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Chemical doping and property tuning in the solid-solution of polyoxometalates

Research Project

Project/Area Number 18K05060
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionYamaguchi University

Principal Investigator

Ryo Tsunashima  山口大学, 大学院創成科学研究科, 准教授 (70466431)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords固溶体 / 分子結晶 / ポリオキソメタレート / 電気伝導性 / 混晶
Outline of Final Research Achievements

For polyoxometalates, molecular Mo and W oxides, mixed crystals consisting of multiple clusters with different electronic states are prepared to realise systems with macroscopic properties that vary with the composition ratio. Various crystalline samples were prepared with parameters such as cation size, valence and redox activity, and physical properties such as solubility, redox activity, electrical conductivity and dielectric properties were investigated with composition ratio. Based on the results obtained, we aimed development in the materials field of heterogeneous catalysts, solid-phase electrolytes, battery materials and electronics materials.

Academic Significance and Societal Importance of the Research Achievements

Siや金属酸化物などの原子性結晶では、ホスト化合物中の原子Aと類似の大きさだが電子状態が異なる原子Bをゲストとして結晶中に導入する。また、遷移金属イオンなどの異なる原子価が可能な場合、酸化還元的過程を介して混合原子価状態にできる。また、合金は置換・混合する量が不純物程度を超える点でドーピングとは異なるが類似の化学である。そこで、触媒や電子材料として注目されている分子性の金属酸化物であるポリオキソメタレートの結晶性固体について、化学的・物理的性質を固溶化により制御できるような可能性を探索した。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (28 results)

All 2022 2021 2020 2019 2018 Other

All Int'l Joint Research (3 results) Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 9 results,  Open Access: 2 results) Presentation (12 results) (of which Int'l Joint Research: 5 results,  Invited: 4 results) Book (1 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] グラスゴー大学(英国)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] グラスゴー大学(英国)

    • Related Report
      2018 Research-status Report
  • [Int'l Joint Research] 北京化工大学(中国)

    • Related Report
      2018 Research-status Report
  • [Journal Article] Molecular solid solutions for advanced materials - homeomorphic or heteromorphic2022

    • Author(s)
      Tsunashima Ryo
    • Journal Title

      CrystEngComm

      Volume: 24 Issue: 7 Pages: 1309-1318

    • DOI

      10.1039/d1ce01632f

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structural Phase Transitions of a Molecular Metal Oxide2020

    • Author(s)
      Fujibayashi Masaru、Watari Yu、Tsunashima Ryo、Nishihara Sadafumi、Noro Shin‐ichiro、Lin Chang‐Gen、Song Yu‐Fei、Takahashi Kiyonori、Nakamura Takayoshi、Akutagawa Tomoyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 50 Pages: 22446-22450

    • DOI

      10.1002/anie.202010748

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Spin Crossover between the High-Spin and Low-Spin States and Dielectric Switching in the Ionic Crystals of a Fe(II) [2 × 2] Molecular Grid2020

    • Author(s)
      Uezu Yuta、Tsunashima Ryo、Tanaka Chiaki、Fujibayashi Masaru、Manabe Jun、Nishihara Sadafumi、Inoue Katsuya
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 93 Issue: 12 Pages: 1583-1587

    • DOI

      10.1246/bcsj.20200207

    • NAID

      130007955888

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Doping of metal-free molecular perovskite with hexamethylenetetramine to create non-centrosymmetric defects2020

    • Author(s)
      Morita Hagino、Tsunashima Ryo、Nishihara Sadafumi、Akutagawa Tomoyuki
    • Journal Title

      CrystEngComm

      Volume: 22 Issue: 13 Pages: 2279-2282

    • DOI

      10.1039/d0ce00173b

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Anisotropic Polyoxometalate Cages Assembled via Layers of Heteroanion Templates2019

    • Author(s)
      Zheng Qi、Kupper Manuel、Xuan Weimin、Oki Hirofumi、Tsunashima Ryo、Long De-Liang、Cronin Leroy
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 34 Pages: 13479-13486

    • DOI

      10.1021/jacs.9b04533

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ferroelectric Behavior of a Hexamethylenetetramine‐Based Molecular Perovskite Structure2019

    • Author(s)
      Morita Hagino、Tsunashima Ryo、Nishihara Sadafumi、Inoue Katsuya、Omura Yuriko、Suzuki Yasutaka、Kawamata Jun、Hoshino Norihisa、Akutagawa Tomoyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 27 Pages: 9184-9187

    • DOI

      10.1002/anie.201905087

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, and Electrochemical Properties of [Na(SO3)2(RPO3)4MoV4MoVI14O49]5- (R = Propyl or t-Butyl)2019

