• Title/Summary/Keyword: Reaction rate constant

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Optimization of fabrication and process conditions for highly uniform and durable cobalt oxide electrodes for anion exchange membrane water electrolysis (음이온 교환막 수전해 적용을 위한 고균일 고내구 코발트 산화물 전극의 제조 및 공정 조건 최적화)

  • Hoseok Lee;Shin-Woo Myeong;Jun-young Park;Eon-ju Park;Sungjun Heo;Nam-In Kim;Jae-hun Lee;Jae-hun Lee;Jae-Yeop Jeong;Song Jin;Jooyoung Lee;Sang Ho Lee;Chiho Kim;Sung Mook Choi
    • Journal of Surface Science and Engineering
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    • v.56 no.6
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    • pp.412-419
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    • 2023
  • Anion exchange membrane electrolysis is considered a promising next-generation hydrogen production technology that can produce low-cost, clean hydrogen. However, anion exchange membrane electrolysis technology is in its early stages of development and requires intensive research on electrodes, which are a key component of the catalyst-system interface. In this study, we optimized the pressure conditions of the hot-pressing process to manufacture cobalt oxide electrodes for the development of a high uniformity and high adhesion electrode production process for the oxygen evolution reaction. As the pressure increased, the reduction of pores within the electrode and increased densification of catalytic particles led to the formation of a uniform electrode surface. The cobalt oxide electrode optimized for pressure conditions exhibited improved catalytic activity and durability. The optimized electrode was used as the anode in an AEMWE single cell, exhibiting a current density of 1.53 A cm-2 at a cell voltage of 1.85 V. In a durability test conducted for 100 h at a constant current density of 500 mA cm-2, it demonstrated excellent durability with a low degradation rate of 15.9 mV kh-1, maintaining 99% of its initial performance.

The Amino-Carbonyl Reaction in the Fructose-Glycine Mixture System (Fructose-Glycine 혼합계에 있어서 Amino-Carbonyl 반응)

  • Lee, Jin-Ho;Han, Kang-Wan
    • Korean Journal of Food Science and Technology
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    • v.21 no.3
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    • pp.351-359
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    • 1989
  • This study was conducted to observe the physico-chemical exchange and effect of amino-carbonyl reaction between fructose and glycine . When various buffer solutions were added to equimolar mixture of fructose and glycine at pH 6.0 and $100^{\circ}C$, the browning effect was markedly observed by Mcllvaine buffer. Among the combinations of temperature and reaction time, the deep browning effect was obtained above $100^{\circ}C$, 3hr A marked browning effect obtained above pH 7.0 but little observed below pH 7.0. The browning effect was markedly increased at high fructose concentration. It required 4.0hrs and 32.9hrs to decrease 50% of initial concentration of fructose and glycine at $100^{\circ}C$ and pH 7 but 0.9hrs and 3.8hrs at $120^{\circ}C$, pH 7.0, respectively. The rate constant of fructose and glycine at $100^{\circ}C\;and\;120^{\circ}C$ were $1.78{\times}10^{-1},\;2.11{\times}10^{-2}\;and\;7.74{\times}10^{-1},\;1.83{\times}10^{-1}$, respectively. The formation of HMF was likely to follow the first order kinetics. The addition of 0.1M sodium sulfite, 0.1M sodium bisulfite and 0.1M calcium chloride to equimolar mixture (0.05M) surpressed the reaction up to 76.8%, 76.8% and 96.4%, respectively.

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Studies on Improved Carbon Cathode Performance in High Rate $Li/SOCl_2$ Cell (고율 방전용 $Li/SOCl_2$ 전지의 카본 양극 개선에 관한 연구)

  • 최정자;조성백;박희숙
    • Journal of the Korean Ceramic Society
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    • v.34 no.3
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    • pp.225-232
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    • 1997
  • The performance characteristics of high rate discharge LiSOCl2 cells are highly affected by carbon cathode. During the cell discharge, SOCl2 reduction takes place at the porous carbon cathode, resulting in the precipitation of reaction products, mainly LiCl, within the pores of the substrate. This leads to eventual passivation of the cathode surface and resulting cell failure. To improve the cathode performance, we ex-amined discharge reactions of cathodes (half-cell, 50 mA/$\textrm{cm}^2$ constant current) with various surface density and thickness. The carbon cathode with the optimum capacity for our application is surface density 0.04 g/$\textrm{cm}^2$ and thickness 1.4mm carbon. The carbon cathode with surface density 0.04g/$\textrm{cm}^2$ and thickness 1.4 mm exhibits decreased polarization, increased discharge duration time and capacity (Ah/$\textrm{cm}^2$) as compared with that with surface density 0.04g/$\textrm{cm}^2$ and thickness 0.8mm. The porosities analyses on the two carbon cathodes show that total pore volume of the carbon cathode with thickness 1.4 mm is larger than that with thickness 0.8mm. The increased volume of mesopores (0.05$\mu$m~0.5$\mu$m) and macropores(>0.5$\mu$m) is ob-served with the carbon cathode with thickness 1.4mm as compared with that with thickness 0.8mm, which can be related with the observed capacity increase. We observed LiCl crystals, cubic crystallites and fused, plate-like aggregates, and some elemental S as discharge products by EDS and XRD.

