• Title/Summary/Keyword: Immobilized catalysts

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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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    • v.13 no.3
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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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    • v.13 no.10
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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.

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

  • 박인호
    • Journal of Plant Biology
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    • v.36 no.4
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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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    • v.33 no.8
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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.

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

  • Jeon, En Ju;Kang, Sung Hwan;Kim, Byung Ug;Rim, Jay Myung
    • Journal of Korean Society of Water and Wastewater
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    • v.13 no.3
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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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Polymerization of Ethylene over $Cp_2ZrCl_2$ Catalyst Supported on Montmorillonite (Montmorillonite에 담지된 $Cp_2ZrCl_2$ 촉매를 이용한 에틸렌 중합특성 연구)

  • Ahn, Sung-Hyun;Lee, Sung-Ho;Choi, Moo-Seok;Im, Jun-Seop;Sheikh, Rizwan;Cho, Deug-Hee;Park, Yeung-Ho
    • Applied Chemistry for Engineering
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    • v.24 no.1
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    • pp.55-61
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    • 2013
  • Heterogeneous metallocene catalysts supported on montmorillonite (MMT), [$Cp_2ZrCl_2$/MMT, $Cp_2ZrCl_2$/MAO/MMT, and $Cp_2ZrCl_2$ + MAO/MMT], were prepared with three different methods of immobilization and tested for ethylene polymerization. The heterogeneous catalysts immobilized on organo clay (30B-MMT) showed the higher metal loading and polymerization activity than those immobilized on natural clay $Na^+-MMT$. These results suggest that the hydroxyl groups of organo clay interlayers react with the MAO and catalyst through the chemical bond. The metallocene catalyst supported directly on MMT showed lower activity for ethylene polymerization compared to the homogeneous systems, while MMT/MAO/$Cp_2ZrCl_2$, catalysts treated with MAO before impregnation, showed a higher activity. The polymers obtained from MMT-supported catalysts have higher melting point, molecular weight and molecular weight distributions than those of homogeneous catalysts. The polymer particles with increasing significant size. Ethylene polymerization over 30B-MMT/MAO/$Cp_2ZrCl_2$ catalyst was also performed varying the process variables to optimize the process conditions.

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

  • Choi, Jae-Hyung;Park, Yong-Beom;Lee, Suk-Hee;Cheon, Jae-Kee;Woo, Hee-Chul
    • Korean Chemical Engineering Research
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    • v.48 no.5
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    • pp.583-588
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    • 2010
  • Esterification of free fatty acid with methanol to biodiesel was investigated in a batch reactor using various solid acid catalysts, such as polymer cation-exchanged resins with sulfuric acid functional group(Amberlyst-15, Dowex 50Wx8), acidic ionic liquids (ILs)-modified silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$) and grafted silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-R-SO_3H$, $SiO_2-R-SO_2Cl$). The effects of reaction time, temperature, reactant concentration(molar ratio of methanol to oleic acid), and catalyst amount were studied. Allylimidazolium-based ILs on modified silica gels were superior to other tested solid acid catalysts. Especially, the performance of $SiO_2-[ASBI][HSO_4]$ (immobilized by grafting of 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate on silica gel) was better than that of a widely known Amberlyst-15 catalyst at the same reaction conditions. A high conversion yield of 96% was achieved in the esterification reaction of the simulated cooking oil at 353 K for 2 h. The high catalytic activity of $SiO_2-[ASBI][HSO_4]$ was attributed to the presence of strong Brønsted acid sites from the immobilized functional groups. The catalyst was recovered and the biodiesel product was separated by simple processes such as decantation and filtration.

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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    • v.26 no.9
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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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    • v.30 no.8
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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.