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Nanospace design and proton conduction of metal-organic nanotube based on bottom-up synthesis

Research Project

Project/Area Number 19K05494
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionKyoto University

Principal Investigator

Otsubo Kazuya  京都大学, 理学研究科, 助教 (90601005)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2020: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsナノチューブ / 疎水性空間 / 水クラスター / 水素結合 / プロトン伝導 / 薄膜材料
Outline of Research at the Start

本研究課題ではボトムアップ合成により得られる高プロトン伝導性の金属-有機ナノチューブを基盤材料に据え、ボトムアップ合成の設計性と多様性の高さに立脚した実験的な材料構築技術から、疎水性空間内の水分子に起因する特異な物性に対する多角的な実験研究を行い、理論的な側面のみが先行している高速プロトン輸送に関する機構の解明と具体的な材料設計指針を提示することを目指す。

Outline of Final Research Achievements

Unique water cluster structures in the hydrophobic nanospace in newly synthesized metal-organic nanotubes (MONTs) has been revealed by X-ray study, and the superprotonic conductivion via hydrogen-bonding networks among water clusters has been successfully clarified from both experimental and theoretical aspects. In addition, we succeeded in synthesizing MONTs with various pore diameters and obtaining valuable insights into the relationship between the pore diameter and proton conduction. We also succeeded in synthesizing the first platinum-dimer based metal-organic framework, and revealed that the protic cation trapped inside its pore works as a preinstalled switch for superprotonic conduction vis water adsorption/desorption.

Academic Significance and Societal Importance of the Research Achievements

本研究課題で着目したナノチューブ内の狭いナノ空間に補足された水分子に関する理解が進めば、水素結合様式に依存したプロトン伝導性の変化等の基礎科学的な知見が得られるだけではなく、将来的には生体膜タンパク質が持つ指向性のあるプロトン/水の輸送現象(高速輸送、選択的輸送、一方向輸送、能動輸送)の解明や生体模倣材料の構築に繋がると期待される。さらには、高効率な水浄化膜や高機能な燃料電池材料等、我々の生活に直結する将来的な機能材料創成にブレークスルーをもたらすと期待される。

Report

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

    (26 results)

All 2022 2021 2020 2019 Other

All Journal Article (15 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 15 results,  Open Access: 2 results) Presentation (10 results) (of which Int'l Joint Research: 3 results,  Invited: 5 results) Remarks (1 results)

  • [Journal Article] A Preinstalled Protic Cation as a Switch for Superprotonic Conduction in a Metal-Organic Framework2022

    • Author(s)
      Otsubo Kazuya、Nagayama Shuya、Kawaguchi Shogo、Sugimoto Kunihisa、Kitagawa Hiroshi
    • Journal Title

      JACS Au

      Volume: 2 Issue: 1 Pages: 109-115

    • DOI

      10.1021/jacsau.1c00388

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dibenzodiazapyracylenes: Doubly N‐Doped Cyclopenta‐Fused Polycyclic Molecules That Exhibit High Carrier Mobility2022

    • Author(s)
      Morimoto Yuki、Koo Yun Hee、Otsubo Kazuya、Kitakado Hidetsugu、Seki Shu、Osuka Atsuhiro、Tanaka Takayuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 14 Pages: 202112589-202112589

    • DOI

      10.1002/anie.202200341

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ni@onion-like carbon and Co@amorphous carbon: control of carbon structures by metal ion species in MOFs2021

    • Author(s)
      Mukoyoshi Megumi、Kobayashi Hirokazu、Kusada Kohei、Otsubo Kazuya、Maesato Mitsuhiko、Kubota Yoshiki、Yamamoto Tomokazu、Matsumura Syo、Kitagawa Hiroshi
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 48 Pages: 5897-5900

    • DOI

      10.1039/d1cc02154k

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A square-shaped complex with an electron-acceptor ligand: unique cubic crystal symmetry and similarity to the inorganic mineral katoite2021

    • Author(s)
      Aoki Kentaro、Otsubo Kazuya、Kitagawa Hiroshi
    • Journal Title

