Studies of Hydrogen Storage in Small Single Crystal and New Functionality by Micro-coil NMR for μg samples

• Project/Area Number: 18350002
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Hokkaido University
• Principal Investigator: TAKEDA Sadamu Hokkaido University, 大学院・理学研究院, 教授 (00155011)
• Co-Investigator(Kenkyū-buntansha): MARUTA Goro 北海道大学, 大学院・理学研究院, 助教 (00333592)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,250,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥2,550,000); Fiscal Year 2008: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2007: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2006: ¥6,200,000 (Direct Cost: ¥6,200,000)
• Keywords: 水素貯蔵物質 / 有機・金属錯体結晶 / 微小試料核磁気共鳴分析法の開発 / 水素分子と貯蔵物質との引力 / 水素分子の量子性と熱運動 / 水素吸蔵錯体 / 固体NMR / 中性子非弾性散乱 / マイクロコイルNMR / 水素吸蔵物質 / 量子的運動 / 重水素 / オルソ・パラ重水素 / 分子性固体 / 物性実験 / 非線形ダイナミクス

Research Abstract

二酸化炭素を排出しないクリーンな燃料であり、かつ場合によっては爆発する危険性を持った水素ガスを安全に貯蔵・運搬できる新規な物質について、水素貯蔵のメカニズムおよび吸蔵状態の基礎研究を行った。水素ガス一気圧下で銅イオンもしくはロジウムイオンと有機分子で構成され、1gあたり40~50mlの水素ガスを吸蔵する物質について、中性子を用いた分光法や安定同位体である重水素分子(2H2またはD2で示す)の核磁気共鳴分光法により、水素ガスを吸蔵・貯蔵できる錯体物質の特異な性質の解明と取り込まれた水素分子の動きや量子論的挙動を詳しく調べ、さらに多くの水素ガスを安全に貯蔵できる物質開発への指針を得た。また、微量な試料でも検査できるマイクロコイル核磁気共鳴分光法の開発を行い、水素吸蔵以外でも新規な磁性(磁場応答)、誘電性(電場応答)の特異な挙動を示す物質の基礎研究を行った。

Research Products

• [Journal Article] Ferroelectricity and polarity control in solid state flipflop supramolecular rotators (2009)
  • Author(s): T. AKUTAGAWA, H. KOSHINAKA, D.SATO, S. TAKEDA, 他
  • Journal Title: Nature Materials 8 Pages: 342-347
  • Peer Reviewed
• [Journal Article] Ferroelectricity and polarity control in solid state flipflop supramole cular rotators (2009)
  • Author(s): T. AKUTAGAWA
  • Journal Title: Nature Materials 8 Pages: 342-347
  • Peer Reviewed
• [Journal Article] Determination of spin susceptibility and intrachain exchange interaction of S=1 / 2 one-dimensional antiferromagnetic Heisenberg chain [Cu(pydz)(OH)(NO3)]H20 by solid-state high-resolution NMR (2009)
  • Author(s): Tetsuya Yamada
  • Journal Title: Polyhedron (Published ON LINE)
  • Peer Reviewed
• [Journal Article] Electron Spin Density Distribution of a Series of Nitroxide Radicals with Five Member Ring as Studied by Solid-State 1^H, 2^H and <13>^C NMR (2009)
  • Author(s): Y. Kawahashi
  • Journal Title: Polyhedron (Published ON LINE)
  • Peer Reviewed
• [Journal Article] Solid-state molecular rotators of anilinium and adamantylammoniumin[Ni(dmit)(2)](-)salts with diverse magnetic properties (2008)
  • Author(s): T. Akutagawa, 他, S. Takeda, T. Nakamura
  • Journal Title: Inorg. Chem. 47 Pages: 5951-5962
  • Peer Reviewed
• [Journal Article] Metal-organic Coordination Architectures with 3-Pyridin-3-yl-benzoate : Crystal Structures, Fluorescent Emission and Magnetic Properties (2008)
  • Author(s): R-Q. Zhong, 他, G. Maruta, S. Takeda, Q. Xu
  • Journal Title: Cryst. Eng. Comm. 10 Pages: 605-613
  • Peer Reviewed
• [Journal Article] Controllable preparation, network structures and properties of unusual metal-organic frameworks constructed from 4, 4'-(hexafluoroisopropylidene)diphthalic acid and 4, 4'-bipyridyl (2008)