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Improvement of Au Leaching from Gold Concentrates Using a Microwave and Thiourea-mixed Solvent (마이크로웨이브를 이용한 금정광 내 금 용출 효율 증가 기작)

  • Kim, Bong-Ju;Kwon, Jang-Soon;Koh, Yong-Kwon;Park, Cheon-Young
    • Economic and Environmental Geology
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    • v.53 no.2
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    • pp.159-166
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    • 2020
  • In this research, we investigate the effect of microwave pretreatment on the recovery of gold from the gold concentrates by thiourea leaching. The changes in mineral phases by decomposition of pyrites in the gold concentrates using microwave were observed, and the result of microwave irradiation showed that the temperature of the irradiated sample increases with increasing irradiation time. With the reaction of temperature increases, Sulfur (S) in pyrites was converted to sulfur dioxide (SO2), and then the content of S in the sample was reduced. The analytical results of XRD and SEM-EDS showed that pyrites are converted to magnetite and hematite, and its surfaces are changed to a porous shape where micro-cracks are developed. The Au leaching efficiency from the irradiated gold concentrates using thiourea-mixed solvent increased with the increases of irradiation time and solvent concentration. The experimental results considering leaching parameters indicate that the mechanism of microwave irradiation increases the maximum leaching efficiency and leaching rate of the gold concentrates, and the solvent does a role for the increasing of leaching rate constant.

Microwave-assisted Photocatalytic Degradation of Methylene Blue (마이크로웨이브가 부가된 광촉매에 의한 메틸렌블루의 분해)

  • Kim, Yu-Bong;Jo, A-Ra;Ra, Deog-Gwan;Park, Jae-Hyeon;Kim, Sun-Jae;Jung, Sang-Chul
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.8
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    • pp.817-822
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    • 2008
  • In this study, the photocatalytic degradation of methylene blue in TiO$_2$ particles-dispersed water solution was carried out by irradiating microwave and UV light simultaneously. A microwave-discharged electrodeless UV lamp was developed to use microwave and UV simultaneously for photocatalytic reactions. The results of photocatalytic degradation of methylene blue showed that the decomposition rate increased with the microwave intensity, the circulating fluid velocity, and the amount of TiO$_2$ particles and auxiliary oxidizing agents added. Especially, the rate constant of H$_2$O$_2$-added photocatalytic reaction increased about three times from 0.0075 min$^{-1}$ to 0.0250 min$^{-1}$ when microwave was additionally irradiated. This study demonstrates that the microwave irradiation can play a very important role in photocatalytic degradation using peroxides although it is not easy to quantitatively assess the effect of microwave on photocatalytic reactions from the experimental data of this study.

Electrochemical Characteristics of PFO pitch Anode prepared by Chemical Activation for Lithium Ion Battery (리튬이온전지용 화학적 활성화로 제조된 석유계 피치 음극소재의 전기화학적 특성)

  • Hwang, Jin Ung;Lee, Jong Dae
    • Korean Chemical Engineering Research
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    • v.55 no.3
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    • pp.307-312
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    • 2017
  • In this study, the electrochemical performance of surface modified carbon using the PFO (pyrolyzed fuel oil) was investigated by chemical activation with KOH and $K_2CO_3$. PFO was heat treated at $390{\sim}400^{\circ}C$ for 1~3h to prepared the pitch. Three carbon precursors (pitch) prepared by the thermal reaction were 3903 (at $390^{\circ}C$ for 3h), 4001(at $400^{\circ}C$ for 1h) and 4002 (at $400^{\circ}C$ for 2h). Also, the effect of chemical activation catalysts and mixing time on the development of porosity during carbonization was investigated. The prepared carbon was analyzed by BET and FE-SEM. It was shown that chemical activation with KOH could be successfully used to develop carbon with specific surface area ($3.12m^2/g$) and mean pore size (22 nm). The electrochemical characteristics of modified carbon as the anode were investigated by constant current charge/discharge, cyclic voltammetry and electrochemical impedance tests. The coin cell using pitch (4002) modified by KOH has better initial capacity (318 mAh/g) than that of other pitch coin cells. Also, this prepared carbon anode appeared a high initial efficiency of 80% and the retention rate capability of 2C/0.1 C was 92%. It is found that modified carbon anode showed improved cycling and rate capacity performance.