      CrystEngComm

      Volume: 23 Issue: 43 Pages: 7691-7697

    • DOI

      10.1039/d1ce00994j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Strain-Controlled Spin Transition in Heterostructured Metal-Organic Framework Thin Film2021

    • Author(s)
      Haraguchi Tomoyuki、Otsubo Kazuya、Sakata Osami、Fujiwara Akihiko、Kitagawa Hiroshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 39 Pages: 16128-16135

    • DOI

      10.1021/jacs.1c06662

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Magnetic Properties of a Dimerized Trinuclear Ni String Complex, [Ni6Cl2(dpa)8](I5)2・0.25I2 (dpa- = 2,2′-Dipyridylamide Anion)2021

    • Author(s)
      Aoki Kentaro、Otsubo Kazuya、Yoshida Yukihiro、Kimura Yojiro、Sugimoto Kunihisa、Kitagawa Hiroshi
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Issue: 21 Pages: 16029-16034

    • DOI

      10.1021/acs.inorgchem.1c02660

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Surface morphology-induced spin-crossover-inactive high-spin state in a coordination framework2021

    • Author(s)
      Sakaida Shun、Otsubo Kazuya、Otake Ken-ichi、Kawaguchi Shogo、Maesato Mitsuhiko、Kitagawa Susumu、Kitagawa Hiroshi
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 12 Pages: 1462-1465

    • DOI

      10.1039/d0cc06682f

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Crystal Size Effect on the Spin-Crossover Behavior of {Fe(py)2[Pt(CN)4]} (py = Pyridine) Monitored by Raman Spectroscopy2020

    • Author(s)
      Sakaida Shun、Otsubo Kazuya、Maesato Mitsuhiko、Kitagawa Hiroshi
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 23 Pages: 16819-16823

    • DOI

      10.1021/acs.inorgchem.0c02874

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] A mixed-valent metal?organic ladder linked by pyrazine2020

    • Author(s)
      Otake Ken-ichi、Otsubo Kazuya、Kitagawa Hiroshi
    • Journal Title

      Journal of Physics: Condensed Matter

      Volume: 33 Issue: 3 Pages: 034002-034002

    • DOI

      10.1088/1361-648x/abbbc7

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] A 2D Mg(II)-MOF with High Density of Coordinated Waters as Sole Intrinsic Proton Sources for Ultrahigh Superprotonic Conduction2020

    • Author(s)
      Chand Santanu、Pal Shyam Chand、Lim Dae-Woon、Otsubo Kazuya、Pal Arun、Kitagawa Hiroshi、Das Madhab C.
    • Journal Title

      ACS Materials Letters

      Volume: 2 Issue: 10 Pages: 1343-1350

    • DOI

      10.1021/acsmaterialslett.0c00358

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Phosphate‐Based Silver-Bipyridine 1D Coordination Polymer with Crystallized Phosphoric Acid as Superprotonic Conductor2020

    • Author(s)
      Pal Arun、Pal Shyam Chand、Otsubo Kazuya、Lim Dae‐Woon、Chand Santanu、Kitagawa Hiroshi、Das Madhab C.
    • Journal Title

      Chemistry - A European Journal

      Volume: 26 Issue: 20 Pages: 4607-4612

    • DOI

      10.1002/chem.201905650

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Remarkably Enhanced Proton Conduction of {NBu2(CH2COOH)2}[MnCr(ox)3] by Multiplication of Carboxyl Carrier in the Cation2020

    • Author(s)
      Okawa Hisashi、Otsubo Kazuya、Yoshida Yukihiro、Kitagawa Hiroshi
    • Journal Title

      Chemical Communications

      Volume: 54 Issue: 45 Pages: 6138-6140

    • DOI

      10.1039/d0cc02192j

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Confined water-mediated high proton conduction in hydrophobic channel of a synthetic nanotube2020

    • Author(s)
      Otake Ken-ichi、Otsubo Kazuya、Komatsu Tokutaro、Dekura Shun、Taylor Jared M.、Ikeda Ryuichi、Sugimoto Kunihisa、Fujiwara Akihiko、Chou Chien-Pin、Sakti Aditya Wibawa、Nishimura Yoshifumi、Nakai Hiromi、Kitagawa Hiroshi
    • Journal Title

