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Development of metal complex/polysilsesquioxane hybrid for eco-friendly hydrogen generation

Research Project

Project/Area Number 16K17951
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Organic and hybrid materials
Research InstitutionHiroshima University (2017-2018)
Tokyo University of Science (2016)

Principal Investigator

Tsukada Satoru  広島大学, 工学研究科, 共同研究講座助教 (60632578)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2018: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords水素 / ヒドロゲナーゼ / モデル錯体 / 多核錯体 / ポリシルセスキオキサン / 有機無機ハイブリッド / プロトン伝導膜 / 有機無機ハイブリッド材料 / 錯体化学 / 鉄錯体
Outline of Final Research Achievements

Development of an eco-friendly hydrogen generation method is desired. In this study, iron-ruthenium trinuclear complex as a model complex of the active site of hydrogenase was successfully synthesized. Crystal structures and electrochemical properties were investigated. Model complex/Nafion-polysiloxane composite electrode was also prepared. This electrode was used to generate hydrogen in the presence of acetic acid by electrochemical reduction.

Academic Significance and Societal Importance of the Research Achievements

ハーバー・ボッシュ法によるアンモニア合成などの工業的用途に加え、燃料電池の原料やロケット燃料として、水素はクリーンな次世代エネルギーである。現在の水素生成は化石燃料に大きく依存し、環境負荷が高いため、低環境負荷な水素発生方法の開発が求められている。本研究では、自然界で水素を生成している酵素ヒドロゲナーゼの活性部位を模倣した金属錯体の合成、およびこの錯体を担持した電極を用いることで、電気化学的還元により酢酸存在下で水素を発生させることに成功した。温和な条件で水素を発生できる本手法は、次世代の水素発生方法の一つになる可能性を秘めている。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (56 results)

All 2019 2018 2017 2016

All Journal Article (11 results) (of which Peer Reviewed: 11 results,  Open Access: 1 results,  Acknowledgement Compliant: 1 results) Presentation (44 results) (of which Int'l Joint Research: 13 results,  Invited: 5 results) Book (1 results)

  • [Journal Article] 2-Triethoxysilylazulene derivatives: Syntheses and optical properties, and hydrolysis-condensation of 2-triethoxysilylazulene2019

    • Author(s)
      Hayami Ryohei、Izumiya Tetsuro、Kokaji Takashi、Nakagawa Hajime、Tsukada Satoru、Yamamoto Kazuki、Gunji Takahiro
    • Journal Title

      Journal of Sol-Gel Science and Technology

      Volume: 印刷中 Issue: 2 Pages: 399-406

    • DOI

      10.1007/s10971-019-04991-8

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation and characterization of stable DQ silicone polymer sols2018

    • Author(s)
      Hayami Ryohei、Nishikawa Izumi、Hisa Takayuki、Nakashima Hiroaki、Sato Yohei、Ideno Yuzuko、Sagawa Takuya、Tsukada Satoru、Yamamoto Kazuki、Gunji Takahiro
    • Journal Title

      Journal of Sol-Gel Science and Technology

      Volume: 88 Issue: 3 Pages: 660-670

    • DOI

      10.1007/s10971-018-4839-z

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Zinc-diethanolamine complex: synthesis, characterization, and formation mechanism of zinc oxide via thermal decomposition2018

    • Author(s)
      Hayami Ryohei、Endo Nagato、Abe Takayuki、Miyase Yuta、Sagawa Takuya、Yamamoto Kazuki、Tsukada Satoru、Gunji Takahiro
    • Journal Title

      Journal of Sol-Gel Science and Technology

      Volume: 87 Issue: 3 Pages: 743-748

    • DOI

      10.1007/s10971-018-4768-x

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Properties and surface morphologies of organic-inorganic hybrid thin films containing titanium phosphonate clusters2018

    • Author(s)
      Hayami Ryohei、Wada Keisuke、Miyase Yuta、Sagawa Takuya、Tsukada Satoru、Yamamoto Kazuki、Gunji Takahiro
    • Journal Title

