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Fablication of chemical energy carrier system by fusion of non-precious metals

Research Project

Project/Area Number 16H04123
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionChuo University

Principal Investigator

Chang Ho-Chol  中央大学, 理工学部, 教授 (60335198)

Co-Investigator(Kenkyū-buntansha) 松本 剛  中央大学, 理工学部, 助教 (40564109)
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2018: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2017: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2016: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
Keywords水素 / 光水素発生 / エネルギーキャリア / 配位子 / 電子移動 / プロトン移動 / ハイドライド / 錯体 / 光駆動型 / フェニレンジアミン / ベンゾキノジイミン / プロトン共役電子移動 / レドックス活性配位子 / 光駆動 / 水素ラジカル / 金属錯体 / 水素キャリア / レドックス活性錯体 / 光反応 / 鉄錯体 / マンガン錯体 / アルコール脱水素 / 非貴金属錯体
Outline of Final Research Achievements

(1) We demonstrated that the photochemical hydrogen evolution reaction of our system can be driven by purely ligand-based processes that have been proved by the isolation of intermediates with ligand-based proton-coupled mixed valent ligands. We also experimentally proved that our system can be modulated by changing metal ions (such as from Fe(II) with d6 electrons to Mn(II) with d5 electrons, substituents (such as t-butyl and Cl groups) on the ligands. (2) To develop photodehydrogenation catalyst, we demonstrated the effects of metal ions (such as Mg(II), Mn(II), Co(II), Zn(II)), substituents (such as t-butyl and Cl groups), and spin states of metal center. As results, the catalytic activity has significantly increased by these chemical factors.

Academic Significance and Societal Importance of the Research Achievements

水素社会の構築は、持続可能社会の形成に必須の技術として注目されている。従来の水素貯蔵材料及び技術は、熱源を必要としエネルギーコストの観点からも本質的なジレンマを有する。一方、本研究の対象は、室温において光により水素を発生する材料の開発に資する金属錯体である。本研究ではopda/bqdi系金属錯体が示す配位子上での逐次的な多電子、多プロトン移動プロセスを実験的に証明したのに加え、これらの光水素キャリアの特性に影響する化学因子の解明に成功した点からも、今後の新しいタイプのエネルギーキャリア開発に寄与する諸知見が得られたと言える。

Report

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

    (39 results)

All 2019 2018 2017 2016 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 2 results) Presentation (30 results) (of which Int'l Joint Research: 9 results,  Invited: 7 results) Remarks (1 results)

  • [Journal Article] The Impact of Group‐10 Metals on the Solvent‐induced Disproportionation of o‐Semiquinonato Complexes2019

    • Author(s)
      Shota Yamada Takeshi Matsumoto Ho-Chol Chang
    • Journal Title

      Chemistry A European Journal

      Volume: in press Issue: 35 Pages: 8268-8278

    • DOI

      10.1002/chem.201900172

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Photochemical C-H Carboxylation of Aromatic Diamines with CO2 under Electron-Donor- and Base-free Conditions2018

    • Author(s)
      Matsumoto Takeshi、Uchijo Daiki、Koike Takuji、Namiki Ryoya、Chang Ho-Chol
    • Journal Title

      Scientific Reports

      Volume: 8 Issue: 1 Pages: 1-10

    • DOI

      10.1038/s41598-018-33060-3

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Tuning the Electron Acceptability of the [Mo6S8] Cluster Core by Decorating It with Methyl Groups on the Face-Bridging μ3-Sulfides2018

    • Author(s)
      Matsumoto Takeshi、Namiki Ryoya、Chang Ho-Chol
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: 2018 Issue: 35 Pages: 3900-3904

    • DOI

      10.1002/ejic.201800587

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tuning the Mesomorphism and Redox-Response of Anionic Ligand-Based Mixed-Valent Ni(II) Complexes via Alkyl-Substituted Quaternary Ammonium Cations2018

    • Author(s)
      Yuichi Nakamura, Takeshi Matsumoto, Yasutaka Sakazume, Junnosuke Murata, Ho-Chol Chang
    • Journal Title

      Chem. Eur. J.