      Nature Communications

      Volume: 11 Issue: 1 Pages: 843-843

    • DOI

      10.1038/s41467-020-14627-z

    • NAID

      120006796419

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A Novel Platinum(III)?Platinum(III) Neutral Dimer Complex, Pt2(cdtb)4I2 (cdtb: 4-Cyanodithiobenzoate)2019

    • Author(s)
      Moriyama Hayato、Otsubo Kazuya、Aoki Kentaro、Maesato Mitsuhiko、Sugimoto Kunihisa、Kitagawa Hiroshi
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 9 Pages: 1035-1037

    • DOI

      10.1246/cl.190355

    • NAID

      130007703014

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Network-Selectivity, Magnetism, and Proton Conduction of 2-D and 3-D Metal-Organic Frameworks of the Constituents {P(CH2OH)4}+/MII (MnII, FeII, or CoII)/[CrIII(ox)3]3?2019

    • Author(s)
      Okawa Hisashi、Yoshida Yukihiro、Otsubo Kazuya、Kitagawa Hiroshi
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 1 Pages: 623-628

    • DOI

      10.1021/acs.inorgchem.9b02861

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Synthesis of a wavy MX-tube complex2022

    • Author(s)
      Kazuya Otsubo、Hiroshi Kitagawa
    • Organizer
      日本化学会第102春季年会2022
    • Related Report
      2021 Annual Research Report
  • [Presentation] A platinum-dimer based metal-organic framework with a pre-installed protic cation for superprotonic conduction2021

    • Author(s)
      Kazuya Otsubo、Shuya Nagayama、Kunihisa Sugimoto、Shogo Kawaguchi、Hiroshi Kitagawa
    • Organizer
      錯体化学会第71回討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Size effect on spin-crossover behavior in 2D Hofmann-like metal-organic framework thin films2021

    • Author(s)
      Kazuya Otsubo, Shun Sakaida, Shogo Kawaguchi, Hiroshi Kitagawa
    • Organizer
      The 1st Asian Conference on Molecular Magnetism (ACMM)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] A platinum-dimer based metal-organic framework having a pre-installed cationic guest for proton conduction2021

    • Author(s)
      Kazuya Otsubo, Shuya Nagayama, Kunihisa Sugimoto, Shogo Kawaguchi, Hiroshi Kitagawa
    • Organizer
      日本化学会第101春季年会2021
    • Related Report
      2020 Research-status Report
  • [Presentation] 金属錯体ナノチューブの 疎水性空間における超プロトン伝導2020

    • Author(s)
      大坪 主弥、大竹 研一、北川 宏
    • Organizer
      第69回高分子討論会2020
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] Structural and Electronic Properties of MX-tube Complexes Dispersed in Organic Media2020

    • Author(s)
      Kazuya Otsubo, Kunihisa Sugimoto, Hiroshi Kitagawa
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 超プロトン伝導性を示す 多孔性金属錯体ナノチューブの化学2019

    • Author(s)
      大坪 主弥
    • Organizer
      第13回超分子若手懇談会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Coordination Nanomaterials Situated in Dimensional Crossover Region2019

    • Author(s)
      Kazuya Otsubo
    • Organizer
      Japan-Germany Bilateral Symposium on Surface-Attached Metal-Organic Framework
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 多孔性金属錯体ナノチューブの 疎水性空間における超プロトン伝導2019

    • Author(s)
      大坪 主弥
    • Organizer
      第4回固体化学フォーラム研究会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Ice-Tube Formation and High Proton Conduction in Metal-Organic Nanotubes2019

    • Author(s)
      Kazuya Otsubo
    • Organizer
      Nanjing University-Kyoto University Bilateral Workshop: Functional Molecular Materials
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] ナノサイズの空間に閉じ込められた水が示す不思議な性質を実証 -高速で水素イオンを運ぶ水の状態を解明-

    • URL

      http://www.kyoto-u.ac.jp/ja/research/research_results/2019/200218_1.html

    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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