion performance was significantly improved in the meta-form compared with the meta-form ligated to cobalt.

• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1233-1238
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• 2000

$Mo/{\gamma}-Al_2O_3catalysts$ modified with Fe, Co, and Ni were prepared by impregnation method and catalytic activity for water gas shift reaction was examined. The optimum amount of Mo loaded for the reaction was 10 wt% $MoO_3$ to ${\gamma}-Al_2O_3.$ The catalytic activity of $MoO_3/{\gamma}-Al_2O_3was$ increased by modifying with Fe, Co, and Ni in the order of Co${\thickapprox}$ Ni > Fe. The optimum amounts of Co and Ni added were 3 wt% based on CoO and NiO to 10 wt% $MoO_3/{\gamma}-Al_2O_3$, restectively. The TPR (temperature-programmed reduction) analysis revealed that the addition of Co and Ni enganced the reducibility of the catalysts. The results of both catalytic activity and TPR experiments strongly suggest that the redox property of the catalyst is an important factor in water gas shift reaction on the sulfided Mo catalysts, which could be an evidence of oxy-sulfide redox mechanism.

• Bulletin of the Korean Chemical Society
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• 제12권3호
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• pp.276-281
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• 1991

Electrochemical behaviors of optically active sparteine-Cu(II) dihalide complexes were investigated by polarography and cyclic voltammetry (CV). These Cu(II) complexes are rather easier to be reduced to Cu(I) states when comparison is made with other nonplaner copper complexes, We have assigned the CV peaks and polarographic waves related to the redox processes for these complexes. We could also observe the exchange reaction of Cu(II) ion in the complex with mercury metal in the cell having mercury pool. The redox mechanism of these complelxes is as follows; The 1st wave appeared at +0.47 V/+0.65 V corresponds to the reaction of $SpCuX_2+ e{\rightleftarrow}SpCuX_{2^-}$ and the 2nd one at +0.26 V/+0.21 V does the reaction of $SpCuX_{2 ^-} +e{\rightleftarrow}SpCuX_2^{2-}$. The 3rd one at -0.35 V/-0.27 V is dueto the reduction of mercury complex formed via exchange reaction. Where, X is chloride ion.

• 한국수소및신에너지학회논문집
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• 제22권5호
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• pp.721-727
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• 2011

All vanadium redox-flow battery (VRFB) has been studied actively as one of the most promising electrochemical energy storage systems for a wide rage of applications such as electric vehicles, photovoltaic arrays, and excess power generated by electric power plants at night time. In this study, carbon felt electrodes were treated by electrochemical oxidation with KOH, and the cyclic voltammetry were studied in order to investigate redox reactivity of vanadium ion species with carbon felt electrodes. Besides the effect of electrochemical oxidation on the surface chemistry of carbon felt electrodes were investigated using the X-ray photoelectron spectroscopy (XPS). After electrochemical oxidation, XPS analysis of PAN based GF20-3 carbon felt electrode revealed on increase in the overall surface oxygen content of the carbon felts after electrochemical oxidation. Redox reaction characteristics using cyclic voltammetry (CV) were ascertained that the electrochemical treated electrode were more reversible than the untreated electrode.