• Title/Summary/Keyword: electrochemical reactions

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Enhancement of oxygen evolution reaction of NiCo LDH nanocrystals using Mo doping (Mo 도핑을 이용한 NiCo LDH 나노결정의 산소발생반응 향상)

  • Kyoungwon Cho;Jeong Ho Ryu
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.34 no.3
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    • pp.92-97
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    • 2024
  • To improve the efficiency of water splitting systems for hydrogen production, the high overvoltages of electrochemical reactions caused by catalysts in the oxygen evolution reaction (OER, Oxygen Evolution Reaction) must be reduced. Among them, LDH (Layered Double Hydroxide) compounds containing transition metal such as Ni, are attracting attention as catalyst materials that can replace precious metals such as platinum that are currently used. In this study, nickel foam, an inexpensive metallic porous material, was used as a support, and NiCo LDH (Layered Double Hydroxide) nanocrystals were synthesized through a hydrothermal synthesis process. In addition, changes in the shape, crystal structure, and water decomposition characteristics of the Mo-doped NiCo LDH nanocrystal samples synthesized by doping Mo to improve OER properties were observed.

Preparation and Characterization of Dimeric Molybdenum(Ⅴ) Complexes with Bis(hydroxyethyl)dithiocarbamate (Bis(Hydroxyethyl)dithiocarbamate 의 이핵 몰리브덴 (Ⅴ) 착물 합성과 그 성질)

  • Yeh Gyung-Hak;Koo Bon-Kweon
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.452-459
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    • 1990
  • A series of oxo-and sulfido-bridged molybdenum (V) complexes, Mo$_2$O$_4$L$_2$, Mo$_2$O$_3$L$_4$, Mo$_2$O$_2$S$_2$L$_2$, and Mo$_2$OS$_3$L$_2$ [L = bis(hydroxyethyl)dithiocarbamate] have been prepared. The complexes with bridging and terminal oxo groups have been synthesized by the reactions of (PyH)$_2$MoOCl$_5$ or MoCl$_5$ and ligand in water. One of the rest two complexes, in which bridging and terminal oxo groups have been replaced by sulfido in Mo$_2$O$_4^{2+}$ core, Mo$_2$O$_2$S$_2$L$_2$ have been prepared by addition of triphenylphosphine to a chloroform solution of Mo$_2$OS$_3$L$_2$. While, Mo$_2$OS$_3$L$_2$ is obtained from aqueous solution of (NH$_4$)$_2$MoS$_4$ and ligand in the presence of sodium dithionite. The complexes are identified by elemental analysis, and spectral data of IR, UV-vis, nmr, and mass. Also, the electrochemical behaviour for the complexes in dimethylsulfoxide has been investigated by the cyclic voltammograms.

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Synthesis and Properties of 1,4-Diboracyclohexene-2 Derivatives (1,4-Dibora-2-cyclohexene 유도체들의 합성과 그 성질)

  • Uhm, Jae-Kook;Hu D.;Zenneek U.;Pritzkow H.;Siebert W.
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.490-497
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    • 1990
  • Two synthetic routes for the 1,4-diboracyclohexene-2 ring 8 have been developed. Method i) starts with 1,2-bis(dichloroaluminyl)ethane, in which the AlCl$_2$ group is replaced by BCl$_2$. Exchange of the chlorine with BI$_3$ in 1,2-bis-(dichloroboryl)ethane yields the corresponding iodo compound, which reacts with the alkynes to heterocycles 8a, b in good yield. In method ii) B$_2$Cl$_4$ is added to alkenes, replacement of chlorine with BI$_3$ yields the bis(diiodoboryl)ethane derivatives which undergo redox reactions with alkynes to give 8c, d. The diiodo derivative 8a forms the pyridine adduct 9a, and reacts with ether to give the ethoxy derivative 8f. 8a-d react with AlMe$_3$ to yield the corresponding dimethyl derivatives 8g-j, which give unstable radical anions when treated with potassium in THF. The ESR parameters are reported. In electrochemical experiments irreversible reductions of 8g-j are observed. 8g-j react with (C$_5$H$_5$)Co(C$_2$H$_4$)$_2$ to give the intermediate 16 VE complexes (C$_5$H$_5$)Co(8), in which C-H activation occurs with formation of the corresponding red 1,4-diboracyclohexadiene complexes 10. The X-ray structure analyses of 10h and 10j are reported.