      Polymer Journal

      Volume: 50 Issue: 12 Pages: 1169-1177

    • DOI

      10.1038/s41428-018-0108-9

    • NAID

      40021735629

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of Ruthenium Dithiolene Complex/Polysiloxane Films and Their Responses to CO Gas2018

    • Author(s)
      Satoru Tsukada, Takuya Sagawa, Kazuki Yamamoto, Takahiro Gunji
    • Journal Title

      Molecules

      Volume: 23 Issue: 4 Pages: 845-845

    • DOI

      10.3390/molecules23040845

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis, characterization and properties of titanium phosphonate clusters2018

    • Author(s)
      Ryohei Hayami, Takuya Sagawa, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Journal Title

      Polyhedron

      Volume: 147 Pages: 1-8

    • DOI

      10.1016/j.poly.2018.02.030

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and reactivity of hydride-bridged ruthenium dithiolene complexes2018

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Journal Title

      Polyhedron

      Volume: 139 Pages: 196-200

    • DOI

      10.1016/j.poly.2017.10.023

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Structure and Electrochemical Properties of a Ruthenium-Diiron Dithiolene Complex2017

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2017 Issue: 32 Pages: 3823-3828

    • DOI

      10.1002/ejic.201700783

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Preparation and properties of organic-inorganic hybrid materials using titanium phosphonate cluster2017

    • Author(s)
      Ryohei Hayami, Keisuke Wada, Izumi Nishikawa, Takuya Sagawa, Kazuki Yamamoto, Satoru Tsukada, Takahiro Gunji
    • Journal Title

      Polym. J.

      Volume: 49 Issue: 9 Pages: 665-669

    • DOI

      10.1038/pj.2017.34

    • NAID

      40021299670

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Fine Electronic State Tuning of Cobaltadithiolene Complexes by Substituent Groups on the Benzene Ring2016

    • Author(s)
      sukada, S.; Kondo, M.; Sato, H.; Gunji, T
    • Journal Title

      Polyhedron

      Volume: 117 Pages: 265-272

    • DOI

      10.1016/j.poly.2016.05.062

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Highly distorted octahedral molybdenum(II) complexes: synthesis, crystal structures, and properties of [Mo(S2C6H4)(CO)2(PMenPh3-n)2] (n = 0-3)2016

    • Author(s)
      Satoru Tsukada, Naoya Abe, and Takahiro Gunji
    • Journal Title

      Polyhedron

      Volume: 117 Pages: 73-79

    • DOI

      10.1016/j.poly.2016.05.035

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] プロトン還元能を有する鉄錯体/プロトン伝導体コンポジットフィルムの調製と性質2018

    • Author(s)
      渡辺雄,塚田学,山本一樹,郡司天博
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 鉄-モリブデンジチオレン二核錯体の合成と性質2018

    • Author(s)
      阿部高之,塚田学,山本一樹,郡司天博
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 酸化亜鉛担持バルク状多孔性シリカの調製と脱硫剤への応用2018

    • Author(s)
      大箸雅大,山本一樹,塚田学,郡司天博
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Preparation of Ruthenium Dithiolene Complex/Polysiloxane Films and Their Responses to CO Gas2018

    • Author(s)
      Satoru Tsukada, Takuya Sagawa, Takahiro Gunji
    • Organizer
      The 12th SPSJ International Polymer Conference (IPC 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Development of thermal insulation materials based on bridged polysilsesquioxane2018

    • Author(s)
      Yuki Nakanishi, Satoru Tsukada, Takayoshi Ishimoto, Hiroyuki Kai, Kenta Okada, Yohei Adachi, Joji Oshita
    • Organizer
      The 12th SPSJ International Polymer Conference (IPC 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Preparation of polysilsesquioxane bearing phosphonic acid anchoring titanium dioxide for self-cleaning film2018

    • Author(s)
      Ryohei Hayami, Wataru Nakamoto, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Organizer
      The 12th SPSJ International Polymer Conference (IPC 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 架橋型ポリシルセスキオキサンを用いた断熱材料の開発2018

    • Author(s)
      中西佑樹,塚田学,石元孝佳,甲斐裕之,岡田健太,安達洋平,大下浄治
    • Organizer
      第67回高分子討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 架橋型ポリシルセスキオキサンをベースとした断熱材料の開発2018

