• 제목/요약/키워드: Oxygen exchange reaction

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1,3-Oxathiolane-3-oxide로 부터 유도되는 술펜산 (Sulfenic Acid Derived from 1,3-Oxathiolane-3-oxide)

  • 이화석;박외숙
    • 대한화학회지
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    • 제31권2호
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    • pp.197-202
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    • 1987
  • cis 및 trans 2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) 및 (c)의 sigmatropic rearrangement에 의하여 생성되는 각각의 sulfenic acid (d) 및 (f)는 deuterium exchange reaction에 의하여 확인되었다. cis와 sulfoxide (b)와 (c)의 이성질화가 중성조건하에서는 일어나지 않으나, 산성촉매 존재하에서는 일어난다는 것이 발견되었다. 중성조건하에서 이성질화가 일어나지 않는 것은 sulfenic acid의 SOH 산소원자와 NH proton 사이의 수소결합이 관여하는 stereospecific recyclization에 기인하거나 기하학적 요구에 기인한다고 설명된다. 한편 cis sulfoxide (b)와 trans sulfoxide (c)의 혼합물을 주는 전구물질 1, 3-oxathiolane의 산화반응에서 benzene seleninic acid를 촉매로 하는 $H_2O_2$의 산화에 의하여 cis sulfoxide (b)가 높은 수율로 선택적으로 얻어졌다.

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수전해 반응에 의한 고분자전해질 연료전지 전극과 막의 열화 (Degradation of Electrode and Membrane in Proton Exchange Membrane Fuel Cell After Water Electrolysis)

  • 정재현;신은경;정재진;나일채;추천호;박권필
    • Korean Chemical Engineering Research
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    • 제52권6호
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    • pp.695-700
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    • 2014
  • 고분자전해질 연료전지로 물을 전기분해하여 수소와 산소를 발생시킬 수 있다. 그러나 1.7V 이상의 높은 전압에서 수전해 반응이 일어나므로 전극과 고분자 전해질 막의 열화가 빠르게 진행된다. 수전해 과정에서 anode의 열화를 방지하기 위해 촉매로 지지체 없는 $IrO_2$를 보통 사용하는데 본 연구에서는 고분자전해질 연료전지용 Pt/C 촉매를 수전해 반응에 그대로 사용했을 때 전극과 막의 열화 현상을 분석하였다. 1.8~2.0 V 전압 범위에서 수전해 반응 후 고분자 전해질 연료전지 구동 조건에서 I-V, CV, 임피던스, LSV를 측정했다. 수전해 전압이 높을수록 전극과 막의 열화 속도가 증가하였다. 2.0 V에서 1분 동안 수전해 반응했을 때 수소 수율은 88%였고, 전극과 고분자 막이 열화되어 0.6 V에서 성능이 49% 감소하였다.

항암제인 Cyclophosphamide의 중간체인 $^{15}N$$^{17}O$-phosphoramide Mustards의 합성 (The Study of Cyclophosphamide Metabolite $^{15}N$ and $^{17}O$ Phosphoramide Mustards)

  • 구교임;염곤
    • 약학회지
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    • 제38권4호
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    • pp.455-461
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    • 1994
  • Each nitrogen and oxygen site isotope enriched the cyclophosphamide metabolite phosphoramide mustard was synthesized. Reaction of N,N-bis(2-chloroethyl)phosphoramidic dichloride$[Cl_2P(O)N(CH_2CH_2Cl)_2]$ with benzyl alcohol and ammonia gave N,N-bis(2-chloroethyl)phosphorodiamidic acid phenylmethyl ester $[BzO(H_2N)P(O)N(CH_2CH_2Cl)_2]$. Catalytic hydrogenation of this benzyl ester followed by the addition of cyclohexylamine provided PM. Incorporation of $^{15}NH_3$ into this general scheme gave PM with a $^{15}NH_2$ moiety. Glycine-$^{15}N$ was converted to bis(2-chloroethyl)amine-$^{15}N$ hydrochloride which, in turn, provided for N,N-bis(2-chloroethyl)phosphorodiamidic-$^{15}N$ dichloride. Use of this compound in the general synthetic pathway yielded PM CHA with $^{15}N$ in the mustard moiety. $^{17}O$-Enriched PM was generated through the use of benzyl alcohol-$^{17}O$. To obtain the alcohol, labelled benzaldehyde was made by exchange with $^{17}OH_2$ and was then reduced with sodium borohydride.

