• Title/Summary/Keyword: oCoA

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Oxidation Reaction of Hydrazobenzene by Activated Catalysts of Oxygen Adducted Tetradentate Schiff Base Cobalt(Ⅱ) Complexes in Methanol Solvent. (Ⅱ) (메탄올 용매에서 산소 첨가된 네자리 Schiff Base Cobalt(II) 착물들의 활성촉매에 의한 Hydrazobenzene의 산화반응 (제 2 보))

  • Ki-Kyung Chjo;Yong-Kook Choi;Sang-Bock Kim;Jong-Ki Park;Dong-Hwa Park
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.894-905
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    • 1992
  • Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$ $10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

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Solvent Effects on the Isotropic NMR Shifts in Quinuclidine and Pyridine-Type Ligands Coordinated to the Paramagnetic Polyomometalate, $[SiW_{11}Co^{II}o_{39}]^{6-}$

  • Hyun, Jaewon;Park, Suk-Min;So, Hyunsoo
    • Bulletin of the Korean Chemical Society
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    • v.18 no.10
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    • pp.1090-1093
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    • 1997
  • The solvent effects on the isotropic NMR shifts in conformationally rigid ligands such as quinuclidine, pyridine, and 4-aminopyridine coordinated to the paramagnetic polyoxometalate, [SiW11CoⅡO39]6- (SiW11Co), are reported. For these complexes the ligand exchange is slow on the NMR time scale and pure 1H NMR signals have been observed at room temperature. The signals for the SiW11Co complexes are shifted upfield whe dimethyl sulfoxide-d6 (DMSO) is added to a D2O solution. The isotropic shifts are separated into contact and pseudocontact contributions by assuming that the contact shifts are proportional to the isotropic shifts of the same ligands coordinated to [SiW11NiⅡO39]6-. It is shown that both the contact and pseudocontact shifts decrease (the absolute values of the pseudocontact shifts increase), when D2O is replaced by DMSO. It is suggested that D2O, a strong hydrogen bond donor, withdraws electron density from [SiW11CoⅡO39]6-, increasing the acidity of the cobalt ion toward the axial ligand. When D2O is replaced by DMSO, the acidity of the cobalt ion in SiW11Co decreases, weakening the Co-N bond. Then both the contact and pseudocontact shifts are expected to decrease in agreement with the observed solvent effects.

Changes of Quality Characteristics on the Cherry Tomatoes during the CA(Controlled Atmosphere) Storage (CA저장 중 방울토마토의 품질특성 변화)

  • 이현동;윤홍선;최종욱
    • Food Science and Preservation
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    • v.8 no.3
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    • pp.239-245
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    • 2001
  • The CA(Controlled Atmosphere) storage of cherry tomatoes were carried out under seven gas compositions including air. The weight loss of cherry tomatoes progressively increased with storage time. In the case of cherry tomatoes stored under CA conditions, increment of weight loss was reduced. However, cherry tomatoes (in air) tut about 15% weight at the end of storage. In CA stored cherry tomatoes lost about 10% weight at the same time. General trend was a decrease in titratable acidity with storage time. In air md 6.4% O$_2$, 4.2% CO$_2$, titratable acidity was lower than that in other storage conditions. During storage of cherry tomatoes, soluble solids increased till 8 days of storage, and then decreased. Stored cherry tomatoes in air and 6.4% O$_2$+4.2% CO$_2$ have lower values. Lycopene contents of cherry tomatoes with 6% O$_2$ storage condition increased and cherry tomatoes with 1% O$_2$+6% CO$_2$ and 3% O$_2$+3.1% CO$_2$maintained s initial contents. In air, flesh firmness decrease till 8 days, and then increase. At 1% O$_2$+6% CO$_2$ ethanol contents were ten times to that of other experimental conditions. Air and 6% O$_2$+7.8% CO$_2$ condition had lowest value for the ethanol content. In changes of organic acid and citric acid decreased slowly during storage, malic acid in air and below 3% O$_2$was disappeared at 8 days. Above 4% O$_2$concentration malic acid contents were maintained till 16 days. In over all acceptability, air and 6.4% O$_2$+7.8% CO$_2$ condition took a good score from the panel. Quality of stored cherry tomatoes was not edible condition in 1% O$_2$+6% CO$_2$. CA storage cherry tomatoes took a good score in firmness and juiciness where as control received good score in color and sweetness. This result was explained that in air ad 6.4% O$_2$+7.8% CO$_2$stored cherry tomato was ripened and full color development, but in CA was break stage because of suppressed ripening.

