• 제목/요약/키워드: Immobilized catalysts

검색결과 29건 처리시간 0.022초

Polymer-Supported Crown Ethers(Ⅳ) Synthesis and Phase-transfer Catalytic Activity

  • Shim Jae Hu;Chung Kwang Bo;Masao Tomoi
    • Bulletin of the Korean Chemical Society
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    • 제13권3호
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    • pp.274-279
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    • 1992
  • Immobilization method of lariat azacrown ethers, containing hydroxyl group in the side arm of crown ring, on the polymer matrix and the phase-transfer catalytic activity of thus obtained immobilized lariat azacrown ethers were studied. Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of crosslinked polystyrene resins containing epoxy groups with monoaza-15-crown-5 or monoaza-18-crown-6. Microporous crosslinked polystyrene resins containing epoxy group for the syntheses of these immobilized lariat crown catalysts were prepared by suspension polymerization of styrene, divinylbenzene (DVB 2%) and vinylbenzylglycidyl ether. The immobilized lariat catalysts with 10-20% ring substitution exhibited maximal activity for the halogen exchange reactions of 1-bromooctane with aqueous KI or NaI under triphase heterogeneous conditions. Immobilized catalyst exhibited higher activity than corresponding catalyst without the hydroxyl group and this result was suggested that the active site have a structure in which the $K^+$ ion was bound by the cooperative coordination of the crown ring donors and the hydroxyl group in the side arm.

Preparation and Characterization of Sulfated TiO2/zeolite Composite Catalysts with Enhanced Photocatalytic Activity

  • Zhao, Yuan;Li, JingXiu;Wang, Ling;Hao, Yanan;Yang, Lin;He, Pingting;Xue, JianJun
    • Nano
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    • 제13권10호
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    • pp.1850117.1-1850117.11
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    • 2018
  • Sulfated $TiO_2$ nanoparticles were successfully immobilized on zeolite through improving hydrolysis-deposition method. Microstructure, crystallization, surface state and surface area of composite catalysts were characterized by SEM, XRD, FTIR spectra, XPS and BET and the photocatalytic activity was evaluated by degradation of methyl orange under UV irradiation. We optimized these factors ($SO^{2-}_4$ ions, calcination temperature and loading amount of sulfated $TiO_2$) on photocatalytic activity and crystallization of composite photocatalysts. The results indicated that the $SO^{2-}_4$ ions are successfully immobilized on the surface of $TiO_2$, and sulfated $TiO_2$/zeolite show the highest photocatalytic activity for methyl orange at the $[SO^{2-}_4 ]/[Ti^{4+}]$ molar rate of 1:1, calcination temperature of $600^{\circ}C$ for 2 h, and sulfated $TiO_2$ loading amount of 40%, respectively.

Polyvinylalcohol에 고정한 시금치 엽록체와 백금 촉매를 이용한 광수소 발생 (Photoproduction of Hydrogen in Polyvinylalcohol-Iimmobilized Spinach Chloroplsats with Platinum Catalysts)

  • 박인호
    • Journal of Plant Biology
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    • 제36권4호
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    • pp.313-319
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    • 1993
  • Photoproduction of hydrogen by free and polyvinylalcohol (PVA)-immobilized spinach chloroplasts was investigated. Immobilization of chloroplast with PVA increased the functional stability of the chloroplast during storage. PVA-immobilized chloroplasts preserved photosynthetic electron transport activity much better than free chloroplasts. The hydrogen production of free chloroplast decreased to 17% of initial activity after storage of six days. The hydrogen production of the PVA-immobilized chloroplast, however, showed 44% of initial activity after storage of 15 days. The maximal rate of hydrogen production was accomplished at 2$^{\circ}C$ under the light intensity above 116 $\mu$E.m-2.s-1. The amount of hydrogen produced was proportional to the chlorophyll concentration. The hydrogen production was inhibited by DCMU treatment, indicating hydrogen production is dependent on photosynthetic electron transport. These results suggest that PVA is a good candidate for the immobilization matrix of chloroplasts for the photoproduction of hydrogen.

