• Title/Summary/Keyword: selective oxidation

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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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    • v.35 no.3
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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.

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

  • Choi, Jae Won;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.28 no.6
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    • pp.619-625
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    • 2017
  • In this study, the formation of hydroxyl radical and decomposition characteristics of bisphenol A (BPA) was investigated by quantifying hydrogen peroxide formed as a reaction by-product during the formation stage of hydroperoxyl radical. The direct oxidation reaction by ozone only decomposed BPA just like the Criegee mechanism under the condition where radical chain reactions did not occur. Non-selective oxidation reactions occurred under the conditions of pH 6.5 and 9.5 where radical chain reactions do occur, confirming indirectly the formation of hydroxyl radical. The decomposition efficiency of BPA by the added catalysts appeared in the order of $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone. 0.03~0.08 mM of hydrogen peroxide were continuously measured during the oxidation reactions of ozone/catalyst processes. In the case of $O_3$/high pH process, BPA was completely decomposed in 50 min of the oxidation reaction, but reaction intermediates formed by oxidation reaction were not oxidized sufficiently with 29% of the removal ratio for total organic carbon (TOC, selective oxidation reaction). In the case of $O_3/H_2O_2$ and $O_3$/PAC processes, BPA was completely decomposed in 40 min of the oxidation reaction, and reaction intermediates formed by the oxidation reaction were oxidized with 57% and 66% of removal ratios for TOC, respectively (non-selective oxidation reactions).

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

  • Lee, Kil-Don
    • Journal of the Korean Solar Energy Society
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    • v.31 no.4
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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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    • v.29 no.7
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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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    • v.31 no.12
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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.

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

  • Lee, Kil-Dong
    • Journal of the Korean Solar Energy Society
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    • v.35 no.4
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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.

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

  • Lee, Kil-Dong
    • Journal of the Korean Solar Energy Society
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    • v.33 no.4
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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.

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

  • Jeon, Sun-Ho;Shin, Kwang-Soo;Sohn, Ho-Sang;Kim, Dai-Ryong
    • Korean Journal of Metals and Materials
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    • v.46 no.7
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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.

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 ($La_{0.5}Ce_{0.5}Co_{1-x}Cu_xO_{3-{\alpha}}$ Perovskite촉매의 선택적 CO 산화반응 및 특성 분석에 관한 연구)

  • Sohn, Jung-Min
    • Journal of Hydrogen and New Energy
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    • v.18 no.2
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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.

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

  • Lee, Hyun Hee;Kim, Ki Wang;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.24 no.5
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    • pp.494-498
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    • 2013
  • In this study, selective catalytic oxidation (SCO) of $NH_3$ using $Ce/TiO_2$ catalyst was examined to control the slipped NH3 from various pollutants. It was found that the catalytic activity increased with increasing the Ce loadings till reaching 10 wt% Ce loading. However, when Ce loaded over 10 wt%, the activity of catalysts rather decreased than that of catalysts, below 10 wt% Ce. Therefore, the composition of $Ce/TiO_2$ catalyst optimized in this study can be applied to industrial fields.