  • Author(s): R-Q. Zhong, 他, G. Maruta, S.Takeda, Q. Xu
  • Journal Title: Dalton Trans. Pages: 2346-2354
  • Peer Reviewed
• [Journal Article] Preparation, crystal structure and properties of a novel microporous CuIIcoordination polymer with 6-quinolinecarboxylate (2008)
  • Author(s): M. Du, 他, S. Takeda, Q. Xu
  • Journal Title: Inorg. Chim. Acta 361 Pages: 1827-1831
  • Peer Reviewed
• [Journal Article] Microporous coordination polymers ofcobalt(II)and manganese(II)2, 6-naphthalenedicarboxylate : preparations, structures and gas sorptive and magnetic properties (2008)
  • Author(s): B. Liu, 他, G. Maruta, S. Takada,Q. Xu
  • Journal Title: Micropor. Mesopor. Mat. 111 Pages: 470-477
  • Peer Reviewed
• [Journal Article] A solid-state supramolecular rotator assembled front a Cs-crown ether polyoxometalate hybrid : (Cs+)(3)([18]crown-6)(3)(H+)(2)[PMo12O40] (2008)
  • Author(s): T. Akutagawa, 他, S. Takeda, L.Cronin, T. Nakamura
  • Journal Title: CRYSTAL GROWTH & DESIGN 8 Pages: 812-816
  • Peer Reviewed
• [Journal Article] A solid-state supramolecular rotator assembled front a Cs-crown ether polyoxometalate hybrid : (Cs^+)(3)([18]crown-6)(3)(H^+)(2)[PMo_<12>O_<40>] (2008)
  • Author(s): T. Akutagawa
  • Journal Title: CRYSTAL GROWTH & DESIGN 8 Pages: 812-816
  • Peer Reviewed
• [Journal Article] Microporous coordination polymers of cobalt(II) and manganese(II) 2, 6 -naphthalenedicarboxylate : preparations, structures and gas sorptive and magnetic properties (2008)
  • Author(s): Bo Liu
  • Journal Title: Micropor. Mesopor. Mat. 111 Pages: 470-477
  • Peer Reviewed
• [Journal Article] Preparation, crystal structure and properties of a novel microporous Cu^<II>coordination polymer with 6-quinolinecarboxylate (2008)
  • Author(s): Miao Du
  • Journal Title: Inorg. Chim. Acta 361 Pages: 1827-1831
  • Peer Reviewed
• [Journal Article] Controllable preparation, network structures and properties of unusual metal-organic frameworks constructed from 4, 4'-(hexafluoroisopropylidene)diphthalic acid and 4, 4'-bipyridyl (2008)
  • Author(s): Rui-Qin Zhong
  • Journal Title: Dalton Trans. 2008 Pages: 2346-2354
  • Peer Reviewed
• [Journal Article] Metal-organic Coordination Architectures with 3-Pyridin-3-yl-benzoate : Crystal Structures, Fluorescent Emission and Magnetic Properties (2008)
  • Author(s): Rui-Qin Zhong
  • Journal Title: Cryst. Eng. Comm. 10 Pages: 605-613
  • Peer Reviewed
• [Journal Article] Solid-state molecular rotators of anilinium and adamantylammonium in [Ni(dmit)(2)](-) salts with diverse magnetic properties (2008)
  • Author(s): T. Akutagawa
  • Journal Title: Inorg. Chem. 47 Pages: 5951-5962
  • Peer Reviewed
• [Journal Article] Multi Rotations of(Anilinium+)([18]crown-6)Supramolecular Cation Structure in Magnetic [Ni(dmit)2]-Salt (2007)
  • Author(s): S. Nishihara, T. Akutagawa, D. Sato, S. Takeda, S. Noro, and T. Nakamura
  • Journal Title: Chemistry-an Asian Journal 2 Pages: 1083-1090
  • Peer Reviewed