    • Author(s)
      Fujibayashi Masaru、Shiga Misaki、Tsunashima Ryo、Nakamura Takayoshi
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 92 Issue: 5 Pages: 918-922

    • DOI

      10.1246/bcsj.20180347

    • NAID

      130007649780

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Structural Phase Transition Behavior Observed for a Single Crystal of the Tetrabutylammonium Salt of a Mo18 Polyoxometalate2018

    • Author(s)
      Oki Hirofumi、Shiga Misaki、Nakamura Ippei、Nishida Kazuki、Ichihashi Katsuya、Nishihara Sadafumi、Inoue Katsuya、Akutagawa Tomoyuki、Tsunashima Ryo
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2019 Issue: 3-4 Pages: 492-495

    • DOI

      10.1002/ejic.201801044

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chemo-chromism in an orthogonal dabco-based Co(ii) network assembled by methanol-coordination and hydrogen bond formation2018

    • Author(s)
      Shiga Misaki、Kawaguchi Shogo、Fujibayashi Masaru、Nishihara Sadafumi、Inoue Katsuya、Akutagawa Tomoyuki、Noro Shin-ichiro、Nakamura Takayoshi、Tsunashima Ryo
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 23 Pages: 7656-7662

    • DOI

      10.1039/c8dt01220b

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] Design of Symmetry Defect in the Molecular Perovskite Structure2021

    • Author(s)
      Ryo Tsunashima, Hagino Morita, Tomoe Koga, Junpei Moriguchi
    • Organizer
      Materials Research Meeting 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Co-DABCO一次元鎖からなるK[Co(dabco)(OCN)3]の構造相転移2021

    • Author(s)
      藤川 奈緒美、高橋 仁徳、中村 貴義、綱島 亮
    • Organizer
      日本化学会春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] ヘキサメチレンテトラミンを用いた分子性ペロブスカイト化合物ABI3の構造と誘電物性2021

    • Author(s)
      本田 弘樹、綱島 亮、森田 萩乃
    • Organizer
      日本化学会春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] 光連結異性化を示すCo(III)ニトリト錯体の誘電特性2021

    • Author(s)
      知念 真妃郎、綱島  亮
    • Organizer
      日本化学会春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Exploring a Macroscopic Solid-state Property of Polyoxometalate-based Hybrids2020

    • Author(s)
      綱島亮
    • Organizer
      錯体化学討論会
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] アンモニウムを内包した四面体型錯体の結晶構造と誘電特性2020

    • Author(s)
      田中千晶、綱島亮、中村貴義、高橋仁徳
    • Organizer
      日本化学会中国四国支部大会
    • Related Report
      2020 Research-status Report
  • [Presentation] プロトン化したhexamethylenetetramineとdabcoからなるイオン性置換型固溶体における結晶構造と誘電性2020

    • Author(s)
      綱島亮、森田萩乃、芥川智行
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 球状σ系有機分子の高自由度を活かす電子・機能材料の開発2019

    • Author(s)
      綱島亮
    • Organizer
      電子情報通信学会 有機エレクトロニクス研究会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Molecular metal-oxide; exploring the fine synthetic method and designing solid state property2019

    • Author(s)
      R. Tsunashima
    • Organizer
      13th Conduction and Photoconduction in Organic Solids and Related Phenomena
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Solid-state Properties of Molecular Metal Oxide; Functionality Designed by Inter-cluster Space2019

    • Author(s)
      R. Tsunashima
    • Organizer
      7th Asian Conference On Coordination Chemistry (ACCC7)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 分子断片化した金属酸化物が示す固体物性2018

    • Author(s)
      綱島亮
    • Organizer
      日本化学会中国・四国支部大会
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Macroscopic Electrical Properties of the Mixed-valence Polyoxometalate2018

    • Author(s)
      R. Tsunashima
    • Organizer
      43th International Conference on Coordination Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Book] 機能材料2020

    • Author(s)
      森田萩乃、綱島亮
    • Total Pages
      8
    • Publisher
      シーエヌシー出版
    • Related Report
      2019 Research-status Report
  • [Remarks] 綱島研

    • URL

      http://web.cc.yamaguchi-u.ac.jp/~ryotsuna/tsunashima/index.html

    • Related Report
      2019 Research-status Report
  • [Remarks] 研究室HP

    • URL

      http://web.cc.yamaguchi-u.ac.jp/~ryotsuna/tsunashima/index.html

    • Related Report
      2018 Research-status Report
  • [Patent(Industrial Property Rights)] 安全無害なペロブスカイト型強誘電体材料およびその製造方法2020

    • Inventor(s)
      綱島亮、森田萩乃
    • Industrial Property Rights Holder
      綱島亮、森田萩乃
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2019 Research-status Report

URL: 

Published: 2018-04-23   Modified: 2023-01-30  

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