• Title/Summary/Keyword: $H_2O_2$ 촉매 분해

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On-stream Activity and Surface Chemical Structure of CoO2/TiO2 Catalysts for Continuous Wet TCE Oxidation (습식 TCE 분해반응에서 CoO2/TiO2 촉매의 반응활성 및 표면화학적 구조)

  • Kim Moon Hyeon;Choo Kwang-Ho
    • Journal of Environmental Science International
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    • v.14 no.2
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    • pp.221-230
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    • 2005
  • Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

Millimeter-Scale Aligned Carbon Nanotubes Synthesized by Oxygen-Assisted Microwave Plasma CVD (MPCVD를 이용하여 밀리미터 길이로 수직 정렬된 탄소나노튜브의 합성)

  • Kim, Y.S.;Song, W.S.;Lee, S.Y.;Choi, W.C.;Park, C.Y.
    • Journal of the Korean Vacuum Society
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    • v.18 no.3
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    • pp.229-235
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    • 2009
  • Millimeter-scale aligned arrays of thin-multiwalled carbon nanotube (t-MWCNT) on layered Si substrates have been synthesized by oxygen-assisted microwave plasma chemical vapor deposition (MPCVD). We have succeeded in growth of vertically aligned MWCNTs up to 2.7 mm in height for 150 min. The effect of $O_2$ and water vapour on growth rate was systematically investigated. In the case of $O_2$ gas, the growth rate was ${\sim}22{\mu}m/min$, which is outstanding growth rate comparing with those of conventional thermal CVD (TCVD). Scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and Raman spectroscopy were used to analyze the CNT morphology, composition and growth mechanism. The role of $O_2$ gas during the CNT growth was discussed on.

Crystallization of the Titania Coated on Kaolinite Powder using Sol-Gel Method (졸-겔법에 의해 카올리나이트 분말에 코팅된 티타니아의 결정화)

  • Yang, Young-Cheol;Jeong, Soo-Bok;Kim, Byoung-Gyu
    • Journal of the Mineralogical Society of Korea
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    • v.21 no.3
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    • pp.247-259
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    • 2008
  • $TiO_2$ coatings on kaolinite powders by sol-gel method were carried out using mixture of titanium isopropoxide, ethanol as solvent, HCl as a catalyst and $H_{2}O$ for hydrolysis. The mole ratio of reaction mixture, stirring time. aging time, crystallization time and crystallization temperature influenced to the crystallization of $TiO_2$ coated on kaolinite and metakaolinite Powders. Optimum condition for $TiO_2$ coatings on kaolinite was as follows; TIP 0.1 mol, $H_{2}O$ 0.15 mol, HCl 0.005 mol, ethanol 100 ml, raw kaolinite 50 g, stirring time 4 hrs, aging time 24 hrs, crystallization time 2 hrs and crystallization temperature $1050^{\circ}C$. The crystallinity of the anatase under optimum condition was about 17.61%. The anatase crystallinity of the $TiO_2$ coated on raw kaolinitc powders (17.61% at $1050^{\circ}C$) was higher at the lower calcination temperature compared with metakaolinite (17.39% at $1200^{\circ}C$).

A Study on the Hydrolysis of Sarin and Soman by Merrifield-Type Diaminatedpolystyrene-Cu (II) Heterogeneous Polymers (Merrifield-Type Diaminatedpolystyrene-Cu (II) 불균일 촉매에 의한 Sarin과 Soman 분해반응 연구)

  • 정우영;계영식
    • Journal of the Korea Institute of Military Science and Technology
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    • v.3 no.1
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    • pp.164-175
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    • 2000
  • Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

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Endogenous Phenoloxidase Purified from an Earthworm, Lumbricus rubellus (붉은 지렁이(Lumbricus rubellus) 체내로부터 정제한 Phenoloxidase)

