• Title/Summary/Keyword: Electrochemical advanced oxidation

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Electrochemical Properties and Synthesis of Poly(ether)tailed Cobalt(II)bipyridine Complex (폴리(에테르)사슬이 결합된 Cobalt(II)bipyridine 착물의 합성과 전기화학적 성질)

  • Kim, II Kwang;Jun, II Chul;Murray, Royce W.
    • Analytical Science and Technology
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    • v.9 no.3
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    • pp.292-301
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    • 1996
  • The synthesis of poly(ether)tailed bipyridine complex as redox reaction probes has advanced attempts to interpret very slow diffusion and heterogeneous electron transfer. Diffusion coefficients as low as $1.5{\times}10^{-15}cm^2/s$ have been observed for the oxidation of neat $Co(bpy(ppgm)_2)_{3^-}(ClO_4)_2$ with $LiClO_4$ electrolyte. Heterogeneous electron transfer rate constants of materials were found to vary with diffusion coefficient. The decrease in k as the diffusion coefficient decreases was actually caused by the decreasing D. Diffusion coefficient for compound of strong ion pairing anion($ClO{_4}^-$) was much smaller than the diffusion coefficient for compound of weak ion pairing anion($CF_3COO^-$).

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A study on reactive chlorine species generation enhanced by heterojunction structures on surface of IrO2-based anodes for water treatment (IrO2 기반 수처리용 산화 전극의 표면 이종 접합 구성에 따른 활성 염소종 발생 증진 특성 연구)

  • Hong, Sukhwa;Cho, Kangwoo
    • Journal of Korean Society of Water and Wastewater
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    • v.32 no.4
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    • pp.349-355
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    • 2018
  • This study interrogated multi-layer heterojunction anodes were interrogated for potential applications to water treatment. The multi-layer anodes with outer layers of $SnO_2/Bi_2O_3$ and/or $TiO_2/Bi_2O_3$ onto $IrO_2/Ta_2O_5$ electrodes were prepared by thermal decomposition and characterized in terms of reactive chlorine species (RCS) generation in 50 mM NaCl solutions. The $IrO_2/Ta_2O_5$ layer on Ti substrate (Anode 1) primarily served as an electron shuttle. The current efficiency (CE) and energy efficiency (EE) for RCS generation were significantly enhanced by the further coating of $SnO_2/Bi_2O_3$ (Anode 2) and $TiO_2/Bi_2O_3$ (Anode 3) layers onto the Anode 1, despite moderate losses in electrical conductivity and active surface area. The CE of the Anode 3 was found to show the highest RCS generation rate, whereas the multi-junction architecture (Anode 4, sequential coating of $IrO_2/Ta_2O_5$, $SnO_2/Bi_2O_3$, and $TiO_2/Bi_2O_3$) showed marginal improvement. The microscopic observations indicated that the outer $TiO_2/Bi_2O_3$ could form a crack-free layer by an incorporation of anatase $TiO_2$ particles, potentially increasing the service life of the anode. The results of this study are expected to broaden the usage of dimensionally stable anodes in water treatment with an enhanced RCS generation and lifetime.

Development of Micro-Tubular Perovskite Cathode Catalyst with Bi-Functionality on ORR/OER for Metal-Air Battery Applications

  • Jeon, Yukwon;Kwon, Ohchan;Ji, Yunseong;Jeon, Ok Sung;Lee, Chanmin;Shul, Yong-Gun
    • Korean Chemical Engineering Research
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    • v.57 no.3
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    • pp.425-431
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    • 2019
  • As rechargeable metal-air batteries will be ideal energy storage devices in the future, an active cathode electrocatalyst is required with bi-functionality on both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during discharge and charge, respectively. Here, a class of perovskite cathode catalyst with a micro-tubular structure has been developed by controlling bi-functionality from different Ru and Ni dopant ratios. A micro-tubular structure is achieved by the activated carbon fiber (ACF) templating method, which provides uniform size and shape. At the perovskite formula of $LaCrO_3$, the dual dopant system is successfully synthesized with a perfect incorporation into the single perovskite structure. The chemical oxidation states for each Ni and Ru also confirm the partial substitution to B-site of Cr without any changes in the major perovskite structure. From the electrochemical measurements, the micro-tubular feature reveals much more efficient catalytic activity on ORR and OER, comparing to the grain catalyst with same perovskite composition. By changing the Ru and Ni ratio, the $LaCr_{0.8}Ru_{0.1}Ni_{0.1}O_3$ micro-tubular catalyst exhibits great bi-functionality, especially on ORR, with low metal loading, which is comparable to the commercial catalyst of Pt and Ir. This advanced catalytic property on the micro-tubular structure and Ru/Ni synergy effect at the perovskite material may provide a new direction for the next-generation cathode catalyst in metal-air battery system.

Effects of Sulfur Substitution on Chemical Bonding Nature and Electrochemical Performance of Layered LiMn0.9Cr0.1O2-xSx

  • Lim, Seung-Tae;Park, Dae-Hoon;Lee, Sun-Hee;Hwang, Seong-Ju;Yoon, Young-Soo;Kang, Seong-Gu
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1310-1314
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    • 2006
  • Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

Characteristics of Decomposition for Refractory Organic Compounds in Aqueous Solution by Sonolysis and Electrolysis (초음파와 전기분해를 이용한 수중의 난분해성 유기물질의 분해 특성)