      Volume: in press Issue: 29 Pages: 7398-7409

    • DOI

      10.1002/chem.201706006

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Coordination Behaviour of N,N'-Bis(diisopropylphosphinoacetyl)-o-phenylenediamine with Ni(II) and Cu(I) Ions2017

    • Author(s)
      Takahiro Ito, Takeshi Matsumoto, Masanori Wakizaka, Ho-Chol Chang
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2017 Issue: 29 Pages: 3498-3507

    • DOI

      10.1002/ejic.201700433

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Coordination Network with Ligand-centered Redox Activity Based on facial-[CrIII(2-mercaptophenolato)3]3- Metalloligands2017

    • Author(s)
      Masanori Wakizaka, Takeshi Matsumoto, Atsushi Kobayashi, Masako Kato, Ho-Chol Chang
    • Journal Title

      Chem. Eur. J.

      Volume: 23 Issue: 41 Pages: 9919-9925

    • DOI

      10.1002/chem.201701613

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structural and spectroscopic studies on the interactions of ortho-phenylenediamine and Li+, Na+, Mg2+, or Ca2+ ions2017

    • Author(s)
      Takeshi Matsumoto, Junki Ishii, Masanori Wakizaka, Ho-Chol Chang
    • Journal Title

      Chem. Lett.

      Volume: 46 Issue: 2 Pages: 232-235

    • DOI

      10.1246/cl.160997

    • NAID

      130005317076

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dehydrogenation of Anhydrous Methanol at Room Temperature by o-Aminophenol-based Photocatalysts2016

    • Author(s)
      Masanori Wakizaka, Takeshi Matsumoto, Ryota Tanaka, Ho-Chol Chang
    • Journal Title

      Nature Commun.

      Volume: 7 Issue: 1 Pages: 1-11

    • DOI

      10.1038/ncomms12333

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] Molecular-level Mechanism of External Stimuli-induced Disproportionation of Group 10 Metal Complexes with Semiquinonato2019

    • Author(s)
      Shota Yamada, Takeshi Matsumoto, Ho-Chol Chang
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] o-アミノフェノラート3d金属錯体が示すメタノールの光脱水素化における補助配位子効果2019

    • Author(s)
      小池 翔太、松本 剛、張 浩徹
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 二置換芳香族アミン/アルコール/チオール類のCO2下における光化学反応2019

    • Author(s)
      阿部 叶、小池 翔太、松本 剛、張 浩徹
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 電子吸引基を有する新規o-フェニレンジアミンFe(II)錯体の合成と光反応性2019

    • Author(s)
      高橋 良季、秋澤 秀明、松本 剛、張 浩徹
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Solvent-induced Disproportionation of Group 10 Metal Complexes with o-Semiquinonato2018

    • Author(s)
      Shota Yamada, Takeshi Matsumoto, Ho-Chol Chang
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Study on the Solvent-induced Disproportionation of Semiquinonato Complexes with Redox-active ligand2018

    • Author(s)
      Shota Yamada, Takeshi Matsumoto, Ho-Chol Chang
    • Organizer
      International Symposium on Nano & Supramolecular Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Redox-active Ligands as Photo-responsive Electron/Proton Poolers2018

    • Author(s)
      Ho-Chol Chang
    • Organizer
      43rd International Conference on Coordination Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] レドックス活性錯体によるメタノールの光脱水素反応の制御2018

    • Author(s)
      小池 翔太、内城 大貴、松本 剛、張 浩徹
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Photo-induced Hydrogen Transfer via Redox-active Ligand2018

    • Author(s)
      Ho-Chol Chang
    • Organizer
      the I2CNER International Workshops 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Photochemical Hydrogen Evolution Assisted by Nonprecious Metal Complexes Bearing Redox-active Ligands2018

    • Author(s)
      Takeshi Matsumoto and Ho-Chol Chang
    • Organizer
      International Congress on Pure & Applied Chemistry 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 二酸化炭素雰囲気下におけるトリス-o-フェニレンジアミン鉄(II)錯体の光化学反応2017

    • Author(s)
      内城 大貴、松本 剛、張 浩徹
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      日吉
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] o-フェニレンジアミン鉄(II)錯体が示す光水素発生反応2017

    • Author(s)
      小池 拓司、山本 莉紗、 松本 剛、 張 浩徹
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      日吉
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 新規置換o-フェニレンジアミン/o-ベンゾキノジイミン錯体の合成と電子・プロトン移動能2017

    • Author(s)
      秋澤 秀明、山本 莉紗、松本 剛、張 浩徹
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      日吉
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] o-フェニレンジアミン/o-ベンゾキノジイミン鉄(II)錯体に基づく多電子・多プロトン貯蔵システムの構築2017