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High Selective Oxidation of Alcohols Based on Trivalent Ion (Cr3+ and Co3+) Complexes Anchored on MCM-41 as Heterogeneous Catalysts

  • Shojaei, Abdollah Fallah;Rafie, Mahboubeh Delavar;Loghmani, Mohammad Hassan
    • Bulletin of the Korean Chemical Society
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    • 제33권8호
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    • pp.2748-2752
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    • 2012
  • Cr(III) and Co(III) complexes with acetylacetonate were anchored onto a mesoporous MCM-41 through Schiff condensation. The materials were characterized by XRD, FT-IR, BET, CHN and ICP techniques. Elemental analysis of samples revealed that one C=N bond was formed through Schiff condensation on MCM-41 surface. The catalysts were tested for the alcohol oxidations using t-butyl hydroperoxide (TBHP) and $H_2O_2$ as oxidant. The catalytic experiments were carried out at both room temperature and reflux condition. Various solvents such as dichloromethane, acetonitrile and water were examined in the oxidation of alcohols. Among the different solvents, catalytic activity is found more in acetonitrile. Further, the catalysts were recycled three times in the oxidation of alcohols and no major change in the conversion and selectivity is observed, which shows that the immobilized metal-acetylacetonate complexes are stable under the present reaction conditions.

정수처리용 TiO2 고정화 촉매 비교 (Comparision of Immobilized TiO2 Catalyst for Water Purification)

  • 전은주;강성환;김병욱;임재명
    • 상하수도학회지
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    • 제13권3호
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    • pp.101-106
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    • 1999
  • This research aims to compare immobilized catalysts prepared by various methods and determine suitable $TiO_2$ catalyst for water purification. Sol-gel method by Anderson and powder coation method by Tanaka ate famous in the methods to immobilize catalyst. Therefore, the $TiO_2$ catalyst for this research was prepared by sol-gel method and powder coating method. Its structure was tested by X-ray diffractometer (XRD), Scanning electron microseope (SEM). Durability of a catalyst-support couple in an solution was investigated. too. Experimental results were summarized as following; i) Optimum ratio of Ti : $H_2O$ : $H^+$ to obtain stable sol was 1 : 10 : 0.1 and the XRD patterns of $TiO_2$ film immobilized by sol-gel method which were fired at $700^{\circ}C$ showed that the catalyst had an anatase structure. ii) The particle size of $TiO_2$ prepared by sol-gel method was less than $5{\mu}$, but it was observed that coated side was not unifiom. iii) Sol-gel method was very effective to obtain $TiO_2$ catalyst of thin film, but spreadability and durability of a catalyst-support couple in a solution were than $TiO_2$ film immobilized by powder coating method. iv) The particle size of $TiO_2$ immobilized by powder coating method was a little larger than it prepared by sol-gel method, but spreadability and uniformity of $TiO_2$ film and durability of a catalyst-support couple in a solution were better than it immobilized by sol-gel method.

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Montmorillonite에 담지된 $Cp_2ZrCl_2$ 촉매를 이용한 에틸렌 중합특성 연구 (Polymerization of Ethylene over $Cp_2ZrCl_2$ Catalyst Supported on Montmorillonite)

  • 안성현;이성호;최무석;임준섭;;조득희;박융호
    • 공업화학
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    • 제24권1호
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    • pp.55-61
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    • 2013
  • $Cp_2ZrCl_2$ 촉매를 Montmorillonite (MMT) 담체에 각기 다른 3가지 방법[MMT/$Cp_2ZrCl_2$, MMT/MAO/$Cp_2ZrCl_2$, MMT/(MAO + $Cp_2ZrCl_2$)]을 적용하여 불균일 촉매를 제조하였고, 이를 이용하여 에틸렌 중합 특성을 조사하였다. 유기점토인 30B-MMT에 담지한 불균일계 촉매가 자연점토인 $Na^+-MMT$에 담지한 촉매보다 높은 담지율을 나타내었고, 에틸렌 중합에서 높은 활성을 보였다. 이는 유기점토의 층간사이에 존재하는 하이드록시기가 MAO 및 촉매와의 화학적 결합을 유도한다고 할 수 있다. MMT에 직접 메탈로센을 담지하여 에틸렌 중합에 사용할 경우 균일계 촉매에 비해 낮은 활성을 보이지만, MMT를 MAO로 처리해서 만든 MMT/MAO/$Cp_2ZrCl_2$ 촉매에 MMAO의 조촉매를 사용하여 중합시에는 높은 활성을 나타내었다. MMT 담지촉매로 제조된 폴리에틸렌은 담지방법에 관계없이 균일계 촉매에 비해 높은 용융점, 분자량, 분자량 분포를 보였으며, 또한 입자형상에 있어 크기가 상당히 증가한 구형의 입자를 나타내었다. 또한 가장 안정적인 담지 반응과 높은 활성을 나타낸 30B-MMT/MAO/$Cp_2ZrCl_2$ 촉매로 최적의 중합조건을 찾기 위해 공정변수에 따라 에틸렌 중합을 수행하였다.

