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Macromolecular Synthesis by Air Oxidative Polymerization through Multi-electron Transfer

Research Project

Project/Area Number 12650870
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionKeio University

Principal Investigator

YAMAMOTO Kimihisa  Fac. Sci. Technol. Dept. Chem., Keio University, Assoc. Prof., 理工学部, 助教授 (80220458)

Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2001: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2000: ¥3,100,000 (Direct Cost: ¥3,100,000)
KeywordsOxidative Polymerization / Air / Polymer Synthesis / ポリアニン / 酸化重合触媒 / 2電子移動 / 高分子錯体 / 電子過程 / ポリアニリン / 酸素
Research Abstract

Research of the four-electron reduction of oxygen to water is important in order not only to determine the life mechanism but also to make novel catalysts.
As face-to-face Cobalt Dinuclear Porphyrins (CoP2) are known as excellent catalysts to promote the reaction. Polymer complexes of CoP2 with Polyaniline were prepared on the electrode as a catalyst. Electrochemical properties of Polyaniline-CoP2 complex was investigated and proved to catalyze 4-electron reduction by 80%, compared to 50% by CoP2 modified electrode. In order to establish essential factor to promote catalytic efficiency of CoP2, various conducting polymers including self-dope polyaniline, and proton transfer redox polymer were synthesized. It probed that the efficiency of 4-electron reduction is strongly dependent on the redox potential of the polymer-matrix, indicating that redox potential of polymer is an important factor in this catalytic system. As PCAn acts as an efficient electron mediator even in neutral conditions due to its stable redox activity over wide pH range, catalytic reduction of oxygen was carried out using PCAn-CoP2 complex in neutral conditions (pH=6.2). A catalytic efficiency up to 95% toward 4-electron reduction of oxygen was observed by RDV, and RRDV measurements. One-step 4-electron reduction was occurred, not two steps 2-electron transfer by RRDV. It is because PCAn has acidic domain in the polymer matrix, which is thought to keep acidity in the film to some extent, even in neutral conditions, that 4-electron reduction of oxygen occurs in the neutral conditions.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] K.Yamamoto., et al.: "Electrochemistry of Co-Ru Hetero-Dinuclear Porphyrin Complex in Nafion Matrix"J.Chem.Soc.Phys.Chem.Chem.Phys.. 3. 4462-4468 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Yamamoto., et al.: "Self-Assembly of a Porphyrin Array via the Molecular Recognition Approach : Synthesis and Properties of a Cyclic Zinc(II) Porphyrin Trimer Based on Coordinaition and Hydrogen Bonding"Inorg.Chem.. 40. 3395-3405 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Yamamoto., et al.: "Electrochemical Catalytic Reduction of Oxygen by Self-doped Polyaniline-Co-porphyrin Complex Modified Glassy Carbon"J.Inorg.Organometal.Polym.. 9. 231-243 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K. Yamamoto et al.: "Electrochemistry of Co-Ru Hetero-Dinuclear Porphyrin Complex in Nation Matrix"Phys. Chem. Chem. Phys.. 3. 4462 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K. Yamamoto et al.: "Self-Assembly of a Porphyrin Array via the Molecular Recognition Approach: Synthesis and Properties of a Cyclic Zinc(II) Porphyrin Trimer Based on Coordination and Hydrogen Bonding"Inorg. Chem.. 40. 3395 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K. Yamamoto et al.: "Electrochemical Catalytic Reduction of Oxygen by Self-doped Polyaniline-Co-porphyrin Complex Modified Glassy Carbon Electrode"J. Inorg. Organometal. Polym.. 9. 231 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Yamamoto et al.: "Electrochemistry of Co-Ru Hetero-Dinuclear Porphyrin Complex in Nafion Matrix"J.Chem.Soc.Phys.Chem.Chem.Phys.. 3. 4462-44683 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Yamamoto et al.: "Self-Assembly of a Porphyrin Array via the Molecular Recoanition Approach : Synthesis and Propeties of a Cyclic Zinc(II) Porphyrin Trimer Based on Coordination and Hvdrogen Bonding"Inorg.Chem.. 40. 3395-3405 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Yamamoto et al.: "Electrochemical Catalytic Reduction of Oxygen by Self-doped Polyaniline-Coporphyrin Complex Modified Glassy Carbon Electrode"J.Inorg.Organometal.Polym.. 9. 231-243 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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