• 제목/요약/키워드: selective oxidation

검색결과 256건 처리시간 0.022초

N3S-ligated Copper(II) Complex Catalyzed Selective Oxidation of Benzylic Alcohols to Aldehydes under Mild Reaction Conditions

  • Dharmalingam, Sivanesan;Koo, Eunhae;Yoon, Sungho;Park, Gyoosoon
    • Bulletin of the Korean Chemical Society
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    • 제35권3호
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    • pp.715-720
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    • 2014
  • A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively oxidizes the benzylic alcohols using TEMPO/$O_2$ under mild reaction conditions to corresponding aldehydes without forming any over-oxidation product. Moreover, the catalyst can be recovered and reused multiple times for further oxidation reactions, thus minimizing the waste generation.

오존/촉매 산화공정에서 비스페놀 A의 분해와 생성된 과산화수소의 농도 비교 (A Comparison between the Decomposition of Bisphenol A and the Concentration of Hydrogen Peroxide Formed during Ozone/Catalyst Oxidation Process)

  • 최재원;이학성
    • 공업화학
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    • 제28권6호
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    • pp.619-625
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    • 2017
  • 본 연구에서는 하이드로퍼옥시 라디칼 생성단계에서 반응 부산물로 생성되는 과산화수소를 정량하여 수산화라디칼의 생성 및 비스페놀 A (BPA)의 분해특성을 조사하였다. 라디칼 연쇄반응이 일어나지 않는 조건에서는 Criegee mechanism과 동일하게 오존에 의한 직접산화반응만이 BPA를 분해시키는 것으로 나타났다. 라디칼 연쇄반응이 일어나는 pH 6.5 및 9.5의 조건에서는 비선택적 산화반응이 일어나 수산화라디칼의 생성을 간접적으로 확인할 수 있었다. 투입된 촉매에 의한 BPA의 분해효율은 $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone 공정 순으로 나타났다. 오존/촉매공정들의 산화반응 동안에는 0.03~0.08 mM의 과산화수소가 지속적으로 측정되었다. $O_3$/high pH 공정의 경우, BPA가 반응시작 50 min 만에 완전히 분해되었지만, TOC (총유기탄소) 제거율은 29%로 산화반응 중 생성된 중간물질을 충분히 산화시키지 못하는 것으로 나타났다(선택적 산화반응). $O_3/H_2O_2$$O_3$/PAC 공정에서는 BPA가 반응시작 40 min 만에 완전히 분해되었으며, TOC 제거율은 각각 57% 및 66% 정도로 반응 중간체들을 산화(비선택적 산화반응)시키는 것으로 나타났다.

흑색 코발트 태양 선택흡수막의 광학적특성과 구조 (Optical Properties and Structure of Black Cobalt Solar Selective Coatings)

  • 이길동
    • 한국태양에너지학회 논문집
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    • 제31권4호
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    • pp.48-56
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    • 2011
  • Black cobalt solar selective coatings were prepared by thermal oxidation of electroplated cobalt metal on copper and nickel substrates. The optical properties and structure of the black cobalt selective coating for solar energy utilizations were characterized by glow discharge spectrometry (GDS), ultraviolet-visible-near infrared (UV-VIS-NIR) spectrometer, atom force microscopy(AFM) and X-ray photoelectron spectroscopy(XPS). The optical properties of optimum black cobalt selective coating prepared on copper substrate were a solar absorptance of 0.82 and a thermal emittance of 0.01. From the GDS depth profile analysis of these coatings, the concentration of cobalt particles near the interface was higher than at the surface, but oxygen concentration at the surface was higher than at the interface. These results suggest that the selective absorption was dominated by this chemical composition variation in the coating. The surface of this film exhibited morphology with root-mean-square(rms) roughness of about 144.3nm. XPS measurements data showed that several phases of Co coexist($Co_3O_4$,CoO) in the film.