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마이크로 추력장치용 과산화수소 촉매 반응기 (Catalytic Reactor of Hydrogen Peroxide for a Micro Thruster)

  • 이대훈;조정훈;권세진
    • 한국연소학회:학술대회논문집
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    • 한국연소학회 2002년도 제25회 KOSCI SYMPOSIUM 논문집
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    • pp.237-240
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    • 2002
  • Micro catalytic reactors are alternative propulsion device that can be used on a nano satellite. When used with a monopropellant, $H_2O_2$, a micro catalytic reactor needs only one supply system as the monopropellant reacts spontaneously on contact with catalyst and releases heat without external ignition, while separate supply lines for fuel and oxidizer are needed for a bipropellant rocket engine. Additionally, $H_2O_2$ is in liquid phase at room temperature, eliminating the burden of storage for gaseous fuel and carburetion of liquid fuel. In order to design a micro catalytic reactor, an appropriate catalyst material must be selected. Considering the safety concern in handling the monopropellants and reaction performance of catalyst, we selected hydrogen peroxide at volume concentration of 70% and perovskite redox catalyst of lantanium cobaltate doped with strondium. Perovskite catalysts are known to have superior reactivity in reduction-oxidation chemical processes. In particular, lantanium cobaltate has better performance in chemical reactions involving oxygen atom exchange than other perovskite materials. In the present study, a process to prepare perovskite type catalyst, $La_{0.8}Sr_{0.2}CoO_3$, and measurement of its propellant decomposition performance in a test reactor are described.

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연료전지 자동차 내 수소 공급 시스템에서 드레인 밸브 특성에 따른 드레인 로직 최적화 및 연비와 운전안정성을 고려한 물 관리 전략 개발 (Optimization of Condensate Water Drain Logic Depending on the Characteristics of Drain Valve in FPS of Fuel Cell Vehicle and Development of Anode Water Management Strategy to Achieve High Fuel Efficiency and Operational Stability)

  • 안득균;이현재;심효섭;김대종
    • 한국수소및신에너지학회논문집
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    • 제27권2호
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    • pp.155-162
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    • 2016
  • A proton exchange membrane fuel cell (PEMFC) produces only water at cathode by an electrochemical reaction between hydrogen and oxygen. The generated water is transported across the membrane from the cathode to the anode. The transported water collected in water-trap and drained to the cathode within the humidifier outlet. If the condensate water is not being drained at the appropriate time, condensate water in the anode can cause the performance degradation or fuel efficiency degradation of fuel cell by the anode flooding or unnecessary hydrogen discharge. In this study, we proposed an optimization method of condensate water drain logic for the water drain performance and the water drain algorithm as considered the condensate water generating speed prep emergency case. In conclusion, we developed the water management strategy of fuel processing system (FPS) as securing fuel efficiency and operating stability.

Ce $L_Ⅲ$-edge X-ray Absorption Spectroscopic Studies on the Tetrameric Ce-polyoxyhydroxy Cation Intercalated Aluminosilicate

  • 윤주병;황성호;김동국;강성구;최진호
    • Bulletin of the Korean Chemical Society
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    • 제21권3호
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    • pp.305-309
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    • 2000
  • The cerium ion intercalated aluminosilicate was prepared by ion exchange reaction between $Na^+$ in montmorillonite and $Ce^{+4}$ in aqueous solution. The X-ray absorption near edge structrure(XANES) analyses indicate that the $Ce^{+4}$ ions are partially reduced to the $Ce^{+3}$ ones during the intercalation into layered aluminosilicate due to a charge transfer between host and intercalant. From the EXAFS analysis, two different (Ce-O) bonding pairs could be characterized with the distances and coordination numbers of 2.31 $({\pm}0.02){\AA}$ ${\times}$ 8.2 $({\pm}1.5)$ and 2.66 $({\pm}0.02){\AA}$ ${\times}$ 2.7 $({\pm}1.0)$, respectively, with the oxygen atoms as the first nearest neighbor, and two (Ce-Ce) pairs at 3.78 ${\AA}$ as the second neighbor. It is therefore concluded that the most probable Ce-species stabilized in the interlayer space of aluminosilicate after the intercalation is the tetrameric Ce-polyoxy/hydorxy cations with the mixed valent state of 0.75 $Ce^{+4}$.0.25 $Ce^{+3}$.

전자밀도함수이론을 이용한 세륨 산화물의 (111) 표면에서 일어나는 물 흡착 과정 분석 (Theoretical Investigation of Water Adsorption Chemistry of CeO2(111) Surfaces by Density Functional Theory)

  • 최혁;강은지;김현유
    • 한국재료학회지
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    • 제30권5호
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    • pp.267-271
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    • 2020
  • Cerium oxide (ceria, CeO2) is one of the most wide-spread oxide supporting materials for the precious metal nanoparticle class of heterogeneous catalysts. Because ceria can store and release oxygen ions, it is an essential catalytic component for various oxidation reactions such as CO oxidation (2CO + O2 2CO2). Moreover, reduced ceria is known to be reactive for water activation, which is a critical step for activation of water-gas shift reaction (CO + H2O → H2 + CO2). Here, we apply van der Waals-corrected density functional theory (DFT) calculations combined with U correction to study the mechanism of water chemisorption on CeO2(111) surfaces. A stoichiometric CeO2(111) and a defected CeO2(111) surface showed different water adsorption chemistry, suggesting that defected CeO2 surfaces with oxygen vacancies are responsible for water binding and activation. An appropriate level of water-ceria chemisorption energy is deduced by vdW-corrected non-local correlation coupled with the optB86b exchange functional, whereas the conventional PBE functional describes weaker water-ceria interactions, which are insufficient to stabilize (chemisorb) water on the ceria surfaces.

