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Development of innovative nanocluster catalyst by using amphiphilic nanoporous crystal

Research Project

Project/Area Number 19H02508
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 27020:Chemical reaction and process system engineering-related
Research InstitutionSojo University

Principal Investigator

Kusakabe Katsuki  崇城大学, 工学部, 教授 (30153274)

Co-Investigator(Kenkyū-buntansha) 大河平 紀司  有明工業高等専門学校, 創造工学科, 教授 (60629210)
櫻木 美菜 (水谷美菜)  崇城大学, 工学部, 准教授 (90646829)
Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,680,000 (Direct Cost: ¥13,600,000、Indirect Cost: ¥4,080,000)
Fiscal Year 2021: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2020: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2019: ¥9,230,000 (Direct Cost: ¥7,100,000、Indirect Cost: ¥2,130,000)
Keywords触媒 / 多孔質 / 結晶 / ナノ孔 / 多孔質材料 / 金ナノクラスター / 光触媒 / 固定化触媒 / 多孔質結晶 / 発光挙動 / フラーレン / ポルフィリン / 結晶化 / パラジウムナノクラスター / ナノリアクター / 触媒反応 / 金属ナノクラスター / 金属有機構造体
Outline of Research at the Start

両親媒性ナノ孔結晶であるシクロデキストリン系金属有機構造体(CD-MOF)は親水性と疎水性のナノ孔が連結したネックレス型チャネル構造を持つことが特徴である。例えば塩化金酸のメタノール溶液中にCD-MOFを浸漬すると、塩化金酸は親水性ナノ孔(径1.7nm)に孤立化するために、グルコースユニットの還元作用でサイズ2 nm以下の金ナノクラスターがCD-MOF内に高分散で高密度に創成する。本研究では、貴金属ナノクラスターを起点にPd-Ru合金ナノクラスター、酸化物ナノクラスター及び有機分子触媒内包CD-MOFの創成に挑戦し、これらのナノクラスター触媒の触媒特性を明らかにする。

Outline of Final Research Achievements

Cyclodextrin-based metal-organic Frameworks (CD-MOFs), which are porous organic crystals, were crystallized. Catalytically active noble metals and molecules were efficiently introduced into the nanopores of the CD-MOFs by adsorption and co-crystallization methods. CD-MOF with palladium nanoparticles showed high catalytic activity for the Suzuki coupling reaction, and even with 1/25 of the catalyst amount, the catalytic activity was similar to that of commercial Pd/C catalyst. When cobalt porphyrin, an organometallic catalyst, was introduced into CD-MOF, it showed almost the same catalytic activity as the corresponding homogeneous catalyst, but the reaction rate decreased due to the intra-crystal diffusion. Finally, CD-MOF with fullerene C60 showed high photocatalytic activity in the hydroxylation reaction of phenylboronic acid.

Academic Significance and Societal Importance of the Research Achievements

有機金属触媒や有機分子触媒は医薬系の分野で使用されている。これらの触媒は高価であるため多孔質材料へ高分散導入することで、再生使用することが望まれる。シクロデキストリン系金属有機構造体(CD-MOF)は生体に安全な材料であり、ドラッグキャリアーとしての応用が期待されている。本研究ではCD-MOF内にコバルトポルフィリンやフラーレンC60を高効率、高分散導入する手法を開発し、これらの不均一CD-MOF触媒は均一触媒の触媒活性に匹敵することを明らかにし、医薬系材料開発の触媒として適していることがわかった。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (23 results)

All 2021 2020 2019

All Journal Article (4 results) (of which Peer Reviewed: 4 results,  Open Access: 1 results) Presentation (18 results) (of which Int'l Joint Research: 7 results) Book (1 results)

  • [Journal Article] Cocrystallization of 1-Pyrenemethylamine/CD-MOF Composite Using THF as a Cosolvent2021

    • Author(s)
      Nagai Anna、Harada Shoki、Okobira Tadashi、Kusakabe Katsuki
    • Journal Title

      JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

      Volume: 54 Issue: 1 Pages: 44-49

    • DOI

      10.1252/jcej.20we147

    • NAID

      130007970954

    • ISSN
      0021-9592, 1881-1299
    • Year and Date
      2021-01-20
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of Co-porphyrin catalyst encapsulated in cyclodextrin-based metal-organic framework for coupling reaction2021

    • Author(s)
      A. Nagai, T. Hontake, Y. Abe, W. Michida, K. Inokawa, M. Sakuragi, T. Okobira, G. Guan, K. Kusakabe
    • Journal Title

      E3S Web of Conference

      Volume: 287 Pages: 1-5

    • DOI

      10.1051/e3sconf/202128702008

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Co-Oligomerization of Electroconductive Monomers in a Cyclodextrin-Based Metal–Organic Framework2020

    • Author(s)
      K. Kusakabe, A. Nagai, K. Nagao, M. Sakuragi, W. Michida
    • Journal Title

      JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

      Volume: 53 Issue: 9 Pages: 504-508

    • DOI

      10.1252/jcej.19we233

    • NAID

      130007906182

    • ISSN
      0021-9592, 1881-1299
    • Year and Date
      2020-09-20
    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fluorescence Emission Behaviors of the L-Cysteine/Au(I) Complex in a Cyclodextin-Based Metal-Organic Framework2020

