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2006 Fiscal Year Final Research Report Summary

Development of polyoxometalate-based selective oxidation catalysts

Research Project

Project/Area Number 16206077
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Catalyst/Resource chemical process
Research InstitutionThe University of Tokyo

Principal Investigator

MIZUNO Noritaka  The University of Tokyo, Graduate School of Engineering, Professor, 大学院工学系研究科, 教授 (50181904)

Co-Investigator(Kenkyū-buntansha) UCHIDA Sayaka  The University of Tokyo, Graduate School of Engineering, Assistant Professor, 大学院工学系研究科, 助手 (10361510)
HIKICHI Shiro  Kanagawa University, Faculty of Engineering, Professor, 工学部, 教授 (10282857)
Project Period (FY) 2004 – 2006
Keywordspolyoxometalate / hydrogen peroxide / molecular oxygen / epoxidation / Bayer-Villiger oxidation / ionic crystal / macro cation / selective sorption
Research Abstract

(1)Efficient epoxidation catalysts with hydrogen peroxide. (a) Peroxotungstate. The highly chemo-, regio-, and diastereoselective and stereospecific epoxidation of various allylic alcohols with only 1 equivalent of hydrogen peroxide in water could be efficiently catalyzed by an dinuclear peroxotungstate, [{W(=O)(O_2)_2(H_2O)}_2(μ-O)]^<2->. The peroxotungstate could be immobilized on ionic liquid-modified SiO_2. (b) Lacunary silicotungstate. The epoxidation with H_2O_2 catalyzed by lacunary silicodecatungstate ([γ-SiW_<10>O_<34>(H_2O)_2]^<4->) proceeded with 【greater than or equal】99% selectivity to epoxide, 【greater than or equal】99% efficiency of H_2O_2 utilization, high stereospecificity, and the easy recovery of the catalyst. A novel S-shaped disilicoeicosatungustate, [γ-SiW_<10>O_<32>(H_2O)_2)_2(μ-O)_2]^<4->, efficiently promoted the H_2O_2-based Baeyer-Villiger oxidations of cycloalkanones. (c) Di-vanadium or titanium-substituted silicotungstate. [γ-1,2-H_2SiV_2W_<10>O_<40>]^<4-> … More with the {VO-(μ-OH)_2-VO} core could catalyze epoxidation of olefins using only one equivalent H_2O_2 with the high epoxide yield and high efficiency of H_2O_2 utilization. Notably, this system showed unique stereospecificity, diastereoselectivity, and regioselectivity. A stereospecific epoxidation with hydrogen peroxide proceeded with a titanium-substituted silicotungstate cluster of [{γ-SiTi_2W_<10>O_<36>(OH)_2}_2(μ-O)_2]^<8->.
(2)Bis (μ-oxo) bridged di-iron site on the lacunary POM as an efficient epoxidation catalyst with molecular oxygen. Bis (μ-oxo) bridged di-iron site on the lacunary POM has been used as catalysts for the oxygenation of alkenes in homogeneous reaction media using molecular oxygen as an oxygen donor. It is remarkable that selectivity to cyclooctene oxide and turnover number reached up to 98% and 10000, respectively, for the oxygenation of cyclooctene.
(3)Microstructured POMs as a shape-selective catalyst. The Keggin-type POM, SiW_<12>O_<40>^<4->, and Cr(III) trinuclear cation, Cr_3O(OOCH)_6(H_2O)_3^+, assembled to create a channeled complex K_3[Cr_3O(OOCH)_6(H_2O)_3]SiW_<12>O_<40>・16H_2O with an opening of 0.5 x 0.8 nm. The complex reversibly absorbed water and polar organic molecules smaller than C2. The guest inclusion was highly selective and even a difference of one methylene group in the organic guest molecule was discriminated. Less

  • Research Products

    (14 results)

All 2006 2005 2004

All Journal Article (13 results) Book (1 results)

  • [Journal Article] Channel-Selective Independent Sorption and Collection of Hydrophilic and Hydrophobic Molecules by Cs_2[Cr_3O(OOCC_2H_5)_6(H_2O)_3]_2[α-SiW_<12>O_<40>] Ionic Crystal2006