  • 백승렬;조은정;유경희;김유삼;서정진;장정순
    • The Korean Journal of Zoology
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    • v.39 no.1
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    • pp.36-46
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    • 1996
  • An endogenous phenoloxidase (EPO) from earthworm, Lumbricus rubellus, has been purified and characterized. The purified EPO using ammonium sulfate fractionation, Blue-2, Phenyl-, and Q-sepharose chromatography steps was revealed in SDS-PAGE as a single protein banri with Mr. of 59 kl)a. A native strudure of the enzyme was examined with an in situ staining of a nondenatudng-PAGE using DL-dopa as a substrate. The result showed that a single band due to the EPO activity was located siighdy above a standard polypeptide with Mr. of 210 kl)a. These fads indicate that the EPO is an oligomeric enzyme. The presence of a monophenolase activity of the purified EPO, which hydroxylates tyrosine to dopa, was confirmed by observing dopachrome accumulation at 475 nm at PH 8.0 with a typical lag phase during 60 mm. of meausrement. A series of inhibition study has been performed for the enzyme with several divalent cation chelators such as phenyithiourea (Flu), 1, lO-phenanthroline, EDTA, and EGTA. Among them, only V'flj inhibited the enzyme with 1C0.5 of 65 MM, which indicated that copper was critical for the catalysis of EPO. The enzyme was maximally active at 35'C and pH 8.0 when L-dopa to dopachrome conversion was spectrophotometricaily monitored at 475 nm. The apparent Km values of P0 for L-opa were obtained as 1.86 mM and 13.8 mM at pH 6.5 and 8.0, respectively. The catalytic efficiencies at both pH were almost identical [(kat/Km)pH8.0/(kcat/Km)pH6.5 = O.92] while the Vmax at p11 8.0 was 6.6-fold higher than that at pH 6.5. This fact may indicate that pH affeds the catalysis at substrate and/or enzyme-substrate complex level rather than the enzyme itself. Taken together, the EPO was an oligomeric enzyme which did not require proteolysis for its activation. These results also indicated that the enzyme can exist, at least, in part as a latent form In vivo, which might be distinct from the prophenoloxidase activating system. Therefore, it is pertinent to consider that there must be certain regulatory molecules or phenomena in L. rubellus which make the 1,0 in a latent form in vivo before the foreign invasions.

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A Study on Oxygen Reduction Reaction of PtM Electrocatalysts Synthesized by a Modified Polyol Process (수정된 폴리올 방법을 적용하여 합성한 PtM 촉매들의 산소환원반응성 연구)

  • Yang, Jongwon;Hyun, Kyuwhan;Chu, Cheunho;Kwon, Yongchai
    • Applied Chemistry for Engineering
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    • v.25 no.1
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    • pp.78-83
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    • 2014
  • In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.

Effect of Continuous Cultivation Years on Soil Properties, Weed Occurrence, and Rice Yield in No-tillage Machine Transplanting and Direct Dry-seeding Culture of Rice (벼 무경운 기계이앙 및 건답직파 연속재배년수가 토양특성, 잡초발생 및 벼 생육에 미치는 영향)

  • Park, Hong-Kyu;Kim, Sang-Su;Choi, Won-Yong;Lee, Ki-Sang;Lee, Jae-Kil
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.47 no.3
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    • pp.167-173
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    • 2002
  • This experiment was conducted to figure out the change of soil physical properties, rice growth and yield with the years of continuous cultivation in direct dry-seeding and no-tillage machine transplanting. Experiments were conducted at NHAES(National Honam Agricultural Experiment Station, RDA, Iksan, Cheon Buk Province, South Korea) with a rice variety "Dongjinbyeo" from 1995 to 2000. In no-tillage machine transplanting cultivation, organic matter in soil was higher than that on direct dry-seeding and was significantly high in topsoil. Problematic weed species were E. crus-galli B., A. keisak H., and L. japonica M. Plant height and tiller number m-2 were higher in common-tillage during the total growth duration. The highest weedy rice occurrence of 27.5% was observed in live years' continuous direct dry-seeding and followed by 6.2%, in four years', and 3.7%, in three years'. The highest yield reduction of 38% was observed in five years' continuous direct dry-seeding. The reduction may resulted from the competition between weedy rice and cultivated rice.

