• Title/Summary/Keyword: Mesoporous catalyst

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Chiral Mesoporous Silica for Asymmetric Metal-free Catalysis: Enhancement of Chirality thorough Confinement Space by Plug Effect

  • Jeong, Eun-Yeong;Im, Cheong-Rae;Park, Sang-Eon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.199-199
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    • 2011
  • The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

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Carbon Dioxide Reforming of Methane Over Mesoporous $Ni/SiO_2$ Catalyst

  • Kim, Dae Han;Sim, Jong Ki;Seo, Hyun Ook;Jeong, Myung-Geun;Kim, Young Dok;Lim, Dong Chan;Kim, Sang Hoon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.166-166
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    • 2013
  • Mesoporous $SiO_2$-supported Ni catalysts (Ni/$SiO_2$ and Ni/$TiO_2$/$SiO_2$) were fabricated by atomic layer deposition (ALD), and their catalytic activity and stability were investigated in carbon dioxide reforming of methane (CRM) reaction at $800^{\circ}C$ The Ni/$SiO_2$ catalysts showed high stability as a result of confinement of Ni particles with a mean size of ~10 nm within the pores of $SiO_2$ support. Besides, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that the Ni nanoparticles were partially buried inside the $SiO_2$ support. The strong interaction between Ni and the $SiO_2$ support could also be advantageous for long-term stability of the catalyst. In case of the Ni/$TiO_2$/$SiO_2$ catalyst, it was found that the catalytic activity of 10 nm-sized Ni nanoparticles was not much influenced by $TiO_2$ addition.

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Carbon-silica composites supported Pt as catalyst for asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate

  • Mao, Cong;Zhang, Jie;Xiao, Meitian;Liu, Yongjun;Zhang, Xueqin
    • Current Applied Physics
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    • v.18 no.12
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    • pp.1480-1485
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    • 2018
  • Mesoporous carbon-silica composites supported Pt nanoparticle catalysts (Pt/MCS) were firstly applied to the heterogeneous asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate (EOPB). A series of different silica contents were investigated in the fabrication of this mesoporous material. When the volume of added tetraethyl orthosilicate (TEOS) during the preparation of composites is 8 mL, Pt/MCS-8 holds carbon and silica as the main components and possesses relatively strong acidity, mesoporous structures with micropores, appropriate Pt nanoparticle size and high dispersibility showing by XRD, XPS, TPD, $N_2$ sorption and TEM. These properties cause its good catalytic performance in the heterogeneous asymmetric hydrogenation of EOPB with the enantiomeric excess value and conversion up to 85.6% and 97.8%, respectively.

Synthesis of New Bimetallic Chiral Salen Catalyst Bearing Co(BF4)2 Salt and Its Application in Asymmetric Ring Opening of Epoxide

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2973-2979
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    • 2010
  • The newly synthesized homogeneous chiral Co(III) salen complexes were anchored non-covalently on the acidic sites of mesoporous Al-SBA-15. The Bronsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. XRD, BET, TEM, FT-IR and ESCA (XPS) analyses were performed to characterize the property of support, and the structure of new homogeneous and heterogeneous chiral Co salen catalyst. The homogeneous and heterogeneous catalysts could be applied in asymmetric ring opening of epichlorohydrine (ECH) by water. They showed very high enantioselectivity and a good yield up to 99% in the catalytic synthesis of optically active products.

Synthesis of Optically Active Monoesters via Kinetic Resolution by Chiral Co (Salen) Complex Immobilized on Mesoporous BEA (메조세공 BEA에 고정화된 키랄 Co살렌 착체의 동적분할을 통한 고광학순도의 키랄 모노에스테르 합성)

  • Choi, Seong Dae;Park, Geun Woo;Lee, Gyung Chan;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.26 no.2
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    • pp.132-137
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    • 2015
  • BEA-zeolite was modified by alkaline solution to introduce mesoporosity in the crystals and the homogeneous chiral Co(III) salen was immobilized in the mesopores. The dinuclear chiral Co(salen)-$GaCl_3$ catalyst immobilized on mesoporous BEA-zeolite showed high activity for the regioselective ring opening of terminal epoxides by carboxylic acids. Various chiral monoester derivatives could be synthesized with moderate enantioselectivity (47~69 ee%) from racemic epoxides through above reaction. When the chiral (S)-ECH was used as a reactant, it was efficiently resolved by carboxylic acid with a high enantioselectivity in the presence of heterogenized chiral salen catalyst, and the ring opened product afforded optically pure monoester epoxide (R)-GB (up to 98 ee%) through the ring closing in the basic solution by elimination of HCl. The heterogeneous catalyst could be fabricated easily, and the catalytic activity was retained for several times reuse without any further regeneration step.