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Numerical Studies of a Separator for Stack Temperature Control in a Molten Carbonate Fuel Cell (용융탄산염 연료전지 스택 온도 조절을 위한 분리판에 관한 수치 해석 연구)

  • Kim, Do-Hyung;Kim, Beom-Joo;Lim, Hee-Chun
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.3
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    • pp.305-312
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    • 2011
  • The use of a separator to control stack temperature in a molten carbonate fuel cell was studied by numerical simulation using a computational fluid dynamics code. The stack model assumed steady-state and constant-load operation of a co-flow stack with an external reformer at atmospheric pressure. Representing a conventional cell type, separators with two flow paths, one each for the anode and cathode gas, were simulated under conditions in which the cathode gas was composed of either air and carbon dioxide (case I) or oxygen and carbon dioxide (case II). The results showed that the average cell potential in case II was higher than that in case I due to the higher partial pressures of oxygen and carbon dioxide in the cathode gas. This result indicates that the amount of heat released during the electrochemical reactions was less for case II than for case I under the same load. However, simulated results showed that the maximum stack temperature in case I was lower than that in case II due to a reduction in the total flow rate of the cathode gas. To control the stack temperature and retain a high cell potential, we proposed the use of a separator with three flow paths (case III); two flow paths for the electrodes and a path in the center of the separator for the flow of nitrogen for cooling. The simulated results for case III showed that the average cell potential was similar to that in case II, indicating that the amount of heat released in the stack was similar to that in case II, and that the maximum stack temperature was the lowest of the three cases due to the nitrogen gas flow in the center of the separator. In summary, the simulated results showed that the use of a separator with three flow paths enabled temperature control in a co-flow stack with an external reformer at atmospheric pressure.

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.

Effects of Calcination Temperature on Characteristics of Electrospun TiO2 Catalyst Supports for PEMFCs (열처리 온도가 전기방사방법을 이용하여 제조한 PEMFC용 TiO2 담체의 물리적 특성에 미치는 영향)

  • Kwon, Chorong;Yoo, Sungjong;Jang, Jonghyun;Kim, Hyoungjuhn;Kim, Jihyun;Cho, Eunae
    • Transactions of the Korean hydrogen and new energy society
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    • v.24 no.3
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    • pp.223-229
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    • 2013
  • Polymer Electrolyte Membrane Fuel Cell (PEMFC) is a power generation system to convert chemical energy of fuels and oxidants to electricity directly by electrochemical reactions. As a catalyst support for PEMFCs, carbon black has been generally used due to its large surface area and high electrical conductivity. However, under certain circumstances (start up/shut down, fuel starvation, ice formation etc.), carbon supports are subjected to serve corrosion in the presence of water. Therefore, it would be desirable to switch carbon supports to corrosion-resistive support materials such as metal oxide. $TiO_2$ has been attractive as a support with its stability in fuel cell operation atmosphere, low cost, commercial availability, and the ease to control size and structure. However, low electrical conductivity of $TiO_2$ still inhibits its application to catalyst support for PEMFCs. In this paper, to explore feasibility of $TiO_2$ as a catalyst support for PEMFCs, $TiO_2$ nanofibers were synthesized by electrospinning and calcinated at 600, 700, 800 and $900^{\circ}C$. Effects of calcination temperature on crystal structure and electrical conductivity of electrospun $TiO_2$ nanofibers were examined. Electrical conductivity of $TiO_2$ nanofibers increased significantly with increasing calcination temperature from $600^{\circ}C$ to $700^{\circ}C$ and then increased gradually with increasing the calcination temperature from $700^{\circ}C$ to $900^{\circ}C$. It was revealed that the remarkable increase in electrical conductivity could be attributed to phase transition of $TiO_2$ nanofibers from anatase to rutile at the temperature range from $600^{\circ}C$ to $700^{\circ}C$.

Scaleup of Electrolytic Reactors in Pyroprocessing (Pyroprocessing 공정에 사용되는 전해반응장치의 규모 확대)

  • Yoo, Jae-Hyung;Kim, Jeong-Guk;Lee, Han-Soo
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.7 no.4
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    • pp.237-242
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    • 2009
  • In the pyroprocessing of spent nuclear fuels, fuel materials are recovered by electrochemical reactions on the surface of electrodes as well as stirring the electrolyte in electrolytic cells such as electrorefiner, electroreducer and electrowinner. The system with this equipment should first be scaled-up in order to commercialize the pyroprocessing. So in this study, the scale-up for those electrolytic cells was studied to design a large-scale system which can be employed in a commercial process in the future. Basically the dimensions of both electrolytic cells and electrodes should be enlarged on the basis of the geometrical similarity. Then the criterion of constant power input per unit volume, characterizing the fluid behavior in the cells, was introduced in this study and a calculation process based on trial-and-error methode was derived, which makes it possible to seek a proper speed of agitation in the electrolytic cells. Consequently examples of scale-up for an arbitrary small scale system were shown when the criterion of constant power input per unit volume and another criterion of constant impeller tip speed were respectively applied.