Syntheses and Properties of Copolymers of Tetramethyldisiloxane and 1,4-Bis(dimethylhydroxysilyl)benzene (Tetramethyldisiloxane-1,4-bis(dimethylhydroxysilyl)benzene 공중합체의 합성 및 특성)

  • Kim, Sun-ll;Yun, Young-Jae;Na, Jae-Woon
    • Applied Chemistry for Engineering
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    • v.7 no.3
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    • pp.490-495
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    • 1996
  • Low molecular weight linear chlorine terminated siloxanes (yields;71.2~86.5%) were prepared by reactions of cyclotri-, cyclotetra- and cyclopentasiloxane with dimethyldichlorosilane in the presence of pyridine N-oxide catalyst. The amine terminated siloxane oligomers were obtained in good yields(76.2~85.3%) by the reaction of linear chlorine terminated siloxanes with dimethylamine at $0^{\circ}C$. In this investigation, we have studied on the syntheses and properties of copolymers (yields;58.0~71.0%) obtained from the reaction of amine terminated siloxane oligomers with 1,4-bis(dimethylhydroxysilyl)benzene. The structures and properties of the copolymers were examined by FT-IR, $^1H$-NMR, TGA and DSC. Initial degradation temperatures($T_D{^i}$) of the polymer I and IV were confirmed as 476 and $485^{\circ}C$, respectively. The thermal stabilities of the polymers were found to be increased with increasing n of $(R_2SiO)_n$. The glass transition temperatures(Tg) of the polymers were increased with decreasing n of $(R_2SiO)_n$, and the lowest Tg revealed $-76^{\circ}C$ when n=5.

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Research on the Gas Diffusion Electrode for the Brine Electrolysis (염수 전해용 가스확산 전극에 관한 연구)

  • Lee, D.H.;Lee, G.H.;Han, J.W.;Lim, J.T.;Lee, O.S.;Lee, J.D.
    • Journal of the Korean Electrochemical Society
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    • v.5 no.1
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    • pp.7-12
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    • 2002
  • The gas diffusion electrodes as oxygen cathodes f3r the brine electrolysis process were investigated. The gas diffusion electrode consists of a reaction layer, a gas diffusion layer, and a current distributor. The reaction layer was made from hydrophilic carbon black, hydrophobic carbon black, PTFE(polyterafluoroethylene), and Ag catalyst loaded by the silver mirror reaction or impregnation method. The gas diffusion layer was made from hydrophobic carbon black and PTFE, and Ni mesh was used as the current distributor in the reaction layer. The result that the gas diffusion electrode $(10wt\%\;Ag\;catalyst\;and\;20wt\%\;binder)$ manufactured by applying impregnation method to the carbon black f3r reaction layer showed the better performance was obtained from experiments. From the half-cell test, the measured overpotential of this oxygen cathode was about 700mV, And through the electrolysis experiment under the condition of $80^{\circ}C,\;32wt\%$ NaOH, and $300mA/cm^2$, the electrolysis voltage of this electrode was about 2.2 V, The gas diffusion electrodes manufactured in the present research were capable of continuous operations for three months.

Enzymatic Synthesis of Meth.yl Fructoside by Immobilized Invertase (고정화 전화당 효소에 의한 메틸 프룩토시드의 합성)

  • 허주형;김해성
    • KSBB Journal
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    • v.8 no.4
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    • pp.313-319
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    • 1993
  • Methyl fructoside was synthesized from sucrose and methanol using an immobilized invertase. The enzyme was covalently bound by glutaraldehyde on porous silica coated with polyethyleneimine to give loading capacity of 120mg of invertase per one gram of dry porous silica and effective activity of 100U per one milligram of bound invertase. Polyethyleneimine coating imparted a hydrophillic character, good activity retention and high loading capacity to the surface of porous silica as well as hydrophillic microenviroment in the vicinity of bound invertase. The immobilized enzyme was formed into an alginate-enclosed silica bead to have enough activity for methyl fructoside synthesis from aqueous methanol-sucrose solution. Using the alginate-enclosed biocatalyst the yield of methyl fructoside was obtained as high as 55.9% from aqueous 30% (v/v) methanol and 0.291mo1/l sucrose with 2U/ml activity at $25^{\circ}C$, pH 4.8.

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