An Environmentally Benign Synthesis of 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane Tribromide and Its Application as an Efficient and Selective Reagent for Oxidation of Sulfides to Sulfoxides in Solution and Solvent-free Conditions

  • Pourmousavi, S.A.;Salehi, P.
    • Bulletin of the Korean Chemical Society
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    • 제29권7호
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    • pp.1332-1334
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    • 2008
  • Stable crystalline 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide (BABOT), can be readily synthesized from the reaction of the corresponding bromide with $HNO_3$ and aqueous KBr. Selective Oxidation of a variety of dialkyl and alkyl Aryl sulfides to the corresponding sulfoxides in high yield was achieved by this reagent in solution ($CH_3CN/H_2O$) and solvent free conditions. The reaction proceeds under neutral and mild conditions and can be carried out easily at room temperature with regeneration of BABOT. In this method purification of products is straightforward and no over oxidation to sulfone was noted.

Selective Oxidation of Olefins Catalyzed by Polymer-anchored Nickel(II) Complex in Water Medium

  • Islam, Manirul;Hossain, Dildar;Mondal, Paramita;Roy, Anupam Singha;Mondal, Sanchita;Mobarak, Manir
    • Bulletin of the Korean Chemical Society
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    • 제31권12호
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    • pp.3765-3770
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    • 2010
  • Selective oxidation of olefins has been carried out in water medium with tert-butylhydroperoxide (TBHP, 70% aqueous) as an oxidant using polymer-anchored Ni(II) complex as a catalyst. Several parameters were varied to optimize the reaction conditions. Under the optimized reaction conditions olefins gave selectively allylic oxidation products. The present polymer anchored Ni(II) complex can be recycled five times without any appreciable loss in catalytic activity.

흑색 코발트 태양 선택흡수막의 열퇴화 (Thermal Degradation of Black Cobalt Solar Selective Coatings)

  • 이길동
    • 한국태양에너지학회 논문집
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    • 제35권4호
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    • pp.9-15
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    • 2015
  • Black cobalt solar selective coatings were prepared by using an electroplating method. The changes in the optical properties of the black cobalt selective coating due to thermal degradation were analyzed by using the Auger electron spectroscopy (AES) and spectrophotometer. The black cobalt selective coating was prepared on a copper substrate by using a synthesized electrolyte with $CoCl_2$ and KSCN at a current density of ${\sim}0.5A/dm^2$ for 45s ~ 60s. Its optical properties were a solar absorptance (${\alpha}$) of the order of 0.80 ~ 0.84 and a thermal emittance (${\epsilon}$) of 0.01. From the AES depth profile analysis of heated sample, thermal degradation of the black cobalt selective coating heated for 33 hours at temperature of $350^{\circ}C$ occurred primarily due to interdiffusion at interface of cobalt and copper substrate. This results were predictable that the ${\alpha}$ decreases due to the thermal oxidation and diffusion.

태양 선택흡수막의 특성 분석 (Property Analysis of Solar Selective Coatings)

  • 이길동
    • 한국태양에너지학회 논문집
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    • 제33권4호
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    • pp.31-38
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    • 2013
  • The chemical composition of the black Cr solar selective coatings electrodeposited were investigated for property analysis by using a XPS(X-ray photoelectron spectroscopy) before and after annealing in air at $300^{\circ}C{\sim}500^{\circ}C$ for 120 hours. Black Cr selective coating exposed by solar radiation for 5 months was compared with annealed sample. In addition, The Cu solar selective coatings were prepared by thermal oxidation method for low temperature application. The samples obtained were characterized by using the optical reflectance measurements by using a spectrometer. Optical properties of oxidized Cu solar coatings were solar absorptance $({\alpha}){\simeq}0.62$ and thermal emittance $({\epsilon}){\simeq}0.41(100^{\circ}C)$. In the as-prepared Cr black selective coating, the surface of the coating was found to have Cr hydroxide and Cr. The Cr hydroxide of the major component was converted to $Cr_2O_3$ or $CrO_3$ form after annealing at $500^{\circ}C$ with the desorption of water molecules. The black Cr selective coating was degraded significantly at temperature of $500^{\circ}C$. The main optical degradation modes of this coating were diffusion of Cu substrate materials.