• [Journal Article] Mixed-Valence States Stabilized by Proton Transfer in a Hydrogen-Bonded Biimidazolate Rhenium Dimer (2007)
  • Author(s): M. Tadokoro, 他, S. Takeda, 他
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5938-5942
  • Peer Reviewed
• [Journal Article] Spin and charge fluctuation occurringin valence tautomerism and cooperative effects in the solid-state (2007)
  • Author(s): Y. Kadohashi, G. Maruta and S.Takeda
  • Journal Title: Polyhedron 26 Pages: 2342-2346
  • Peer Reviewed
• [Journal Article] Spin and charge fluctuation occurring in valence tautomerism and cooperative effects in the solid-state (2007)
  • Author(s): Yusuke Kadohashi
  • Journal Title: Polyhedron 26 Pages: 2342-2346
  • Peer Reviewed
• [Journal Article] Multi Rotations of(Anilinium^+)([181crown-6)Supramolecular Cation Structure in Magnetic[Ni(dmit)_2]^- Salt (2007)
  • Author(s): Sadafumi Nishihara
  • Journal Title: Chemistry-an Asian Journal 2 Pages: 1083-1090
  • Peer Reviewed
• [Journal Article] Mixed-Valence States Stabilized by Proton Transfer in a Hydrogen-Bonded Biimidazolate Rhenium Dimer (2007)
  • Author(s): M. Tadokoro
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5938-5942
  • Peer Reviewed
• [Journal Article] Supramolecular Rotor: Adamantylammonium([18]crown-6)in[Ni(dmit)2]-Salt. (2007)
  • Author(s): D. Sato
  • Journal Title: Inorg. Chem. 46 Pages: 363-365
  • Peer Reviewed
• [Journal Article] Supramolecular Rotor : Adamantylammonium([18]crown-6) in [Ni(dmit)2]-Salt (2007)
  • Author(s): D.Sato, T.Akutagawa, S.Takeda, S.Noro, T.Nakamura
  • Journal Title: Inorganic Chemistry 46 Pages: 363-365
• [Journal Article] Spin and charge fluctuation occurring in valence tautomerism and cooperative effects in the solid-state (2007)
  • Author(s): Yusuke Kadohashi, Goro Maruta, Sadamu Takeda
  • Journal Title: Polyhedron available on line
• [Presentation] 一次元金属錯体結晶に吸蔵されたH2、D2分子の挙動 : 固体NMRおよび中性子非弾性散乱による研究 (2009)
  • Author(s): 武田定
  • Organizer: 日本化学会第89春季年会(日本大学理工学部船橋キャンパス)
  • Place of Presentation: 千葉
• [Presentation] 一次元金属錯体結晶に吸蔵されたH_2、D_2分子の挙動 : 固体NMRおよび中性子非弾性散乱による研究 (2009)
  • Author(s): 武田定
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス
• [Presentation] 固体NMRでみるトリアゾール配位銅錯体の磁気特性 (2009)
  • Author(s): 山田哲也
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス
• [Presentation] 固体NMRによる配位高分子錯体の重水素吸蔵状態の解明 (2008)
  • Author(s): 武内大隼
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-29
• [Presentation] 低次元金属錯体のガス吸着特性 (2008)
  • Author(s): 野呂真一郎
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-29
• [Presentation] トリアゾール配位子を持つ銅(II)錯体の三次元ネットワーク構造と物性 (2008)
  • Author(s): 山田哲也
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-27
• [Presentation] 強誘電超分子ローター構造を含む[Ni(dmit)_2】塩の物性 (2008)
  • Author(s): 芥川智行
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-26
• [Presentation] 配位高分子錯体に取り込まれた水素の動的挙動に関する研究 (2008)
  • Author(s): 武田定
  • Organizer: 分子化学討論会
  • Place of Presentation: 福岡国際会議場福岡
• [Presentation] 固体NMRによる配位高分子錯体の重水素吸蔵状態の解明 (2008)
  • Author(s): 武田定
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学池袋キャンパス東京