Electrochemistry for Redox Polymer Film of N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium Ion (N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium이온의 산화-환원 고분자 피막에 대한 전기화학)

  • Cha, Seong-Keuck
    • Polymer(Korea)
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    • v.25 no.1
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    • pp.6-14
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    • 2001
  • The monomer N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium$(PF_6)_2$ was electrochemically polymerized on glassy carbon electrode surface. This polymer film electrode has electroactive sites on its bipyridinium ions distributed at the polymer strands. The formal potentials of the electrodes were -0.41V and -0.81V(vs. SSCE) for each step at phosphate buffer(pH=5.70). The diffusion coefficients of the dopants ions into the polymer matrix were $1.57{\times}10^{-4}$ and $4.35{\times}10^{-5}cm^2s^{-1}$ for first and second redox couple, respectively. The rate constants of electron transfer at $V^{2+/+}$ of the first step was a $57.53s^{-1}$, which was 22 times higher than $V^{+/0}$ one having $2.63s^{-1}$ in the solution. The charge transfer resistance of the polymer film was influenced by the dopant ion of the electrolyte. Thus the resistances were 22.63, 16.81, 12.44 and $11.36k{\Omega}$ for $LiClO_4,\;NaClO_4,\;KClO_4$, and phosphate buffer, respectively. The reaction order of the electropolymerization was first order and the rate constant of the polymerization was $1.31{\times}10^{-1}s^{-1}$ as determined by EQCM method. The G.C./p-BPB type electrode doped with phosphate ions showed a stability and reproducibility in CV procedure over 20 cycles.

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Characteristics of Copper-catalyzed Cyanide Decomposition by Electrolysis (전해법에 의한 구리함유 시안의 분해특성)

  • Lee Jin-Yeung;Yoon Ho-Sung;Kim Sung-Don;Kim Chul-Joo;Kim Joon-Soo;Han Choon;Oh Jong-Kee
    • Resources Recycling
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    • v.13 no.1
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    • pp.28-38
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    • 2004
  • The characteristics of cyanide decomposition in aqueous phase by electric oxidization have been explored in an effort to develop a process to recycle waste water. Considering current efficiency and voltage, the free cyanide decomposition experiment by electric oxidization indicated that 5 V of voltage and copper catalytic Cu/CN mole ratio 0.05 was the most appropriate condition, where current efficiency was 26%, and decomposition speed was 5.6 mM/min. High voltage and excess copper addition increased decomposition speed a little bit but not current efficiency. The experiment of free cyanide density change proves that high density cyanide is preferred because speed and current efficiency increase with density. Also, the overall decomposition reaction could be represented by the first order with respcect to cyanide with the rate constant of $1.6∼7.3${\times}$10^{-3}$ $min^{-1}$ The mass transfer coefficient of electric oxidization of cyanide came out as $2.42${\times}$10^{-5}$ $min^{-1}$ Furthermore, the Damkohler number was calculated as 5.7 in case of 7 V and it was found that the mass transfer stage was the rate determining step.

Molecular Conductance Switching Processes through Single Ruthenium Complex Molecules in Self-Assembled Monolayers

  • Seo, So-Hyeon;Lee, Jeong-Hyeon;Bang, Gyeong-Suk;Lee, Hyo-Yeong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.27-27
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    • 2011
  • For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.

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Electrochemical Characteristics of Lithium Battery Anode Materials Using Petroleum Pitches (석유계 피치를 사용한 리튬전지 음극소재의 전기화학적 특성)

  • Hwang, Jin Woong;Lee, Jong Dae
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.534-538
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    • 2017
  • In this study, the molecular weight controlled pitches derived from pyrolyzed fuel oil (PFO) were prepared using solvent extraction and were carbonized. Electrochemical characteristics of lithium battery anode materials were investigated using these petroleum pitches. Three pitch samples prepared by the thermal reaction were 3903 (at $390^{\circ}C$ for 3 h), 4001 (at $400^{\circ}C$ for 1 h) and 4002 (at $400^{\circ}C$ for 2 h). The prepared hexane insoluble pitches were analysed by XRD, TGA, SEM and Gel permeation Chromatography (GPC). The electrochemical characteristics of the PFO-derived pitch as an anode material were investigated by constant current charge/discharge, cyclic voltammetry and electrochemical impedance tests. The coin cell using pitch (4001) and the electrolyte of $LiPF_6$ in organic solvents (EC : DMC = 1 : 1 vol%, VC 3 wt%) has better initial capacity (310 mAh/g) than that of other pitch coin cells. Also, this carbon anode showd a high initial efficiency of 82%, retention rate capability at 2 C/0.1 C of 90% and cycle retention of 85%. It was found that modified pitches improved the cycling and rate capacity performance.