실리카겔에 고정화된 산성 이온성 액체 촉매를 이용한 올레산의 에스터화 반응연구 (The Esterification of Oleic Acid Using Acidic Ionic Liquid Catalysts Immobilized on Silica Gel)

  • 최재형;박용범;이석희;천재기;우희철
    • Korean Chemical Engineering Research
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    • 제48권5호
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    • pp.583-588
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    • 2010
  • 유리지방산 함량이 높은 원료의 효율적인 바이오디젤 생산을 위해 다양한 고체산 촉매를 사용하여 회분식 반응기에서 유리지방산의 에스터화 반응에 대한 연구를 수행하였다. 고체산 촉매는 상용 촉매인 황산기를 지닌 이온교환수지(Amberlyst-15, Dowex 50Wx8)와 실리카겔에 술폰기 및 염화술폰기 지닌 산성 이온성 액체가 고정화된 촉매($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$), 단순히 실리카겔에 술폰기 및 염화술폰기의 산성적 기능기를 도입한 촉매들을 사용하여 반응특성을 비교하였다. 또한 에스터화 반응 실험변수로써 반응시간, 온도, 반응물간의 몰 비율(메탄올:올레산), 촉매량에 대한 영향을 조사하였다. 사용된 고체산 촉매들 중 실리카겔에 고정화된 알릴이미다졸리움을 포함한 산성 이온성 액체 촉매가 가장 우수한 반응성을 나타내었다. 특히 실리카겔에 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate가 고정화된 $SiO_2-[ASBI][HSO_4]$ 촉매가 같은 반응조건에서 기존의 알려진 Amberlyst-15보다 더 나은 성능을 보였으며, 353 K 반응온도와 5 wt%의 촉매량, 메탄올/올레산의 몰 비율 20의 조건에서 2시간 동안 약 96%의 높은 전환율을 나타내었다. $SiO_2-[ASBI][HSO_4]$의 높은 촉매 활성은 실리카에 고정화된 강한 브뢴스테드산의 작용기에 기인한 것으로 생각된다. 바이오디젤로부터 촉매의 분리 및 회수는 간단한 경사법 혹은 여과법에 의해 쉽게 분리할 수 있고, 이를 회수하여 재사용이 가능하다.

Significant Improvement of Catalytic Efficiencies in Ionic Liquids

  • Song, Choong-Eui;Yoon, Mi-Young;Choi, Doo-Seong
    • Bulletin of the Korean Chemical Society
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    • 제26권9호
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    • pp.1321-1330
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    • 2005
  • The use of ionic liquids as reaction media can confer many advantages upon catalytic reactions over reactions in organic solvents. In ionic liquids, catalysts having polar or ionic character can easily be immobilized without additional structural modification and thus the ionic solutions containing the catalyst can easily be separated from the reagents and reaction products, and then, be reused. More interestingly, switching from an organic solvent to an ionic liquid often results in a significant improvement in catalytic performance (e.g., rate acceleration, (enantio)selectivity improvement and an increase in catalyst stability). In this review, some recent interesting results which can nicely demonstrate these positive “ionic liquid effect” on catalysis are discussed.

Asymmetric Ring Opening of Terminal Epoxides Catalyzed by Chiral Co(III)-BF3 Salen Complex Immobilized on SBA-16

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • 제30권8호
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    • pp.1771-1777
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    • 2009
  • The homogeneous B$F_3$ containing chiral Co(III) salen complexes were anchored non-covalently on the surfaces of mesoporous SBA-16 silica containing aluminum species. The Brönsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. The FT-IR, UV, ESCA, and NMR analyses were performed to determine the structure of synthesized chiral salen catalysts. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by water and phenol derivatives. They showed very high enantioselectivity and yield more than 98% in the catalytic synthesis of optically active products.