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2004 Fiscal Year Final Research Report Summary

Preparation of environmental benign nano-structured catalysts composed of clay and metal complexes

Research Project

Project/Area Number 15550137
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Environmental chemistry
Research InstitutionCHIBA UNIVERSITY

Principal Investigator

SHIMAZU Shogo  CHIBA UNIVERSITY, FACULTY OF ENGINEERING, PROFESSOR, 工学部, 助教授 (10178957)

Project Period (FY) 2003 – 2004
Keywordsclay minerals / intercalation / molecular recognizing catalysts / solid state NMR / nano-complexes / green catalysts / self-assembly / porphyrin complexes
Research Abstract

Novel nano-structured composites were synthesized from clays and pillar complexes with long alkyl spacers by simple cation exchange methods, where pillar complexes were rhodium(I) bipyridines and cobalt porphyrins derivatives.
The nano-structured clays were characterized by FT-IR,XRD,SEM,TEM and high-resolution solid state NMR. The loading amount of pillar complexes into LiTN was detected by CHN analysis, UV-vis, and TG-DTA. The powder XRD measurements revealed that the basal spacing of the nano-structured clay was expanded after the intercalation. The modified taeniolites with long alkyl chains (n>7) showed sharp diffraction peaks comparable to the original taeniolite. The high crystallinity of clay layers can be achieved by the hydrophobic interaction of alkyl groups in the layers. The C.S.(clearance space=basal spacing (d_<001>)-thickness of layer (0.96 nm)) of the nano-structured clays calculated from XRD increases in proportional to the length of alkyl groups (slope : 0.14 nm/CH_2). The interlayer space estimated from TEM image of the nano-structured clays is well consistent to the C.S.calculated from the powder XRD measurement. High-resolution solid-state ^<13>C NMR study for nano-structured clays elucidated the conformation of the pillar complexes in the clay to be all-trans.
Synthesized pillar complexes and nano-structured clays were used for the catalytic hydrogenation reactions and epoxidation of olefins. In case of pillar complexes, catalytic activity was decreased with increasing the alkyl chain length except for [Rh(COD)C23-bpy]ClO_4. On the contrary, the activity of the nano-structured clays increased with C.S.of the nano-structured clays. Moreover, shape selectivity of the substrate was observed fro the nano-structured clays and the interlayer space was clearly related to the stereo selectivity. Furthermore, we found that nano-structured clays were recyclable catalysts in hydrogenation.

  • Research Products

    (18 results)

All 2005 2004 2003

All Journal Article (18 results)

  • [Journal Article] Acidic Property of Fe(III)-Taeniolite2005

    • Author(s)
      S.SHIMAZU, H.SHOJI, T.ODASHIMA, T.SEKI
    • Journal Title

      Journal of Ion Exchange 16・1

      Pages: 1-5

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Studies on tris(β-diketonato)zirconium(IV); syntheses, characterization and catalytic activity for regioselective ring-opening of oxiranes2005

    • Author(s)
      Y.PERMANA, S.SHIMIZU
    • Journal Title

      Catalysis Communications 6(in press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Acidic Property of Fe(III)-Taeniolite2005

    • Author(s)
      S.SHIMAZU et al.
    • Journal Title

      J.Ion Exch. 16(1)

      Pages: 60-64

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Studies on tris(β-diketonato)zirconium(IV) ; Syntheses, characterization and catalytic activity for regioselective ring-opening of oxiranes2005

    • Author(s)
      Y.Permana, S.Shimazu
    • Journal Title

      Catal.Commun. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Selective Synthesis of Primary Methoxypropanol Using Clay Supported Tris(2,4-pentadionato)zirconium(IV)2004

    • Author(s)
      Y.PERMANA, S.SHIMAZU
    • Journal Title

      Journal of Molecular Catalysis A : Chemical 221・1-2

      Pages: 141-144

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Nano-structured Clays : Unique Conformation of Pillar Complexes2004

    • Author(s)
      N.YAMAGUCHI, S.SHIMAZU
    • Journal Title

      Chemistry Letters 33・3

      Pages: 208-209

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Activation of Bulk MoO_3 Catalysis by Spray Reaction Method fro Propene Photometathesis Reaction2004

    • Author(s)
      N.ICHIKUNI, S.SHIMAZU
    • Journal Title

      Catalysis Letters 93・3-4

      Pages: 177-180

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Selective Synthesis of Primary Methoxypropanol Using Clay Supported Tris(2,4-pentadionato)zirconium(IV)2004

    • Author(s)
      Y.Permana, S.Shimazu
    • Journal Title

      J.Molecular Catalysis A : Chemical 221(1-2)

      Pages: 141-144

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of nano-structured clays : unique conformation of pillar complexes2004

    • Author(s)
      N.Yamaguchi, S.Shimazu
    • Journal Title

      Chem.Lett. 33(3)

      Pages: 208-209

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Activation of Bulk MoO_3 Catalysts by Spray Reaction Method for Propene Photometathesis Reaction.2004

    • Author(s)
      N.Ichikuni, S.Shimazu
    • Journal Title

      Catalysis Letters 93(3-4)

      Pages: 177-180

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric Hydrogenation of Acetophenone by Rh(I)-BINAP Supported on Smectites with Various Interlayer Distances2003

    • Author(s)
      S.SHIMAZU, M.SUZUKI, N.ICHIKUNI, T.UEMATSU
    • Journal Title

      Journal of Ion Exchange 14

      Pages: 397-400

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Au/TiO_2 catalysts by suspension spray reaction method and their catalytic property for CO oxidation2003

    • Author(s)
      L.Fan, N.Ichikuni, S.Shimazu, T.Uematsu
    • Journal Title

      Journal of Ion Exchange 14

      Pages: 397-400

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of mesoporous silica anchored Mo Catalysis and in-situ XAFS characterization under photometathesis reaction2003

    • Author(s)
      N.Ichikuni, T.Eguchi, H.Murayama, K.Bando, S.Shimazu et al.
    • Journal Title

      Studies in Surface Science and Catalysis 146

      Pages: 359-362

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] 層間修飾による分子認識スメクタイト触媒の開発2003

    • Author(s)
      島津省吾
    • Journal Title

      スメクタイト 13

      Pages: 25-30

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Asymmetric Hydrogenation of Acetophenone by Rh(I)-BINAP Supported on Smectites with Various Interlayer Distances2003

    • Author(s)
      S.SHIMAZU.M.SUZUKI, N.ICHIKUNI, T.UEMATSU
    • Journal Title

      J.Ion Exch. 14

      Pages: 397-400

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Au/TiO_2 catalysts by suspension spray reaction method and their catalytic property for CO oxidation2003

    • Author(s)
      L.Fan, N.Ichikuni, S.Shimazu, T.Uematsu
    • Journal Title

      Appl.Catal.A : General 246

      Pages: 87-95

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of mesoporous silica anchored Mo catalysts and in-situ XAFS characterization under propene photometathesis reaction2003

    • Author(s)
      N.Ichikuni, T.Eguchi, H.Murayama, K.K Bando, S.Shimazu et al.
    • Journal Title

      Studies in Surface Science and Catalysis 146

      Pages: 359-362

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of smectite catalysts for molecular recognizing reactions by chemical modification of clays2003

    • Author(s)
      S.Shimazu
    • Journal Title

      Smectites 13(1)

      Pages: 25-30

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2006-07-11  

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