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2017 Fiscal Year Annual Research Report

Design of asymmetric nano-space in ionic crystals

Publicly Offered Research

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 17H05356
Research InstitutionThe University of Tokyo

Principal Investigator

内田 さやか  東京大学, 大学院総合文化研究科, 准教授 (10361510)

Project Period (FY) 2017-04-01 – 2019-03-31
Keywordsイオン結晶 / 複合材料・物性 / 分子性固体
Outline of Annual Research Achievements

本研究は、無機金属酸化物クラスターであるポリオキソメタレートアニオン(POM)を構成ブロックとし、適切なカチオンやポリマーとの複合化において、電荷・サイズ・対称性・配位子・電子配置・分子量などをパラメーターとして、イオン結晶である結晶性複合体の合成とその機能創製を目的としている。イオン結合は等方的かつ長距離まで働くため、イオン結晶は一般に対称性が高く等方的な構造に結晶化するが、上述のパラメーターの工夫により異方性のある構造や空間が構築される。 今回、研究例の多いKeggin型に代えてより酸性度が高いことで知られるPreyssler型POM と、平均分子量の異なる二種類のポリエチレングリコール(PEG400と1000)との結晶性複合体を合成し、これらのプロトン伝導度を比較した。無加湿・368 Kにおいて、PEG400、1000との複合体はそれぞれ2.5×10-4 S/cm、1.7×10-4 S/cmという比較的高いプロトン伝導度を示し、伝導性にはPEGの分子量の違いに基づくセグメント運動の大小が関わることを明らかにした。次に、ポリマーとPOMの結合強化による構造安定化やプロトンサイトの増加による伝導度向上を指向し、PEGに代えてカチオン性のポリマーであるポリアリルアミンを用いて複合体を合成した結果、プロトン伝導度が一桁向上した。さらに、ポリマーはPEGのままで、POMをNaからBi中心のものに置き換えて(アニオンの負電荷減少)複合体を合成したところ、PEGのセグメント運動がより活発になり、伝導性が一桁近く向上した。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

キラル空間の創出には至っていないが、結晶構造への非対称性の導入には成功しているため。

Strategy for Future Research Activity

キラル空間の創出に注力する

  • Research Products

    (13 results)

All 2018 2017 Other

All Int'l Joint Research (1 results) Journal Article (5 results) (of which Peer Reviewed: 5 results) Presentation (6 results) (of which Int'l Joint Research: 6 results,  Invited: 6 results) Book (1 results)

  • [Int'l Joint Research] 北京化工大学(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      北京化工大学
  • [Journal Article] Rapid Uptake / Release of Cs+ in Isostructural Redox-Active Porous Ionic Crystals with Large Molecular Size and Easily Reducible Dawson-Type Polyoxometalates as Building Blocks2018

    • Author(s)
      S. Hitose, S. Uchida
    • Journal Title

      Inorg. Chem.

      Volume: 57 Pages: 4833-4836

    • DOI

      10.1021/acs.inorgchem.8b00801

    • Peer Reviewed
  • [Journal Article] Cu Species Incorporated into Amorphous ZrO2 with High Activity and Selectivity in CO2-to-methanol Hydrogenation2018

    • Author(s)
      S. Tada, A. Katagiri, K. Kiyota, T. Honma, H. Kamei, A. Nariyuki, S. Uchida, S. Satokawa
    • Journal Title

      J. Phys. Chem. C

      Volume: 122 Pages: 5430-5442

    • DOI

      10.1021/acs.jpcc.7b11284

    • Peer Reviewed
  • [Journal Article] Highly pH-Dependent Facile-Preparation of Amorphous High Surface Area Aluminum Hydroxide-Bicarbonates with [e-Al13O4(OH)24(H2O)12]7+2018

    • Author(s)
      Y. Kinoshita, R. Osuga, J. N. Kondo, Y. Ogasawara, S. Uchida
    • Journal Title

      Chem. Lett.

      Volume: 47 Pages: 668-670

    • DOI

      10.1246/cl.180103

    • Peer Reviewed
  • [Journal Article] High Proton Conduction in Crystalline Composites Based on Preyssler-type Polyoxometalates and Polymers under Non-humidified or Humidified Conditions2017

    • Author(s)
      K. Niinomi, S. Miyazawa, M. Hibino, N. Mizuno, S. Uchida
    • Journal Title

      Inorg. Chem.

      Volume: 56 Pages: 15187-15193

    • DOI

      10.1021/acs.inorgchem.7b02524

    • Peer Reviewed
  • [Journal Article] Proton Conduction in Alkali Metal Ion-Exchanged Porous Ionic Crystals2017

    • Author(s)
      S. Uchida, R. Hosono, R. Eguchi, R. Kawahara, R. Osuga, J. N. Kondo, M. Hibino, N. Mizuno
    • Journal Title

      Phys.Chem.Chem.Phys.

      Volume: 19 Pages: 29077-29083

    • DOI

      10.1039/C7CP04619G

    • Peer Reviewed
  • [Presentation] Cation Uptake and Conduction in Porous Ionic Crystals Based on Polyoxometalates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      The 1st International Symposium on Coordination Ionic Compounds
    • Int'l Joint Research / Invited
  • [Presentation] Selective and Rapid Cation Uptake and Conduction in Porous Ionic Crystals Based on Polyoxometalates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      4th Japan-Canada Joint Symposium on Coordination Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Selective and Fast Ion Uptake / Conduction in Porous Ionic Crystals Based on Polyoxometalates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      11th Japan-China Joint Symposium on Metal Cluster Compounds
    • Int'l Joint Research / Invited
  • [Presentation] Porous Ionic Crystals based on Polyoxometlates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      Post-symposium of Frontiers in Metal Oxide Cluster Science-V
    • Int'l Joint Research / Invited
  • [Presentation] Cation Uptake and Conduction in Redox-Active Porous Ionic Crystals Based on Polyoxometalates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      Frontiers in Metal Oxide Cluster Science-V (FMOCS V)
    • Int'l Joint Research / Invited
  • [Presentation] Cation Uptake and Conduction in Redox-Active Porous Ionic Crystals Based on Polyoxometalates2017

    • Author(s)
      Sayaka Uchida
    • Organizer
      Pre-symposium of Frontiers in Metal Oxide Cluster Science-V
    • Int'l Joint Research / Invited
  • [Book] Polyoxometalate-Based Assemblies and Functional Materials2018

    • Author(s)
      Sayaka Uchida (Yufei Song, Ed.)
    • Total Pages
      167
    • Publisher
      Springer
    • ISBN
      978-3-319-75904-3

URL: 

Published: 2018-12-17  

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