Development of solid proton conducting materials based on local structure analysis

• Project/Area Number: 26286002
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Nanostructural chemistry
• Research Institution: Kanazawa University
• Principal Investigator: Mizuno Motohiro 金沢大学, 新学術創成研究機構, 教授 (70251915)
• Co-Investigator(Kenkyū-buntansha): 井田 朋智 金沢大学, 物質化学系, 准教授 (30345607) ; 大橋 竜太郎 金沢大学, 物質化学系, 助教 (50533577)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥16,640,000 (Direct Cost: ¥12,800,000、Indirect Cost: ¥3,840,000); Fiscal Year 2016: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2014: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
• Keywords: ナノ構造化学 / プロトン伝導体 / 固体NMR / 分子運動 / 水素結合 / 高分子 / 複合材料・物性 / 高分子構造・物性 / 物性実験 / 燃料電池

Outline of Final Research Achievements

In the present work, the detailed analysis of local structure and dynamics in the proton conducting organic crystals and polymer composites including imidazole were performed to elucidate the mechanism of proton conduction. We tried to develop high proton conducting materials using material design based on the information of local structure and proton conduction mechanism. The isotropic rotation of imidazole molecule was found to play an important role in proton conduction. So simulation method of deuteron NMR spectrum for detailed analysis of isotropic rotation of proton carrier molecules was developed. The high proton conduction materials were obtained by improving mobility of imidazole molecule.

Research Products

• [Journal Article] 19F/119Sn/207Pb NMR Studies on Ion Dynamics in Tetragonal PbSnF4; Spectroscopic Evidence for Defect-Driven Conductivity (2017)
  • Author(s): M. Murakami, Y. Morita, M. Mizuno
  • Journal Title: J. Phys. Chem. C Volume: 121 Issue: 5 Pages: 2627-2634
  • DOI: 10.1021/acs.jpcc.6b13053
  • Peer Reviewed
• [Journal Article] Structure and Dynamic Behavior of Na-Diglyme Complex in the Graphite Anode of Sodium Ion (2016)
  • Author(s): K. Gotoh, H. Maruyama, T. Miyatou, M. Mizuno, K. Urita, H. Ishida
  • Journal Title: J. Phys. Chem. C Volume: 120 Issue: 49 Pages: 28152-28156
  • DOI: 10.1021/acs.jpcc.6b10962
  • Peer Reviewed
• [Journal Article] Phase Transition Behavior of Hydrogen bonded Liquid Crystal (6BA)2-(BPy)x as Studied by (2016)
  • Author(s): M. Mizuno, K. Tabota, T. Oigawa, T. Miyatou, Y. Kumagai, R. Ohashi, T. Ida
  • Journal Title: Hyperfine Interact. Volume: 237 Issue: 1 Pages: 135-135
  • DOI: 10.1007/s10751-016-1324-3
  • Peer Reviewed
• [Journal Article] An NMR Study on the Mechanisms of Freezing and Melting of Water Confined in Spherically Mesoporous Silicas SBA-16 (2016)
  • Author(s): T. Miyatou, R. Ohashi, T. Ida, S. Kittaka, M. Mizuno
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 18 Issue: 27 Pages: 18555-18562
  • DOI: 10.1039/c6cp03111k
  • Peer Reviewed
• [Journal Article] Coronene-Based Charge-Transfer Complexes (2016)
  • Author(s): Y. Yoshida, K. Isomura, Y. Kumagai, M. Maesato, H. Kishida, M. Mizuno, G. Saito
  • Journal Title: J. Phys. Condens. Matter Volume: 28 Pages: 304001-304001
  • Peer Reviewed