Benzyl Alcohol Oxidation over H5PMo10V2O40 Catalyst Chemically Immobilized on Sulfur-containing Mesoporous Carbon (황이 포함된 중형기공성 탄소에 화학적으로 고정화된 H5PMo10V2O40 촉매 상에서 Benzyl Alcohol 산화반응)

  • Gim, Min Yeong;Kang, Tae Hun;Choi, Jung Ho;Song, In Kyu
    • Korean Chemical Engineering Research
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    • v.54 no.3
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    • pp.419-424
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    • 2016
  • $H_5PMo_{10}V_2O_{40}$ ($PMo_{10}V_2$) catalyst chemically immobilized on sulfur-containing mesoporous carbon (S-MC) was prepared, and it was applied to the benzyl alcohol oxidation reaction. S-MC was synthesized by a templating method using SBA-15 and p-toluenesulfonic acid as a templating agent and a carbon precursor, respectively. S-MC was then modified to have a positive charge, and thus, to provide sites for the immobilization of $PMo_{10}V_2$. By taking advantage of the overall negative charge of $[PMo_{10}V_2O4_{40}]^{5-}$, $PMo_{10}V_2$ catalyst was immobilized on the S-MC support as a charge matching component. It was revealed that $PMo_{10}V_2$ species were finely and molecularly dispersed on the S-MC via chemical immobilization. In the vapor-phase oxidation of benzyl alcohol, $PMo_{10}V_2$/S-MC catalyst showed higher conversion of benzyl alcohol and higher yield for benzaldehyde and benzoic acid than unsupported $PMo_{10}V_2$ catalyst. The enhanced catalytic performance of $PMo_{10}V_2$/S-MC was due to fine dispersion of $PMo_{10}V_2$ species on the S-MC via chemical immobilization.

Effect of Chemical Modification of Carbon Supports on Electrochemical Activities for Pt-Ru Catalysts of Fuel Cells (탄소지지체의 화학적 변형에 따른 연료전지용 백금-루테늄 촉매의 전기화학적 활성의 영향)

  • Kim, Byung-Ju;Park, Soo-Jin
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.94.1-94.1
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    • 2011
  • In this work, ordered mesoporous carbons (OMCs) were prepared by the conventional templating method using mesoporous silica (SBA-15) for Pt-Ru catalyst supports in fuel cells. The influence of surface modification on carbon supports on the electrochemical activities of Pt-Ru/OMCs was investigated with different pH. The neutral-treated OMCs (N-OMCs), base-treated OMCs (B-OMCs), and acid-treated OMCs (A-OMCs) were prepared by treating OMCs with 2 M $C_6H_6$, 2 M KOH, and 2 M $H_3PO_4$, respectively. The surface characteristic of the carbon supports were determined X-ray photoelectron spectroscopy (XPS). The electrochemical activities of the Pt-Ru catalysts had been enhanced when the OMCs supports were treated by basic or neutral agents, while the electrochemical activities had been decayed for the A-OMCs supported Pt-Ru.

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Catalytic Upgrading of Geodae-Uksae 1 over Mesoporous MCM-48 Catalysts

  • Jeon, Ki-Joon;Jin, Sung Ho;Park, Sung Hoon;Jeon, Jong-Ki;Jung, Sang-Chul;Ryu, Changkook;Park, Young-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.1951-1955
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    • 2014
  • Catalytic pyrolysis of Geodae-Uksae 1, a kind of miscanthus found in Korea, was carried out over mesoporous MCM-48 catalysts. For rapid product analysis and catalyst evaluation, pyrolysis-gas chromatography/mass spectrometry was used. X-ray diffraction, nitrogen sorption, pyridine adsorbed Fourier transform infrared, and NH3 temperature programmed desorption were utilized to analyze the properties of the catalysts. Compared to non-catalytic reaction, catalytic upgrading over mesoporous Al-MCM-48 catalysts produced a higher-quality bio-oil with a high stability and low oxygen content. Al-MCM-48 exhibited higher deoxygenation ability than Si-MCM-48 due to its higher acidity.

Preparation and Characterization of Ni Catalyst Supported on Mesoporous Silica for Methanation (메탄화 반응을 위한 중형 기공성 실리카 물질에 담지된 니켈 촉매의 제조와 특성 분석)

  • Yi, Jong-Heop;Kim, Woo-Young;Kang, Mi-Yeong;Cho, Won-Jun
    • Journal of the Korean Institute of Gas
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    • v.13 no.5
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    • pp.26-32
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    • 2009
  • Ni catalysts on mesoporous silica and commercial silica were prepared for the methanation. XRD and TPR analyses indicated that Ni/mesoporous silica had smaller metal particle size and higher metal dispersion than that of Ni/commercial silica. In addition, Ni/mesoporous silica had stronger metal-support interaction. In methanation, Ni/mesoporous silica showed higher CO conversion and methane yield (65%) than Ni/commercial silica (58%). In the characterization results of catalysts after reaction, Ni/commercial silica was deactivated by the collapse of structure and metal sintering, but Ni/mesoporous silica showed stable catalytic performance.

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