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Synthesis and Characterization of a Ternary Nanocomposite Based on CdSe Decorated Graphene-TiO2 and its Application in the Quantitative Analysis of Alcohol with Reduction of CO2

  • Ali, Asghar;Biswas, Md Rokon Dowla;Areerob, Yonrapach;Nguyen, Dinh Cung Tien;Oh, Won-Chun
    • Journal of the Korean Ceramic Society
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    • v.55 no.4
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    • pp.381-391
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    • 2018
  • In this work, photocatalytic $CO_2$ reduction over a CdSe-graphene-$TiO_2$ nanocomposite has been studied. The obtained material was successfully fabricated via ultrasonic technique. The physical properties of the as-synthesized materials were characterized by some physical techniques. The $TiO_2$ and CdSe dispersed graphene nanocomposite showed excellent results of strong reduction rates of $CO_2$ compared to the results of bare $TiO_2$ and binary CdSe-graphene. An outstanding point of the combination of CdSe-$TiO_2$ and graphene appeared in the form of great photocatalytic reduction capability of $CO_2$. The photocatalytic activity of the asfabricated composite was tested by surveying for the photoreduction of $CO_2$ to alcohol under UV and visible light irradiation, and the obtained results imply that the as-prepared CdSe-graphene-$TiO_2$ nanocomposite is promising to become a potential candidate for the photocatalytic $CO_2$ reduction.

Synthesis of Silicon Carbide Whiskers (I) : Reaction Mechanism and Rate-Controlling Reaction (탄화규소 휘스커의 합성(I) : 반응기구의 율속반응)

  • 최헌진;이준근
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1329-1336
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    • 1998
  • A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.

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DC Accelerated Aging Characteristics of $Pr_{6}O_{11}$-Based ZnO Varistors with CoO Content (CoO 첨가량에 따른 $Pr_{6}O_{11}$계 ZnO 바리스터의 DC 가속열화특성)

  • Kim, Hyang-Suk;Jung, Young-Chul;Nahm, Choon-Woo
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.11b
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    • pp.467-471
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    • 2001
  • DC accelerated aging characteristics of $Pr_{6}O_{11}$-based ZnO varistors, which are composed of $ZnO+Pr_{6}O_{11}+CoO+Cr_{2}O_{3}+Dy_{2}O_{3}$ ceramics were investigated with CoO content in the range of 0.5 - 5.0 mol%. The varistors doped with 1.0 mol% revealing maximum value(66.61) in the nonlinear exponent exhibited excellent stability, in which the variation rates of the varistor voltage, the nonlinear exponent and leakage current are -1.93%, -10.48%, and +288.79%, respectively, under DC accelerated aging stress, such as $(0.85V_{lmA}/115^{\circ}C/24h)+(0.90V_{lmA}120^{\circ}C/24h)+(0.95V_{lmA}/125^{\circ}C/24h)+(0.95V_{lmA}/150^{\circ}C/24h)$. Next the varistors doped with 2.0 mol% exhibiting the nonlinear exponent of 47.39 showed high stability.

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DC Accelerated Aging Characteristics of $Pr_{8}O_{11}$-Based ZnO Varistors with CoO Content (CoO 첨가량에 따른 $Pr_{8}O_{11}$계 ZnO 바리스터의 DC 가속열화특성)

  • 김향숙;정영철;남춘우
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.11a
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    • pp.467-471
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    • 2001
  • DC accelerated aging characteristics of Pr$_{6}$O$_{11}$-based ZnO varistors, which are composed of ZnO+Pr$_{6}$O$_{11}$+CoO+Cr$_2$O$_3$+Dy$_2$O$_3$ ceramics were investigated with CoO content in the range of 0.5~5.0 mol%. The varistors doped with 1.0 mol% revealing maximum value(66.61) in the nonlinear exponent exhibited excellent stability, in which the variation rates of the varistor voltage, the nonlinear exponent and leakage current are -1.93%, -10.48%, and 288.79%, respectively, under DC accelerated aging stress, such as (0.85 V$_{1mA}$/115$^{\circ}C$/24h)+(0.90 V$_{1mA}$/12$0^{\circ}C$/24h)+(0.95 V$_{1mA}$/1$25^{\circ}C$/24h)+(0.95 V$_{1mA}$/15$0^{\circ}C$/24h). Next the varistors doped with 2.0 mol% exhibiting the nonlinear exponent of 47.39 showed high stability,ity,ability,ity,

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Method for Improvement of Reduction Reactivity at High Temperature in a Chemical-Looping Combustor (매체순환식 가스연소기에서 고온 환원반응성 증대 방법)