• [Journal Article] Unraveling Inter- and Intra-chain Electronics in Polythiophene Assemblies Mediated by Coordination Nanospaces (2016)
  • Author(s): Michael W. A. MacLean, Takashi Kitao, Takeo Suga, Motohiro Mizuno, Shu Seki, Takashi Uemura, Susumu Kitagawa
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 2 Pages: 708-713
  • DOI: 10.1002/anie.201510084
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Proton Order－Disorder Phenomena in a Hydrogen-Bonded Rhodium－η5-Semiquinone Complex: A Possible Dielectric Response Mechanism (2015)
  • Author(s): Minoru Mitsumi, Kazunari Ezaki, Yuuki Komatsu, Koshiro Toriumi, Tatsuya Miyatou, Motohiro Mizuno, Nobuaki Azuma, Yuji Miyazaki, Motohiro Nakano, Yasutaka Kitagawa, Takayasu Hanashima, Ryoji Kiyanagi, Takashi Ohhara, and Kazuhiro Nakasuji
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 27 Pages: 9682-9696
  • DOI: 10.1002/chem.201500796
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Arrangement and Dynamics of Diamine, Etheric, and Tetraalkylammonium Intercalates within Graphene or Graphite Oxide Galleries by 2H NMR (2015)
  • Author(s): Kazuma Gotoh, Chika Sugimoto, Ryohei Morita, Tatsuya Miyatou, Motohiro Mizuno, Weekit Sirisaksoontorn, Michael M Lerner, and Hiroyuki Ishida
  • Journal Title: J. Phys. Chem. C Volume: 119 Issue: 21 Pages: 11763-11770
  • DOI: 10.1021/acs.jpcc.5b03016
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] 2H and 13C NMR studies of orientational order and actual amount of n-heptane molecule in liquid crystal phases of the 7CB-n-heptane system (2015)
  • Author(s): Y. Kumagai, R. Ohashi, T. Ida, and M. Mizuno
  • Journal Title: Chem. Phys. Lett. Volume: 639 Pages: 114-119
  • DOI: 10.1016/j.cplett.2015.08.073
  • Peer Reviewed
• [Journal Article] Improved Dynamic Properties of Charge-Transfer-Type Supramolecular Rotor Composed of Coronene and F4TCNQ (2015)
  • Author(s): Yukihiro Yoshida, Yoshihide Kumagai, Motohiro Mizuno, Kazuhide Isomura, Yuto Nakamura, Hideo Kishida, and Gunzi Saito
  • Journal Title: Crystal Growth & Design Volume: 15 Issue: 11 Pages: 5513-5518
  • DOI: 10.1021/acs.cgd.5b01138
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Local Structure and Molecular Motions in Imidazolium Hydrogen Malonate Crystal as Studied by 2H and 13C NMR (2015)
  • Author(s): M. Mizuno, M. Chizuwa, T. Umiyama, Y. Kumagai, T. Miyatou, R. Ohashi, T. Ida, M. Tansho, T. Shimizu
  • Journal Title: Hyperfine Interactions Volume: 230 Issue: 1-3 Pages: 95-100
  • DOI: 10.1007/s10751-014-1081-0
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Local Structure and Dynamics of Imidazole Molecules in Proton-Conducting Poly(vinylphosphonic acid)-Imidazole Composite Material (2014)
  • Author(s): M. Mizuno, A. Iwasaki, T. Umiyama, R. Ohashi, T. Ida
  • Journal Title: Macromolecules Volume: 47 Issue: 21 Pages: 7469-7476
  • DOI: 10.1021/ma5013418
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 固体NMRによるプロトン伝導性ジホスホン酸イミダゾリウム結晶の局所構造解析 (2017)
  • Author(s): 畝 亮太，不破寛規，大橋竜太郎，井田朋智，水野 元博
  • Organizer: 日本化学会 第97春季年会
  • Place of Presentation: 慶応義塾大学日吉キャンパス（横浜）
  • Year and Date: 2017-03-16