    • Author(s)
      山本莉紗、松本 剛、張浩徹
    • Organizer
      日本化学会第97回春季年会
    • Place of Presentation
      日吉
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Redox-active Ligand as Photo-responsive Electrons/Protons Poolers2017

    • Author(s)
      Ho-Chol Chang
    • Organizer
      11th Japan-China Joint Symposium on Metal Cluster Compounds
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Photochemical Dehydrogenationbased on Iron(II) Complexes with Redox-active Ligands2017

    • Author(s)
      Ho-Chol Chang
    • Organizer
      Japan-Italy Bilateral Symposium on Artificial Photosynthesis Using Metal Complexes
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemical Function based on Redox-active Ligands2017

    • Author(s)
      Ho-Chol Chang
    • Organizer
      ISNSC9
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Redox-active Ligand as Photo-responsive Electrons/Protons Poolers2017

    • Author(s)
      Ho-Chol Chang
    • Organizer
      JCJSCC2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Design and Properties of Redox-active Metallomesogens2017

    • Author(s)
      Ho-Chol Chang
    • Organizer
      ACCC6
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] o-フェニレンジアミンFe(II)錯体が示すCO2の光固定化2017

    • Author(s)
      内城 大貴、松本 剛、張 浩徹
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 二酸化炭素雰囲気下におけるトリス-o-フェニレンジアミン鉄(II)錯体の光化学反応2017

    • Author(s)
      内城 大貴、松本 剛、張 浩徹
    • Organizer
      日本化学会第97回年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] o-フェニレンジアミン鉄(II)錯体が示す光水素ラジカル発生反応2017

    • Author(s)
      小池 拓司、松本 剛、張 浩徹
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] o-フェニレンジアミン鉄(II)錯体が示す光水素ラジカル発生反応2017

    • Author(s)
      小池 拓司、松本 剛、張 浩徹
    • Organizer
      第29回配位化合物の光化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Photochemical Hydrogen Evolution Reaction of o-Phenylenediamine Iron(II) Complexes2017

    • Author(s)
      Takuji Koike, Takeshi Matsumoto, Ho-Chol Chang
    • Organizer
      ACCC6
    • Related Report
      2017 Annual Research Report
  • [Presentation] o-フェニレンジアミン鉄(II)錯体が示す光水素発生反応2017

    • Author(s)
      小池 拓司、山本 莉紗、 松本 剛、 張 浩徹
    • Organizer
      日本化学会第97回年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] o-ベンゾキノジイミン錯体の水素化法の開発2017

    • Author(s)
      秋澤 秀明、山本 莉紗、松本 剛、張 浩徹
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Syntheses of o-Phenylenediamine/o-Benzoquinodiimine Complexes and Their Electron/Proton Transfer Processes2017

    • Author(s)
      Hideaki Akisawa, Risa Yamamoto, Takeshi Matsumoto, Ho-Chol Chang
    • Organizer
      ACCC6
    • Related Report
      2017 Annual Research Report
  • [Presentation] オルトフェニレンジアミン/オルトベンゾキノジイミン/Fe(II)錯体による光脱水素 システムの構築2016

    • Author(s)
      山本 莉紗、脇坂 聖憲、松本 剛、張 浩徹
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] Stepwise Ligand-Based Proton-Coupled Redox Reactions of Tris (ortho-Phenylenediamine and ortho-Benzoquinodiimine) Iron(II) Complex2016

    • Author(s)
      Risa Yamamoto, Takeshi Matsumoto, Masanori Wakizaka, and Ho-Chol Chang
    • Organizer
      6th International IUPAC Conference On Green Chemistry
    • Place of Presentation
      Venice, Italy
    • Year and Date
      2016-09-04
    • Related Report
      2016 Annual Research Report
  • [Presentation] o-フェニレンジアミンFe(II)錯体が示す光水素発生反応の機構とその制御因子2016

    • Author(s)
      小池 拓司、田中 亮太、 脇坂 聖憲、 松本 剛、 張 浩徹
    • Organizer
      第28回配位化合物の光化学討論会
    • Place of Presentation
      京都工芸繊維大学
    • Year and Date
      2016-08-08
    • Related Report
      2016 Annual Research Report
  • [Remarks] 分子物性化学研究室HP

    • URL

      http://www.chem.chuo-u.ac.jp/~chang/

    • Related Report
      2017 Annual Research Report

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

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