    • Author(s)
      中西佑樹,塚田学,甲斐裕之,安達洋平,大下浄治,石元孝佳,岡田健太
    • Organizer
      日本セラミックス協会第31回秋季シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 酸化亜鉛担持バルク状メソポーラスシリカの調製と性質2018

    • Author(s)
      郡司天博,大箸雅大,塚田学,山本一樹
    • Organizer
      日本セラミックス協会第31回秋季シンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 中空粒子を含む架橋型ポリシルセスキオキサン自立膜の調製および熱特性評価2018

    • Author(s)
      中西佑樹,塚田学,甲斐裕之,安達洋平,大下浄治,石元孝佳,岡田健太
    • Organizer
      日本ゾル-ゲル学会第16回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Synsthesis and properties of Fe-Mo dithiolene complexes2018

    • Author(s)
      Takayuki Abe, Naoya Abe, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Organizer
      43rd International Conference of Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Preparation of Free-standing Films from Bridged Polysilsesquioxanes and Their Thermal Properties2018

    • Author(s)
      Satoru Tsukada
    • Organizer
      10th US-Japan Hybrid Materials Workshop
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and reactivity of ruthenium complex containing benzene-dithiolate ligand2018

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] メタラジチオレン錯体を側鎖部位に有するπ共役系化合物の合成2018

    • Author(s)
      加藤 歩, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] コラニュレンを骨格に有するメタラジチオレン錯体の合成2018

    • Author(s)
      久保 貴裕, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 1-ホスファアズレンの合成2018

    • Author(s)
      岡本 康平, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 蟻酸を用いた側鎖官能性ポリシルセスキオキサンの合成2018

    • Author(s)
      鈴木 雄大, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] アズレンを側鎖に持つカゴ型シルセスキオキサンの合成2018

    • Author(s)
      小梶 隆史, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] アルコキシシランと塩化鉄を用いたカゴ型シルセスキオキサンの合成2018

    • Author(s)
      小川 拓也, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 水素生成を目指した金属錯体/プロトン伝導体ハイブリッドの調製2018

    • Author(s)
      武正 翠, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 酸化亜鉛を担持したバルク状多孔性シリカの調製と応用2018

    • Author(s)
      大箸 雅大, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 鉄-モリブデンジチオレン二核錯体の合成と構造2018

    • Author(s)
      阿部 高之, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Preparation of metal complex-containing polysiloxane or polysilsesquioxane films2017

    • Author(s)
      Satoru Tsukada
    • Organizer
      19th International Sol-Gel Conference
    • Place of Presentation
      リエージュ(ベルギー)
    • Year and Date
      2017-09-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] 金属錯体およびクラスターを用いたハイブリッド材料の開発2017

    • Author(s)
      塚田学
    • Organizer
      日本セラミックス協会2017年年会サテライトプログラム
    • Place of Presentation
      日本大学駿河台キャンパス(東京都・千代田区)
    • Year and Date
      2017-03-17
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] メタラジチオレン錯体を側鎖部位に有するπ共役系高分子化合物の合成2017

    • Author(s)
      加藤歩, 塚田学, 郡司天博
    • Organizer
      日本化学会第97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
      2017-03-17
    • Related Report
      2016 Research-status Report
  • [Presentation] ヘテロール類を配位子とするメタラジチオレン錯体の合成2017

    • Author(s)
      渡辺翼, 塚田学, 郡司天博
    • Organizer
      日本化学会第97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
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] かご型シルセスキオキサンを置換基としたメタラジチオレン錯体の合成検討2017

    • Author(s)
      渡辺朱音, 塚田学, 郡司天博
    • Organizer
      日本化学会第97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
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 架橋ヒドリドを有するルテニウム二核ジチオレン錯体の合成2017

    • Author(s)
      佐川拓矢, 塚田学, 郡司天博
    • Organizer
      日本化学会第97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
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Development of Polymeric Materials with Metalladithiolene Complexes as Element Block2017