• [Presentation] プロトン伝導体 PVPA /xIm（x ≧ 2）におけるイミダゾールの運動性および局所構造 (2016)
  • Author(s): 成田貴光，大橋竜太郎，井田朋智，水野元博
  • Organizer: 第55回NMR討論会
  • Place of Presentation: 広島国際会議場（広島）
  • Year and Date: 2016-11-16
• [Presentation] 2H NMRによる黒鉛層間エーテル分子の構造および動的挙動の解析 (2016)
  • Author(s): 後藤和馬，丸山寿史，森田凌平，宮東達也，水野元博，瓜田幸幾，石田祐之
  • Organizer: 第55回NMR討論会
  • Place of Presentation: 広島国際会議場（広島）
  • Year and Date: 2016-11-16
  • Int'l Joint Research
• [Presentation] 固体NMRによるプロトン伝導性ジホスホン酸イミダゾリウム結晶の構造解析 (2016)
  • Author(s): 畝亮太，不破寛規，大橋竜太郎，井田朋智，水野元博
  • Organizer: 第55回NMR討論会
  • Place of Presentation: 広島国際会議場（広島）
  • Year and Date: 2016-11-16
  • Int'l Joint Research
• [Presentation] 23Na solid-state NMR analysis of hydration water around sodium ions in cellulose nanocrystal films (2016)
  • Author(s): R. Ohashi, C. Michal, H. Mehr,T. Nguyen, M. MacLachlan, W. Hamad, M. Mizuno
  • Organizer: 2nd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Place of Presentation: 石川県文教会館（金沢）
  • Year and Date: 2016-10-26
  • Int'l Joint Research
• [Presentation] Mobility and local structure of imidazole in proton conductor, PVPA / xIm (x ≧2) (2016)
  • Author(s): T. Narita, R. Ohashi, T. Ida, M. Mizuno
  • Organizer: 2nd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Place of Presentation: 石川県文教会館（金沢）
  • Year and Date: 2016-10-26
  • Int'l Joint Research
• [Presentation] Structural Change and Proton Conductivity of Imidazolium Sebacate Crystal (2016)
  • Author(s): M. Naruse, R. Yamagishi, R. Ohashi, T. Ida, M. Mizuno
  • Organizer: 2nd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Place of Presentation: 石川県文教会館（金沢）
  • Year and Date: 2016-10-26
  • Int'l Joint Research
• [Presentation] 固体ナトリウムＮＭＲによるセルロースナノ結晶フィルムの解析 (2016)
  • Author(s): 大橋竜太郎，Carl Michal，Mark MacLachlan，Wadood Hamad，水野元博
  • Organizer: 第60回固体NMR・材料フォーラム
  • Place of Presentation: 金沢商工会議所会館（金沢）
  • Year and Date: 2016-10-20
• [Presentation] ジホスホン酸イミダゾリウム結晶のプロトン伝導 (2016)
  • Author(s): 畝 亮太，不破寛規，大橋竜太郎，井田朋智，水野元博
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 神戸ファッションマート (神戸)
  • Year and Date: 2016-09-13
• [Presentation] Phase Transition Behavior of Hydrogen bonded Liquid Crystal (6BA)2-(BPy)x as Studied by 2H NMR (2016)
  • Author(s): M. Mizuno, K. Tabota, T. Oigawa, T. Miyatou, Y. Kumagai, R. Ohashi, T. Ida
  • Organizer: HYPERFINE 2016
  • Place of Presentation: Leuven (Belgium)
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Presentation] Relationship Between Local Structure of Imidazole and Proton Conductivity of Poly(vinyl phoshonic acid-Imidazole Composite (2016)
  • Author(s): Takamitsu Narita, Ayano Iwasaki, Ryutaro Ohashi, Tomonori Ida, Motohiro Mizuno
  • Organizer: International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Place of Presentation: 金沢大学
  • Year and Date: 2016-03-10
  • Int'l Joint Research
• [Presentation] Molecular Motion and Proton Conductivity of Imidazolium Diphosphonate Crystals (2016)
  • Author(s): R. Une, H. Fuwa, R. Ohashi, T. Ida, M. Mizuno
  • Organizer: 2nd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Place of Presentation: 石川県文教会館（金沢）
  • Int'l Joint Research