Si, Mn함유 IF 고강도강의 소둔거동 및 도금특성에 미치는 이슬점 온도의 영향 (Effect of Dewpoints on Annealing Behavior and Coating Characteristics in IF High Strength Steels Containing Si and Mn)

  • 전선호;신광수;손호상;김대룡
    • 대한금속재료학회지
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    • 제46권7호
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    • pp.427-436
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    • 2008
  • The effect of dewpoints on annealing behavior and coating characteristics such as wettability and galvannealing kinetics was studied by annealing 0.3wt%Si - 0.1~0.4wt% Mn added interstitial-free high strength steels(IF-HSS). The 0.3wt%Si-0.1wt%Mn steel exhibited good wettability with molten zinc and galvannealing kinetics after annealing when the dewpoint of $H_2-N_2$ mixed gas was above $-20^{\circ}C$. It is shown that the wettability and galvannealing kinetics are directly related to the coverage of the external(surface) oxide formed by selective oxidation during annealing. At $N_2-15%H_2$ annealing atmosphere, the increase of dewpoint results in a gradual transition from external to internal selective oxidation. The decrease of external oxidation of alloying elements with a concurrent increase of their subsurface enrichment in the substrate, showing a larger surface area that was free of oxide particles, contributed to the improved wettability and galvannealing kinetics. On the other hand, the corresponding wettability and galvannealing kinetics were deteriorated with the dewpoints below $-20^{\circ}C$. The continuous oxide layer of network and/or film type was formed on the steel surface, leading to the poor wettability and galvannealing kinetics. It causes a high contact angle between annealed surface and molten zinc and plays an interrupting role in interdiffusion of Zn and Fe during galvannealing process.

$La_{0.5}Ce_{0.5}Co_{1-x}Cu_xO_{3-{\alpha}}$ Perovskite촉매의 선택적 CO 산화반응 및 특성 분석에 관한 연구 (Study on Catalytic Activity of the Selective CO Oxidation and Characterization Using $La_{0.5}Ce_{0.5}Co_{1-x}Cu_xO_{3-{\alpha}}$ Perovskite Catalysts)

  • 손정민
    • 한국수소및신에너지학회논문집
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    • 제18권2호
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    • pp.116-123
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    • 2007
  • [ $La_{0.5}Ce_{0.5}Co_{1-x}Cu_xO_{3-{\alpha}}$ ](X=0, 0.1, 0.3, 0.5) perovskites were prepared by coprecipitation method at pH 7 or pH 11 and its catalytic activity of selective CO oxidation was investigated. The characteristics of these catalysts were analyzed by $N_2$ adsorption, X-ray diffraction(XRD), SEM, $O_2$-temperature programmed desorption(TPD). The pH value at a preparation step made effect on particle morphology. The smaller particle was obtained with a condition of pH 7. The better catalytic activity was observed using catalysts prepared at pH 7 than pH 11. The maximum CO conversion of 98% was observed over $La_{0.5}Ce_{0.5}Co_{0.7}Cu_{0.3}O_{3-{\alpha}}$ at $320^{\circ}C$. Below $200^{\circ}C$, the most active catalyst was $La_{0.5}Ce_{0.5}Co_{0.9}Cu_{0.1}O_{3-{\alpha}}$, of which conversion was 92% at $200^{\circ}C$. By the substitution of Cu, the evolution of ${\alpha}$-oxygen was remarkably enhanced regardless of pH value at preparation step according to $O_2$-TPD. Among the different ${\alpha}$-oxygen species, the oxygen species evolved between $400^{\circ}C$ and $500^{\circ}C$, gave the better catalytic performance for selective CO oxidation including $La_{0.5}Ce_{0.5}CoO_3$ in which Cu was absent.

Ce/TiO2 촉매를 이용한 암모니아의 선택적 산화반응 특성 연구 (Characterization Studies for the Selective Catalytic Oxidation of Ammonia Utilizing Ce/TiO2 Catalyst)

  • 이현희;김기왕;홍성창
    • 공업화학
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    • 제24권5호
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    • pp.494-498
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    • 2013
  • 본 연구에서는, 다양한 오염원에서 발생되는 암모니아를 제어하기 위해 $Ce/TiO_2$ 촉매를 이용한 암모니아의 선택적 촉매 산화반응에 관한 연구가 수행되었다. Ce 함량이 10 wt%가 될 때까지는 Ce 함량이 증가할수록 촉매 성능이 증진됨이 관찰되었다. 그러나 그 이상의 함량에서는 오히려 촉매활성이 감소하였다. 따라서 본 연구에 의한 최적 $Ce/TiO_2$ 촉매는 실제 현장에 적용될 수 있을 것으로 판단된다.