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Mechanism of phase transition in proton-conductive inorganic solid acid salts studied by solid-state NMR

Research Project

Project/Area Number 15K05405
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Physical chemistry
Research InstitutionNational Institute of Advanced Industrial Science and Technology

Principal Investigator

HAYASHI Shigenobu  国立研究開発法人産業技術総合研究所, 計量標準総合センター, 招聘研究員 (00344185)

Research Collaborator JIMURA Keiko  
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords固体NMR / プロトン伝導 / 無機固体酸塩 / 相転移 / 水素結合
Outline of Final Research Achievements

Inorganic solid acid salt Cs2(HSO4)(H2PO4) showed high proton conductivity in the superprotonic phase above 370 K, and the phase was retained on cooling even at room temperature for a long period. These characteristic properties should correlate to the hydrogen bond network connecting the SO4 and PO4 groups. In the present work, the structures of the hydrogen bond network were studied by solid state NMR. We measured 31P, 1H and 133Cs magic-angle-spinning (MAS) NMR spectra, 31P static NMR spectra, 31P{1H} dipolar dephasing experiment, and 1H{31P} rotational-echo double resonance (REDOR). The 31P NMR spectra indicate that all the P sites are crystallographically equivalent. The 31P{1H} dipolar dephasing experiment strongly supports that the number of hydrogen bonds around the PO4 tetrahedron is four. The 1H and 133Cs MAS NMR spectra show that a part of the hydrogen bond network is disordered. Based on those NMR results, we proposed a model structure of the hydrogen bond network.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (15 results)

All 2018 2017 2016 2015

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (11 results)

  • [Journal Article] Hydrogen bond networks in Cs2(HSO4)(H2PO4) as studied by solid state NMR2017

    • Author(s)
      林 繁信、治村 圭子
    • Journal Title

      J. Phys. Chem. C

      Volume: 121 Issue: 23 Pages: 12643-12651

    • DOI

      10.1021/acs.jpcc.7b03824

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Detailed mechanisms of 1H spin-lattice relaxation in ammonium dihydrogen phosphate confirmed by magic angle spinning2017

    • Author(s)
      林 繁信、治村 圭子
    • Journal Title

      Solid State Nucl. Magn. Reson.

      Volume: 87 Pages: 24-28

    • DOI

      10.1016/j.ssnmr.2017.07.002

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Incorporation of ammonium ions in Cs2(HSO4)(H2PO4) confirmed by solid state NMR2017

    • Author(s)
      林 繁信、治村 圭子
    • Journal Title

      Solid State Ionics

      Volume: 311 Pages: 83-89

    • DOI

      10.1016/j.ssi.2017.09.015

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Spin diffusion and 1H spin-lattice relaxation in Cs2(HSO4)(H2PO4) containing a small amount of ammonium ions2017

    • Author(s)
      林 繁信、治村 圭子
    • Journal Title

      Solid State Nucl. Magn. Reson.

      Volume: 88 Pages: 15-21

    • DOI

      10.1016/j.ssnmr.2017.10.004

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] アンモニウムイオンで部分置換したCs2(HSO4)(H2PO4)におけるスピン拡散とスピン-格子緩和2018

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      2017度年計量標準総合センター成果発表会
    • Related Report
      2017 Annual Research Report
  • [Presentation] NH4H2PO4のスピン-格子緩和に対するマジック角回転の効果2017

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      慶應義塾大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Research-status Report
  • [Presentation] プロトン伝導性無機固体酸塩におけるNMRスピン-格子緩和とカチオン置換2017

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      2016度年計量標準総合センター成果発表会
    • Place of Presentation
      産業技術総合研究所つくばセンター(茨城県つくば市)
    • Year and Date
      2017-01-26
    • Related Report
      2016 Research-status Report
  • [Presentation] アンモニウムイオンで部分置換したCs2(HSO4)(H2PO4)におけるスピン拡散とスピン-格子緩和2017

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第56回NMR討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 超プロトン伝導体Cs2(HSO4)(H2PO4)へのアンモニウムイオンの導入2017

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第43回固体イオニクス討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 固体NMRによる、無機固体酸塩Cs2(HSO4)(H2PO4)の室温相における水素結合ネットワーク2016

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第42回固体イオニクス討論会
    • Place of Presentation
      名古屋国際会議場(愛知県名古屋市)
    • Year and Date
      2016-12-05
    • Related Report
      2016 Research-status Report
  • [Presentation] 無機固体酸塩Cs2(HSO4)(H2PO4)におけるアンモニウムイオン置換とスピン-格子緩和2016

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第55回NMR討論会
    • Place of Presentation
      広島国際会議場(広島県広島市)
    • Year and Date
      2016-11-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 水素結合系無機固体酸塩結晶のNMRシグナルにおけるアンモニウムイオンの緩和促進効果2016

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      日本化学会第96回春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス(京都府)
    • Year and Date
      2016-03-27
    • Related Report
      2015 Research-status Report
  • [Presentation] 固体NMRによるプロトン伝導性無機固体酸塩の水素結合ネットワークの解析2016

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      2015年計量標準総合センター成果発表会
    • Place of Presentation
      産業技術総合研究所つくばセンター(茨城県)
    • Year and Date
      2016-02-09
    • Related Report
      2015 Research-status Report
  • [Presentation] 無機固体酸塩Cs2(HSO4)(H2PO4)の室温相における水素結合とプロトンダイナミクス2015

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第41回固体イオニクス討論会
    • Place of Presentation
      北海道大学工学部(北海道)
    • Year and Date
      2015-11-26
    • Related Report
      2015 Research-status Report
  • [Presentation] プロトン伝導性無機固体酸塩Cs2(HSO4)(H2PO4)の室温相における水素結合2015

    • Author(s)
      林 繁信、治村 圭子
    • Organizer
      第54回NMR討論会
    • Place of Presentation
      千葉工業大学津田沼キャンパス(千葉県)
    • Year and Date
      2015-11-08
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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