금속을 이온교환시킨 ZSM-5 촉매 상에서 Nitric Oxide의 환원반응 (Selective Catalytic Reduction of Nitric Oxide over Metal Exchanged ZSM-5 Catalysts)

  • 안성환;김태옥;함현식
    • 한국응용과학기술학회지
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    • 제17권1호
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    • pp.1-5
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    • 2000
  • The selective catalytic reduction(SCR) of nitric oxide by ethane in the presence of oxygen was investigated on Cu-ZSM-5, Co-ZSM-5 and Ga-ZSM-5 catalysts over a range of 400, 450 and $500^{\circ}C$. The catalysts were prepared by ion-exchange method. The composition of the reactant gases were 1000 ppm of NO, 1000 ppm of $C_{2}H_{6}$ and 2.5% of $O_{2}$, and the reaction was conducted in a fixed-bed reactor at 1 atm. For the 20wt% Co-ZSM-5(50) catalyst, the NO conversion reached up to 100%, while the $C_2H_6$ conversion and the CO selectivity were about 50% and 25%, respectively, at $450^{\circ}C$. For the 20wt% Cu-ZSM-5(50) catalyst, the NO conversion and the C2H6 conversion were about 80% and 100%, respectively, but there was no CO produced. The metal ion-exchanged ZSM-5 catalysts exhibited a tendency to increase the NO conversion with the Si/Al ratio of the ZSM-5, that is, NO conversion was inversely proportional to the acidity of the catalysts. But, the effect of the acidity on NO conversion was not so large. From the XRD results of the catalysts before and after SCR reaction it was found that there was no structural change.

구리 제올라이트와 철 제올라이트 촉매에 의한 질소산화물의 암모니아 선택적 촉매환원반응 특성 (Selective Catalytic Reduction of NOx with Ammonia over Cu and Fe Promoted Zeolite Catalysts)

  • 하호정;홍주환;최준환;한종대
    • 청정기술
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    • 제19권3호
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    • pp.287-294
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    • 2013
  • 구리-제올라이트 촉매와 Fe-제올라이트 촉매로 과잉산소 분위기에서 일산화질소의 암모니아 선택적 촉매환원반응을 체계적으로 조사하였다. 촉매는 디젤엔진에서의 SCR기술의 적용을 위하여 구리와 철을 $NH_4$-BEA와 $NH_4$-ZSM-5 제올라이트에 이온교환법과 함침법으로 담지시켜 제조하였다. 촉매의 특성은 BET, XRD, FE-TEM과 SEM/EDS를 사용하여 조사하였다. 고정된 반응조건에서 선택적 촉매환원반응의 활성을 조사한 결과에서 구리를 BEA 제올라이트에 이온교환시켜 제조한 촉매가 $200{\sim}250^{\circ}C$의 저온영역에서 탁월한 성능을 나타내었다. $250^{\circ}C$ 이하의 저온에서 구리-제올라이트 촉매가 Fe-제올라이트 촉매보다 높은 반응활성을 나타내었다. BEA 제올라이트에 담지된 촉매가 ZSM-5 제올라이트에 담지된 촉매보다 $250^{\circ}C$ 이하의 저온에서 우수한 반응활성을 나타내었다.

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

  • 양종원;현규환;추천호;권용재
    • 공업화학
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    • 제25권1호
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    • pp.78-83
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    • 2014
  • 본 연구에서는 수정된 폴리올법에 의해 합성된 백금-이트륨 및 백금-니켈 합금 촉매들의 성능 및 특성 평가를 진행하였다. 그렇게 합성된 합금 촉매들은 고분자전해질연료전지의 공기극 촉매로 사용되며 그 촉매들의 산소환원반응성 및 연료전지의 전기적 성능이 측정되고 상업적으로 사용되는 백금 촉매와 해당하는 결과들이 비교되었다. 성능 및 특성 비교를 위해, 백금 합금 촉매들의 입자크기와 분포는 투과전자현미경에 의해 관측되었고 활성표면적은 반복주사 전압-전류법에 의해 측정되었으며 그들의 산소환원반응성 및 연료전지의 전기적 성능은 회전원판 및 회전-고리 원판전극을 이용한 선형주사 전압-전류법 및 완전지 테스트를 통해 평가되었다. 그 결과 백금 합금 촉매들의 구조적 특성인 입자크기 및 분포 및 활성표면적은 상용 백금 촉매와 그 특성이 비슷하였다. 촉매들의 산소환원반응성의 경우에도 백금 합금 촉매들은 상용 백금 촉매와 비슷하거나 더 나은 반파장전위, 속도론적 전류밀도, 산소분자당 전이되는 전자수, 과산화수소 생성율을 나타내었다. 촉매의 구조적 특성 및 산소환원반응성에 입각해서 완전지 성능을 평가했을 때, 백금 합금 촉매들은 상용백금 촉매보다 더 우수한 0.6 V에서 전류밀도 및 최대출력밀도 값을 나타내었다. 이를 토대로 수정된 폴리올법에 의해 합성된 백금 합금 촉매들은 상용백금 촉매보다 비슷하거나 우수한 산소환원반응성 및 완전지 성능을 가질 수 있음을 제시하였다.