  • Ryu, Ho-Jung;Park, Sang-Soo;Lee, Dong-Ho;Choi, Won-Kil;Rhee, Young-Woo
    • Korean Chemical Engineering Research
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    • v.50 no.5
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    • pp.843-849
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    • 2012
  • When we use NiO based particle as an oxygen carrier in a chemical looping combustion system, the fuel conversion and the $CO_2$ selectivity decreased with increasing reaction temperature within high temperature range (> $900^{\circ}C$) due to the increment of exhaust CO concentration from reduction reactor. To improve reduction reactivity at high temperature, the applicable metal oxide component was selected by calculation of the equilibrium CO concentration of metal oxide components. After that, feasibility of reduction reactivity improvement at high temperature was checked by using solid mixture of the selected metal oxide particle and NiO based oxygen carrier. The reactivity was measured and investigated using batch type fluidized bed. The solid mixture of $Co_3O_4/CoAl_2O_4$(10%) and OCN706-1100(90%) showed higher fuel conversion, higher $CO_2$ selectivity and lower CO concentration than OCN706-1100(100%) cases. Consequently, we could conclude that improvement of reduction reactivity at high temperature range by adding some $Co_3O_4$ based oxygen carrier was feasible.

CO Oxidation Over Manganese Oxide Catalysts: Effect of Calcination Temperature (망간 산화물 촉매상에서 일산화탄소의 산화반응 : 소성온도의 영향)

  • Park, Jung-Hyun;Kim, Yun-Jung;Cho, Kyung-Ho;Kim, Eui-Sik;Shin, Chae-Ho
    • Clean Technology
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    • v.17 no.1
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    • pp.41-47
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    • 2011
  • [ $MnO_2$ ]catalysts were prepared by precipitation method using potassium manganate and manganese acetate. The effect of calcination temperatures of $MnO_2$ catalysts for CO oxidation has been studied and their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$ sorption, temperature programmed reduction of $H_2$ ($H_2-TPR$), and temperature programmed desorption of CO (CO-TPD) techniques. $MnO_2$ calcined at $300^{\circ}C$ catalyst has a large surface area $181m^2/g$ having a narrow pore size distribution at 9 nm. The results of XRD and $H_2-TPR$ showed that the catalysts calcined at different temperatures showed mixed oxidation states of Mn such as $Mn^{4+}$ and $Mn^{3+}$. CO-TPD showed that the quantity of $CO_2$ desorbed was decreased with increasing the calcination temperatures. The catalytic activity over the catalyst calcined at $300^{\circ}C$ exhibited the highest conversion reaching to 100% at $200^{\circ}C$. $H_2O$ vapor showed an inhibiting effect on the efficiency of the catalyst because of co-adsorption with CO on the active sites of manganese oxide catalysts and the initial catalytic activity of CO oxidation could be regenerated by removing $H_2O$ vapor in the reactants.

Syntheses of LiMn1.92Co0.08O4 and LiNi1-yCoyO2 and Electrochemical Properties of their Mixtures for Lithium Secondary Battery (리튬 이차전지용 LiMn1.92Co0.08O4, LiNi1-yCoyO2 의 합성과 그들의 혼합물의 전기화학적 특성)

  • Kwon, IkHyun;Kim, HunUk;Song, MyoungYoup
    • Journal of Hydrogen and New Energy
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    • v.15 no.1
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    • pp.62-71
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    • 2004
  • $LiMn_{1.92}Co_{0.08}O_4-x\;wt.%LiNi_{0.7}Co_{0.3}O_2$를 단순화한 연소법에 의하여 합성하고, 그것들의 전기화학적 특성을 조사하였다. 또한 30분동안 밀링하여 준비한 $LiMn_{1.92}Co_{0.08}O_4-x\;wt.%LiNi_{0.7}Co_{0.3}O_2$ (x=9, 23, 33, 41 and 47) 혼합물 전극의 전기화학적 특성을 조사하였다. x=33 조성의 전극이 가장 큰 초기방전용량(132.0mAh/g at 0.1C)을 나타내었다. x=9조성의 전극은 비교적 큰 초기방전용량(109.9mAh/g at 0.1C)과 우수한 싸이클 특성을 나타내었다. 싸이클링에 따른 혼합물 전극의 방전용량의 감소는 주로 $LiNi_{0.7}Co_{0.3}O_2$의 퇴화에 기인한다고 생각된다. 그런데 $LiNi_{0.7}Co_{0.3}O_2$의 퇴화는 $LiMn_{1.92}Co_{0.08}O_4$로부터 용해된 Mn이 $LiNi_{0.7}Co_{0.3}O_2$를 둘러쌈(coating)으로써 야기되는 것으로 생각된다.