    • Author(s)
      W. Michida, A. Nagai, M. Sakuragi, T. Okobira, K. Kusakabe
    • Journal Title

      Processes

      Volume: 8 Issue: 12 Pages: 1555-1555

    • DOI

      10.3390/pr8121555

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] 形態制御を目指した金ナノクラスターの合成と物性評価2021

    • Author(s)
      永井杏奈、松田元秀、草壁克己
    • Organizer
      第60回セラミックス基礎科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 機能性分子を導入したγ-シクロデキストリン系金属有機構造体の特性評価2021

    • Author(s)
      永井杏奈、松田元秀、櫻木美菜、草壁克己
    • Organizer
      セラ協九州支部秋季研究発表会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 4-メルカプト安息香酸を導入した CD-MOF 内での金ナノクラスターの合成と安定化2021

    • Author(s)
      永井杏奈、松田元秀、田中泰成、副島康幹、草壁克己
    • Organizer
      第52回化学工学会秋季大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Preparation of Co-porphyrin Catalyst Encapsulated in Cyclodextrin-based Metal-organic Framework for Coupling Reaction2021

    • Author(s)
      A. Nagai, Y. Abe, W. Michida, H. Inokawa, M. Sakuragi, T. Okobira, G. Guan, K. Kusakabe
    • Organizer
      International Conference of Process Engineering & Advanced Materials 2020
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 化学修飾したγ-CDを用いたCD-MOF結晶化2020

    • Author(s)
      米村拓真、永井杏奈、草壁克己
    • Organizer
      化学工学会九州支部オンライン学生発表会
    • Related Report
      2020 Annual Research Report
  • [Presentation] CD-MOF 内への疎水性有機化合物の導入2020

    • Author(s)
      野田友稀、永井杏奈、草壁克己
    • Organizer
      化学工学会九州支部オンライン学生発表会
    • Related Report
      2020 Annual Research Report
  • [Presentation] CD-MOFを用いた金ナノ粒子-チタニア複合体の合成2019

    • Author(s)
      米村拓真、永井杏奈、櫻木美菜、草壁克己
    • Organizer
      第56回化学関連支部合同九州大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 機能性分子を包接したCD-MOGの特性評価2019

    • Author(s)
      永井杏奈、佐古良平、櫻木美菜、草壁克己
    • Organizer
      第30回化学工学会九州支部若手エンジニアリング討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 可視応答型光触媒としてのC60/CD-MOFの評価2019

    • Author(s)
      米村拓真、永井杏奈、草壁克己
    • Organizer
      第30回化学工学会九州支部若手エンジニアリング討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] CD-MOF内での非晶質シリカ化合物の合成2019

    • Author(s)
      笹渕光志、永井杏奈、草壁克己
    • Organizer
      第30回化学工学会九州支部若手エンジニアリング討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 共溶媒による疎水性有機化合物を導入したCD-MOFの結晶化2019

    • Author(s)
      原田将希、永井杏奈、米村拓真、草壁克己
    • Organizer
      第30回化学工学会九州支部若手エンジニアリング討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Co-TCPPを導入したCD-MOFの結晶化2019

    • Author(s)
      本武拓海、永井杏奈、米村拓真、草壁克己
    • Organizer
      第30回化学工学会九州支部若手エンジニアリング討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis and Catalytic Activity of Pd Nanocluster in CD-MOF2019

    • Author(s)
      K. Sembon, K. Kusakabe
    • Organizer
      2019 Japan/Taiwan/Korea Chem. Eng. Conf.
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CD-MOF Crystallization of Modified g-Cyclodextrin2019

    • Author(s)
      T. Yonemura, A. Nagai, K. Kusakabe
    • Organizer
      2019 Japan/Taiwan/Korea Chem. Eng. Conf.
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Characterization of cyclodextrin-based metal-organic frameworks with catalyst molecules2019

    • Author(s)
      A. Nagai, W. Michida, M. Sakuragi, K. Kusakabe
    • Organizer
      2019 AIChE Annual Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Detection of Singlet Oxygen Produced by C60 Incorporated inside CD-MOF Crystal2019

    • Author(s)
      A.Nagai, T.Yonemura, R.Sako, H. Yonemura, K. Kusakabe
    • Organizer
      32nd International Symposium on Chemical Engineering
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Various Noble Metal Nanoparticles in Organic nanoporous Crystal2019

    • Author(s)
      K.Sembon, K.Suga, K.Kusakabe
    • Organizer
      32nd International Symposium on Chemical Engineering
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CD-MOF Crystallization of Modified g-Cyclodextrin2019

    • Author(s)
      T.Yonemura, A.Nagai, K. Kusakabe
    • Organizer
      32nd International Symposium on Chemical Engineering
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Book] PCP/MOFおよび各種多孔質材料の 作り方,使い方,評価解析2019

    • Author(s)
      草壁克己、道田 航、永井杏奈他95名
    • Total Pages
      639
    • Publisher
      技術情報協会
    • ISBN
      9784861047695
    • Related Report
      2019 Annual Research Report

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Published: 2019-04-18   Modified: 2023-01-30  

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