• [Presentation] Determination of spin susceptibility and intrachain exchange interaction of S=1 / 2 one-dimensional antiferromagnetic Heisenberg chain [Cu(pydz)(OH)(NO3)1H20 by solid-state high-resolution NMR (2008)
  • Author(s): 山田哲也
  • Organizer: The 11th International Conference on Molecule-based Magnets
  • Place of Presentation: フローレンス、イタリア
• [Presentation] Electron Spin Density Distribution of a Series of Nitroxide Radicals with Five Member Ring as Studied by Solid-State 1^H, 2^H and 13^C NMR (2008)
  • Author(s): 武田定
  • Organizer: The 11th International Conference on Molecule-based Magnets
  • Place of Presentation: フローレンス、イタリア
• [Presentation] 銅三核錯体エCu_3(trz)_3(μ3-O)X_2]H_3O+5H_2O(X=Cl,Br,0. 5SO4)の局所構造の解明 (2008)
  • Author(s): 山田哲也
  • Organizer: 分子科学討論会
  • Place of Presentation: 福岡
• [Presentation] 配位高分子錯体に取り込まれた水素の動的挙動に関する研究 (2008)
  • Author(s): 武内大隼
  • Organizer: 分子科学討論会
  • Place of Presentation: 福岡
• [Presentation] 反強磁性体ナノ粒子の表面効果による磁気的な特異性 (2008)
  • Author(s): 中村泰規
  • Organizer: 分子科学討論会
  • Place of Presentation: 福岡
• [Presentation] 配位高分子錯体への重水素吸蔵状態の固体NMR による研究 (2007)
  • Author(s): 武田定
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-20
• [Presentation] 不飽和五員環骨格構造を持つ有機ラジカル及びその金属錯体の電子スピン密度分布 (2007)
  • Author(s): 川橋保大
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-20
• [Presentation] 固体高分解能2H-NMR で見るCo(phen)(3,5-BQ)2 の原子価互変異性 (2007)
  • Author(s): 角橋祐介
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-20
• [Presentation] 【Fe2(PMAT)2】(BF)(BF4)4・DMF のスピンクロスオーバー現象の固体NMRによる研究 (2007)
  • Author(s): 黒島寛
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-19
• [Presentation] 三核クラスター骨格を持つトリアゾール架橋銅(II)錯体の結晶構造と磁気的性質 (2007)
  • Author(s): 山田哲也
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-19
• [Presentation] 原子価互変異性を示すtrans-Mn(o-benzoquinone)錯体の電子状態 (2007)
  • Author(s): 丸田悟朗
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-18
• [Presentation] ポリマー被覆された反強磁性体ナノ粒子NH4MnF3 の磁気的性質と緩和現象 (2007)
  • Author(s): 中村泰規
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-18
• [Presentation] 1H, 2-NMR スペクトルで見るMpy2Cl2 (M=Co, Cu)の電子スピン密度分布 (2007)
  • Author(s): 村上裕太
  • Organizer: 分子科学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-17
• [Presentation] 配位高分子錯体への重水素吸蔵状態の固体NMRによる研究 (2007)
  • Author(s): 丸田悟朗
  • Organizer: 分子科学討論会
  • Place of Presentation: 東北大学仙台
• [Presentation] 固体NMRによる配位高分子錯体への重水素吸蔵状態の解明 (2007)
  • Author(s): 武田定
  • Organizer: 第46回NMR討論会
  • Place of Presentation: 札幌コンベンションセンター札幌
• [Presentation] 固体高分解能NMRで見る1次元磁性銅(II)錯体の磁気的性質 (2007)
  • Author(s): 山田哲也
  • Organizer: 第46回NMR討論会
  • Place of Presentation: 札幌
• [Presentation] 固体NMRによる配位高分子錯体への重水素吸蔵状態の解明 (2007)
  • Author(s): 武内大隼
  • Organizer: 第46回NMR討論会
  • Place of Presentation: 札幌
• [Presentation] 固体NMRによる[Fe(bpy)2(CN)4Cu2]のスピンクロスオーバー現象の研究 (2007)
  • Author(s): 黒島寛之
  • Organizer: 第46回NMR討論会
  • Place of Presentation: 札幌
• [Presentation] ポリマー被覆された反強磁性体の表面スピンによる磁気的特異性 (2007)
  • Author(s): 中村泰規
  • Organizer: 第46回NMR討論会
  • Place of Presentation: 札幌
• [Remarks]
  • URL: http://barato.sci.hokudai.ac.jp/~ekitai/index.html