    • Author(s)
      C.Jiang, A.Lesbani, R.Kawamoto, S.Uchida, N.Mizuno
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 14240-14241

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Formation of S-Shaped Disilicoeicosatungstate (W20) and the Efficient Baeyer-Villiger Oxidation with Hydrogen Peroxide2006

    • Author(s)
      A.Yoshida, M.Yoshimura, K.Uehara, S.Hikichi, N.Mizuno
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 1956-1960

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Channel-Selective Independent Sorption and Collection of Hydrophilic and Hydrophobic Molecules by Cs_2[Cr_3O(OOCC_2H_5)_6(H_2O)_3]_2[α-SiW_<12>O_<40>] Ionic Crystal2006

    • Author(s)
      C.Jiang, A.Lesbani, R.Kawamoto, S.Uchida, N.Mizuno
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 14240

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Formation of S-Shaped Disilicoeicosatungstate (W2O) and the Efficient Baeyer-Villiger Oxidation with Hydrogen Peroxide2006

    • Author(s)
      A.Yoshida, M.Yoshimura, K.Uehara, S.Hikichi, N.Mizuno
    • Journal Title

      Angew.Chem.Int.Ed 45

      Pages: 1956

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Liquid-Phase Oxidations Catalyzed by Polyoxometalates2006

    • Author(s)
      N.Mizuno, K.Kamata, K.Yamaguchi
    • Journal Title

      Surface and Nanomolecular Catalysis, Taylor and Francis Group

      Pages: 463-492

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Polyoxovanadometalate-Catalyzed Selective Epoxidation of Alkenes with Hydrogen Peroxide2005

    • Author(s)
      Y.Nakagawa, K.Kamata, M.Kotani, K.Yamaguchi, N.Mizuno
    • Journal Title

      Angew. Chem. Int. Ed. 44

      Pages: 5136-5141

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Peroxotungstate Immobilized on Ionic Liquid-modified Silica as a Heterogeneous Epoxidation Catalyst with Hydrogen Peroxide2005

    • Author(s)
      K.Yamaguchi, C.Yoshida, S.Uchida, N.Mizuno
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 530-531

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Polyoxovanadometalate-Catalyzed Selective Epoxidation of Alkenes with Hydrogen Peroxide2005

    • Author(s)
      Nakagawa, K.Kamata, M.Kotani, K.Yamaguchi, N.Mizuno
    • Journal Title

      Angew.Chem.Int.Ed 44

      Pages: 5136

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Peroxotungstate Immobilized on Ionic Liquid-modified Silica as a Heterogeneous Epoxidation Catalyst with Hydrogen Peroxide2005

    • Author(s)
      K.Yamaguchi, C.Yoshida, S.Uchida, N.Mizuno
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 530

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Highly Selective, Recyclable Epoxidation of Allylic Alcohols with Hydrogen Peroxide in Water Catalyzed by Dinuclear Peroxotungstate2004

    • Author(s)
      K.Kamata, K.Yamaguchi, N.Mizuno
    • Journal Title

      Chem. Eur. J. 10

      Pages: 4728-4734

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Zeotype Ionic Crystal of Cs_5[Cr_3O(OOCH)_6(H_2O)_3][α-CoW_<12>O_<40>]・7.5H_2O with Shape-Selective Adsorption of Water2004

    • Author(s)
      S.Uchida, N.Mizuno
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 1602-1603

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Highly Selective, Recyclable Epoxidation of Allylic Alcohols with Hydrogen Peroxide in Water Catalyzed by Dinuclear Peroxotungstate2004

    • Author(s)
      K.Kamata, K.Yamaguchi, N.Mizuno
    • Journal Title

      Chem.Eur.J. 10

      Pages: 4728

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Zeotype Ionic Crystal of Cs_5[Cr_3O(OOCH)_6(H_2O)_3][α-CoW_<12>O_<40>]・7.5H_2O with Shape-Selective Adsorption of Water2004

    • Author(s)
      S.Uchida, N.Mizuno
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 1602

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] Surface and Nanomolecular Catalysis2006

    • Author(s)
      N.Mizuno, K, Kamata, K.Yamaguchi
    • Total Pages
      552
    • Publisher
      Taylor and Francis Group
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2008-05-27  

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