  • Jeong, Jae-Baek;Lee, Seong-Ho;Bae, Jun-Ung
    • Journal of the Korean Chemical Society
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    • v.50 no.6
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    • pp.454-463
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    • 2006
  • refractory organic compounds in aqueous solution are not readily removed by the existing conventional wastewater treatment process. In recent years, the sonolysis and electrochemical oxidation process had been shown to be promising for wastewater treatment due to the effectiveness and easiness in operation. This study was performed to investigate the characteristics of sonolytic and electrolytic decomposition as the basic data for development of the wastewater treatment process. Trichloroethylene(TCE) and 2,4- dichlorophenol(2,4-DCP) were used as the samples, and their destruction efficiency were measured with various operating parameters, such as initial solution concentration, initial solution pH, reaction temperature, sonic power and current density. Also, the decomposition mechanism conformed indirectly with the effect of NaHCO3 as a radical scavenger on the decomposition reaction. Thermal decompositon reaction is predominant for TCE but thermal and radical decompositon reactions were dominant for 2,4-DCP. Results showed that the destruction efficiencies of all samples were above 65% within 120 minutes by sonolysis and electrolysis at the same time, and were increased with increasing initial concentration, sonic power and current density. Destruction efficiency of TCE was high in the acidic solution, but 2,4-DCP showed high destruction efficiency in basic solution.

Preparation of Polyacrylonitrile-based Carbon Nanofibers by Electrospinning and Their Capacitance Characteristics (전기방사에 의한 폴리아크릴로니트릴계 탄소나노섬유 제조와 커패시턴스 특성)

  • Park, Soo-Jin;Im, Se-Hyuk;Rhee, John M.;Park, Seong-Yong;Kim, Hee-Jung
    • Applied Chemistry for Engineering
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    • v.18 no.3
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    • pp.205-212
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    • 2007
  • In this work, polyacrylonitrile (PAN) fiber was prepared by electrospinning methods from dimethyl formamide solutions with various conditions, such as 8~20 kV applied voltage, 5~15 wt% PAN concentration, and 15 cm tip-to-collector distance (TCD). The nanofibers were stabilized by oxidation at $250^{\circ}C$ for 1 h, and then subsequently carbonized at $800{\sim}1000^{\circ}C$ for 1 h. The structured characteristics of the nanofibers before and after carbonization were studied by Fourier transform infrared spectroscopy. The resulting diameter distribution and morphologies of the nanofiber were evaluated by scanning electron microscope analysis. The electrochemical behaviors of the nanofiber were observed by cyclic voltammetry tests. From the results, the diameter of electrospinning nanofibers was predominantly influenced by the concentration of polymer solution and the applied voltage. The average diameter of the fibers was decreased with increasing the polymer concentration up to 10wt%. It was also found that the nanofibers with uniform diameter distribution and fine diameter could be achieved at 15kV input voltage and 15 cm TCD.

Effects of Electrodeposition Parameters on Electrochemical Hydroxyl Radical Evolution of PbO2 Electrode (이산화납 전극 제조 시 전기화학적 증착인자가 수산화라디칼 발생에 미치는 영향)

  • Shim, Soojin;Yoon, Jeyong
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.12
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    • pp.647-655
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    • 2016
  • Lead dioxide ($PbO_2$) is an electrode material that is effective for organic pollutant degradation based on hydroxyl radical ($^{\bullet}OH$) attack. Representative parameters for $PbO_2$ electrodeposition are summarized to current, temperature, reaction time, concentration of Pb(II) and electrolyte agent. In this study, $Ti/PbO_2$ electrodes were fabricated by electrodeposition method under controlled reaction time, current density, temperature, concentration of $HNO_3$ electrolyte. Effects of deposition parameters on $^{\bullet}OH$ evolution were investigated in terms of electrochemical bleaching of p-Nitrosodimethylaniline (RNO). As major results, the $^{\bullet}OH$ evolution was promoted at the $PbO_2$ that was deposited in longer reaction time (1-90 min), lower current density ($0.5-50mA/cm^2$), higher temperature ($5-65^{\circ}C$) and lower $HNO_3$ concentration (0.01-1.0 M). Especially, the $PbO_2$ which was deposited in 0.01 M of lowest $HNO_3$ concentration by applying $20mA/cm^2$ for above 10 min was most effective on $^{\bullet}OH$ evolution. The performance gap between $PbO_2$s that was best and worst in $^{\bullet}OH$ evolution was about 41%. Among the properties of $PbO_2$ related on $^{\bullet}OH$ evolution performance, conductivity of $Ti/PbO_2$ significantly influenced on $^{\bullet}OH$ evolution. The increase in conductivity promoted $^{\bullet}OH$ evolution. In addition, the increase in crystal size of $PbO_2$ interfered $^{\bullet}OH$ evolution at surface of some $PbO_2$ deposits.

Structural and electrochemical characterization of K2NiF4 type layered perovskite as cathode for SOFCs (K2NiF4 type 층상 페롭스카이트 구조 La(Ca)2Ni(Cu)O4-δ의 SOFC 양극 특성 및 결정구조 평가)

  • Myung, Jae-ha;Hong, Youn-Woo;Lee, Mi Jai;Jeon, Dae-Woo;Lee, Young-Jin;Hwang, Jonghee;Shin, Tae Ho;Paik, Jong Hoo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.25 no.3
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    • pp.116-120
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    • 2015
  • $La_2NiO_{4+{\delta}}$ based oxides, a mixed electronic-ionic conductors (MIECs) with $K_2NiF_4$ type structure, have been considerably investigated in recent decades as electrode materials for advanced solid oxide fuel cells (SOFCs) due to their high electrical conductivity, and oxidation reduction reaction (ORR). In this study, structure properties of $La(Ca)_2Ni(Cu)O_{4+{\delta}}$ were studied as a potential cathode for intermediate temperature SOFCs (IT-SOFCs).