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Oxidation of Organic Compounds through the Electrochemical Reaction Using $TiO_{2}$ Photocatalytic Membranes ($TiO_{2}$ 광촉매 막의 전기화학 반응에 의한 유기물의 산화)

  • 현상훈;이기홍
    • Membrane Journal
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    • v.6 no.2
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    • pp.101-108
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    • 1996
  • The oxidation/degradation efficiency of formic acid through the photoelectrochemical reaction has been investigated as a basic research in order to develope the process for degrading toxic organic compounds dissolved in water. A $TiO_{2}$ photoelectro-membrane reactor for purification of water, in which filtration as well as photoelectrocatalytic oxidation of organic compounds could be carried out simultaneously, was developed. Porous $SnO_{2}$ tubes prepared by slip casting and commercial porous stainless steel tubes, being electrically conductive, were used as not only supports but also working electrodes. The UV light with the wavelength of 365 nm was applied as a light source for photocatalytic reactions. The photoelectrocatatytic composite membranes were prepared by coating the support surface with the $TiO_{2}$ sol of pH 1.45. The oxidation efficiency of formic acid increased with the reaction time and the applied voltage, but was almost independent of the solution flux. The results showed that more than 90% of formic acid could he dograded at 27V using the $TiO_{2}$/stainless steel composite membrane, while about 77% in case of the $TiO_{2}/SnO_{2}$ Composite membrane. It was also concluded that the oxidation efficiencies of formic acid could be significantly improved by about 6~7 times by the photoelectrochemical reaction in comparison with those by the photocatalytic reaction only.

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Synthesis and Characterization of Quinoxaline-Based Thiophene Copolymers as Photoactive Layers in Organic Photovoltaic Cells

  • Choi, Yoon-Suk;Lee, Woo-Hyung;Kim, Jae-Ryoung;Lee, Sang-Kyu;Shin, Won-Suk;Moon, Sang-Jin;Park, Jong-Wook;Kang, In-Nam
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.417-423
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    • 2011
  • A series of new quinoxaline-based thiophene copolymers (PQx2T, PQx4T, and PQx6T) was synthesized via Yamamoto and Stille coupling reactions. The $M_ws$ of PQx2T, PQx4T, and PQx6T were found to be 20,000, 12,000, and 29,000, with polydispersity indices of 2.0, 1.2, and 1.1, respectively. The UV-visible absorption spectra of the polymers showed two distinct absorption peaks in the ranges 350 - 460 nm and 560 - 600 nm, which arose from the ${\pi}-{\pi}^*$ transition of oligothiophene units and intramolecular charge transfer (ICT) between a quinoxaline acceptor and thiophene donor. The HOMO levels of the polymer ranged from -5.37 to -5.17 eV and the LUMO levels ranged from -3.67 to -3.45 eV. The electrochemical bandgaps of PQx2T, PQx4T, and PQx6T were 1.70, 1.71, and 1.72 eV, respectively, thus yielding low bandgap behavior. PQx2T, PQx4T, and PQx6T had open circuit voltages of 0.58, 0.42, and 0.47 V, and short circuit current densities of 2.9, 5.29 and 9.05 mA/$cm^2$, respectively, when $PC_{71}BM$ was used as an acceptor. For the solar cells with PQx2T-PQx6T:$PC_{71}BM$ (1:3) blends, an increase in performance was observed in going from PQx2T to PQx6T. The power conversion efficiencies of PQx2T, PQx4T, and PQx6T devices were found to be 0.69%, 0.73%, and 1.80% under AM 1.5 G (100 mW/$cm^2$) illumination.

Electrochemical Properties of Needle Coke through a Simple Carbon Coating Process for Lithium Ion Battery (침상 코크스의 피치 코팅에 따른 리튬 이차전지 탄소계 음극소재의 전기화학적 특성)

  • Hwang, Jin Ung;Lee, Jong Dae;Im, Ji Sun
    • Applied Chemistry for Engineering
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    • v.31 no.5
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    • pp.514-519
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    • 2020
  • Graphite materials for lithium ion battery anode materials are the most commercially available due to their structural stability and low price. Recently, research efforts have been conducted on carbon coatings by improving side reactions at the edge site of carbon materials. The carbon coating process has classified into a CVD by chemical reaction, wet coating process with solvent and dry coating by mechanical impact. In this paper, the rapid crush/coating process was used to solve the problem of which only few parts of the carbon precursor (pitch) can be used and also environmental problems caused by solvent removal in the wet coating process. When the ratio of needle coke to pitch was 8 : 2 wt%, and the rapid crush/coating process was carried out, it was confirmed that the fracture surface was coated by pitch. The pitch-coated sample was treated at 2400 ℃ and 41.8% improvement in 10C/0.1C rate characteristic was observed. It is considered that the material simply manufactured through the simple crush/coating process can be used as an anode electrode material for a lithium ion battery.