• [Presentation] デシルジホスホン酸イミダゾリウムのプロトン伝導 (2015)
  • Author(s): 不破寛規，大橋竜太郎，井田朋智, 水野元博
  • Organizer: 平成27年度北陸地区講演会
  • Place of Presentation: 金沢大学
  • Year and Date: 2015-11-27
• [Presentation] 固体NMRによるプロトン伝導性 poly（vinylphosphonic acid）-イミダゾール複合体中のイミダゾールの状態解析 (2015)
  • Author(s): 成田 貴光，岩崎 彩乃，大橋 竜太郎，井田 朋智，水野 元博
  • Organizer: 第54回NMR討論会
  • Place of Presentation: 千葉工業大学
  • Year and Date: 2015-11-06
• [Presentation] セバシン酸イミダゾリウム結晶におけるプロトン伝導性のヒステリシス (2015)
  • Author(s): 山岸諒, 大橋竜太郎, 井田朋智, 水野元博
  • Organizer: 第9回分子科学討論会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2015-09-16
• [Presentation] アルギン酸-イミダゾール複合体における分子の動的挙動とプロトン伝導 (2015)
  • Author(s): 近井琢磨, 大橋竜太郎, 井田朋智, 水野元博
  • Organizer: 第9回分子科学討論会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2015-09-16
• [Presentation] 透熱系におけるプロトンの量子ダイナミクス (2015)
  • Author(s): 堀優太，井田朋智, 水野元博
  • Organizer: 第9回分子科学討論会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2015-09-16
• [Presentation] 誘起スメクチック相を示す7CB/n-heptane混晶系の7CBとn-heptaneの配向性 (2015)
  • Author(s): 熊谷翼秀, 大橋竜太郎, 井田朋智, 水野元博
  • Organizer: 第9回分子科学討論会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2015-09-16
• [Presentation] 固体プロトン伝導性物質の局所構造とダイナミクスの解析 (2015)
  • Author(s): 水野 元博
  • Organizer: 第57回固体NMR・材料フォーラム
  • Place of Presentation: 理化学研究所横浜キャンパス
  • Year and Date: 2015-05-21
  • Invited
• [Presentation] セバシン酸イミダゾリウム結晶の分子運動とプロトン伝導性 (2015)
  • Author(s): 山岸 諒, 大橋 竜太郎, 井田 朋智, 水野 元博
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 日大船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 固体NMRによる機能性物質の局所構造と分子運動の解析 (2015)
  • Author(s): 水野 元博
  • Organizer: 岡山大学異分野融合研究育成支援事業 シンポジウム
  • Place of Presentation: 岡山大学
  • Year and Date: 2015-02-06
  • Invited
• [Presentation] アルギン酸-イミダゾール複合体の局所構造とプロトン伝導性 (2014)
  • Author(s): 近井 琢磨、 大橋 竜太郎、 井田 朋智、 水野 元博
  • Organizer: 第53回NMR討論会
  • Place of Presentation: 阪大コンベンションセンター
  • Year and Date: 2014-11-04 – 2014-11-06
• [Presentation] 高分子-イミダゾール複合体におけるイミダゾールの分子運動の解析 (2014)
  • Author(s): 近井 琢磨、 大橋 竜太郎、 井田 朋智、 水野 元博
  • Organizer: 第56回 固体ＮＭＲ・材料フォーラム
  • Place of Presentation: 兵庫県民会館 パルテホール
  • Year and Date: 2014-10-24
• [Presentation] Local Structure and Molecular Motions in Imidazolium Hydrogen Malonate Crystal as Studied by 2H and 13C NMR (2014)
  • Author(s): M. Mizuno, M. Chizuwa, T. Umiyama, R. Ohashi, T. Ida, M. Tansho, T. Shimizu
  • Organizer: The 5th Joint International Conference on Hyperfine Interactions and Symposium on Nuclear Quadrupole Interactions
  • Place of Presentation: キャンベラ（豪）
  • Year and Date: 2014-09-21 – 2014-09-26
• [Presentation] アルギン酸-イミダゾール複合体の分子ダイナミクスとプロトン伝導性 (2014)
  • Author(s): 近井琢磨, 大橋竜太郎, 井田朋智, 水野元博
  • Organizer: 分子科学討論会
  • Place of Presentation: 広大東広島キャンパス
  • Year and Date: 2014-09-21 – 2014-09-24
• [Presentation] セバシン酸イミダゾリウム結晶における分子運動とプロトン伝導性 (2014)
  • Author(s): 山岸 諒, 大橋 竜太郎, 井田 朋智, 水野 元博
  • Organizer: 分子科学討論会
  • Place of Presentation: 広大東広島キャンパス
  • Year and Date: 2014-09-21 – 2014-09-24
• [Book] 産業応用を目指した無機・有機新材料創製のための構造解析技術 (2015)
  • Author(s): 米澤徹，陣内浩司，紺谷貴之，竹中幹人，宮崎司，犬束学，田中敬二，一國伸之，一柳光平，野澤俊介，増田亮，瀬戸誠，鈴木宏正，松村晶，清野智志，藪浩，吉澤徳子，田中信夫，荒井重勇，水野元博 他
  • Total Pages: 11
  • Publisher: シーエムシー出版