    • Author(s)
      Satoru Tsukada
    • Organizer
      THE 2nd INTERNATIONAL SYMPOSIUM ON POLYMERIC MATERIALS BASED ON ELEMENT-BLOCKS
    • Place of Presentation
      京都工芸繊維大学(京都府・京都市)
    • Year and Date
      2017-01-18
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] 1-アザアズレンとアズレンからなる直線状分子の合成2017

    • Author(s)
      大津 渓杜, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      第47回複素環化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ゾル・ゲル法による白金担持メソポーラスシリカの調製2017

    • Author(s)
      郡司 天博, 鈴木 遥, 塚田 学
    • Organizer
      日本セラミックス協会 第30回秋季シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis and properties of Fe-Mo dithiolene complexes2017

    • Author(s)
      阿部 高之, 山本 一樹, 塚田 学, 郡司 天博
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis and reactivity of ruthenium dithiolene complexes including bridged hydride2017

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Kazuki Yamamoto, Takahiro Gunji
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis of group 9 metalladithiolene complexes including corannulene framework2017

    • Author(s)
      久保 貴裕, 塚田 学, 山本 一樹, 郡司 天博
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Preparation of metal complex-containing polysiloxane or polysilsesquioxane films2017

    • Author(s)
      Satoru Tsukada, Takuya Sagawa, Midori Takemasa, Takahiro Gunji
    • Organizer
      19th International Sol-Gel Conference
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and properties of cage octasilicate polymers cross-linked by alcohols2017

    • Author(s)
      Takahiro Igarashi, Tkahiro Gunji, Satoru Tsukada
    • Organizer
      19th International Sol-Gel Conference
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Preparation of organic-inorganic hybrid polymer films using [Ti4(μ3-O)(OiPr)3(μ-OiPr)3(PhPO3)3]・thf2017

    • Author(s)
      Tkahiro Gunji, Satoru Tsukada, Ryohei Hayami, Keisuke Wada
    • Organizer
      19th International Sol-Gel Conference
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] COガスと反応する金属錯体/ポリシロキサンハイブリッド自立膜の調製2017

    • Author(s)
      塚田 学
    • Organizer
      シミュレーション研究会キックオフシンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] 元素ブロックとしてのメタラジチオレン錯体、アズレンおよびアザアズレン誘導体2016

    • Author(s)
      塚田学
    • Organizer
      第4回「元素ブロック」若手シンポジウム
    • Place of Presentation
      湯の宿木もれび(滋賀県・大津市)
    • Year and Date
      2016-12-08
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] 金属錯体を元素ブロックとした高分子材料の開発2016

    • Author(s)
      塚田学
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学横浜キャンパス(神奈川県・横浜市)
    • Year and Date
      2016-09-16
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Structure and electrochemical properties of iron-ruthenium trinuclear dithiolene complex2016

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Takahiro Gunji
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学七隈キャンパス(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] Electronic state control of nine group metalladithiolene complexes by ligands2016

    • Author(s)
      Tsubasa Watanabe, Masataka Kondo, Satoru Tsukada, Takahiro Gunji
    • Organizer
      42st International Conference of Coordination Chemistry
    • Place of Presentation
      ブレスト(フランス)
    • Year and Date
      2016-07-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and properties of Fe-Ru trinuclear dithiolene complex2016

    • Author(s)
      Takuya Sagawa, Satoru Tsukada, Takahiro Gunji
    • Organizer
      42st International Conference of Coordination Chemistry
    • Place of Presentation
      ブレスト(フランス)
    • Year and Date
      2016-07-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis and properties of Fe-Mo dinuclear dithiolene complexes2016

    • Author(s)
      Satoru Tsukada, Naoya Abe, Takahiro Gunji
    • Organizer
      42st International Conference of Coordination Chemistry
    • Place of Presentation
      ブレスト(フランス)
    • Year and Date
      2016-07-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Book] “Metalloxane Cage Compounds as an Element-Block” edited by Yoshiki Chujo, “New Polymeric Materials Based on Element-Blocks”2019

    • Author(s)
      Takahiro Gunji, Satoru Tsukada
    • Total Pages
      444
    • Publisher
      Springer Singapore
    • ISBN
      9789811328886
    • Related Report
      2018 Annual Research Report

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Published: 2016-04-21   Modified: 2020-03-30  

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