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Kinetic modelling of the gate adsorption of soft porous crystals based on in-situ stress measurements

Research Project

Project/Area Number 21H01690
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 27010:Transport phenomena and unit operations-related
Research InstitutionKyoto University

Principal Investigator

Watanabe Satoshi  京都大学, 工学研究科, 准教授 (80402957)

Co-Investigator(Kenkyū-buntansha) 平出 翔太郎  京都大学, 工学研究科, 助教 (60853207)
宮原 稔  京都大学, 工学研究科, 教授 (60200200)
Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2023: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2022: ¥7,150,000 (Direct Cost: ¥5,500,000、Indirect Cost: ¥1,650,000)
Fiscal Year 2021: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
KeywordsMetal-organic framework / ゲート吸着 / 構造転移 / 自由エネルギー解析 / 原子間力顕微鏡 / Soft MOF / AFM / 速度論 / エネルギー障壁
Outline of Research at the Start

本研究では,構造柔軟性を持つ多孔性配位錯体(Soft MOF)が示す,分子吸着が誘起する構造転移挙動を対象に,速度論的特性の解析手法確立とその機構解明を目指す。速度論的検討における本質的な困難は,対象とする構造転移挙動がエネルギー障壁を乗り越える活性化過程を伴う現象であり,確率論的な性質を有する点にある。そこで本研究では,構造転移に伴う応力を原子間力顕微鏡を用いて直接測定し,それを積分することで自由エネルギープロファイルを得るという速度論的解析を提案する。提案手法による解析を通じて,構造転移の速度論的挙動を記述可能な工学モデルの構築を試みる。

Outline of Final Research Achievements

Soft porous crystals (SPCs) show a step-wise gas uptake associated with structural transition, called "gate adsorption". It has been reported that the adsorption behavior associated with the structural transition depends on the particle size. To elucidate the particle size dependence of adsorption behavior, it is critical to elucidate the structural transition of single particles, but conventional adsorption isotherm measurements can only measure the averaged behavior of powders. Therefore, a method to measure adsorption behavior associated with structural transition at a single-particle level is required. In this study, we applied an atomic force microscope and measured force curves upon the gate-type structural transition behavior of single particles. By thermodynamically analyzing the obtained repulsive force profiles, we succeeded in observing the gate desorption behavior for each single particle.

Academic Significance and Societal Importance of the Research Achievements

ソフト多孔性錯体は,二酸化炭素の高効率回収などカーボンニュートラルの実現に向け,主要な役割を担い得る新規な吸着材料である。本研究では,このソフト多孔性錯体が示す特殊な吸着挙動の解明に向けて,平均的な挙動ではなく,単一粒子の挙動を明確にすることで,解像度の高い現象理解が可能となった。この成果は,今後の吸着分離プロセスへの実装に向け,基礎となるデータとなることが期待される。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (16 results)

All 2023 2022 2021 Other

All Int'l Joint Research (1 results) Journal Article (3 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 3 results,  Open Access: 1 results) Presentation (11 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results) Book (1 results)

  • [Int'l Joint Research] ドレスデン工科大学(ドイツ)

    • Related Report
      2023 Annual Research Report
  • [Journal Article] Validating the mechanism underlying the slacking of the gate-opening behavior in flexible metal-organic frameworks arising from the application of external force2023

    • Author(s)
      Homare Arima, Shotaro Hiraide, Minoru T. Miyahara, and Satoshi Watanabe
    • Journal Title

      ACS Appl. Mater. Interfaces

      Volume: 15 Issue: 30 Pages: 36975-36987

    • DOI

      10.1021/acsami.3c05923

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fast Gas-Adsorption Kinetics in Supraparticle-Based MOF Packings with Hierarchical Porosity2023

    • Author(s)
      Atsushi Fujiwara, Junwei Wang, Shotaro Hiraide, Alexander Gotz, Minoru T. Miyahara, Martin Hartmann, Benjamin Apeleo Zubiri, Erdmann Spiecker, Nicolas Vogel, and Satoshi Watanabe
    • Journal Title

      Advanced Materials

      Volume: 35 Issue: 44

    • DOI

      10.1002/adma.202305980

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Mechanism of CO2 Capacity Reduction of Flexible Metal-Organic Framework Caused by Water Adsorption2022

    • Author(s)
      Watanabe Satoshi、Hiraide Shotaro、Kunimitsu Hayato、Fujiwara Atsushi、Miyahara Minoru T.
    • Journal Title

      Frontiers in Materials

      Volume: 9 Pages: 1-11

    • DOI

      10.3389/fmats.2022.825592

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] Shaping of flexible metal-organic frameworks and less distinct gate adsorption caused by restricted volume expansion2023

    • Author(s)
      Homare Arima, Shotaro Hiraide, Minoru T. Miyahara, Satoshi Watanabe
    • Organizer
      1st Mediterranean Conference on Porous Materials (MEDPore 2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Mechanism of CO2 Capacity Reduction of Layered MOF (ELM-11) Caused by Water Adsorption2023

    • Author(s)
      Satoshi Watanabe, Shotaro Hiraide, Hayato Kunimitsu, Atsushi Fujiwara, Minoru T. Miyahara
    • Organizer
      1st Mediterranean Conference on Porous Materials (MEDPore 2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] AFMを用いたソフト多孔性錯体が示す構造転移挙動の強制誘起と熱力学的解析2023

    • Author(s)
      永野拓幸, 有馬誉, 平出翔太郎, 渡邉哲
    • Organizer
      化学工学会福井大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 原子間力顕微鏡によるソフト多孔性錯体単粒子への外力印加とゲート型脱着挙動の解析2023

    • Author(s)
      有馬誉, 永野拓幸, 平出翔太郎, 渡邉哲
    • Organizer
      第36回日本吸着学会研究発表会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 原子間力顕微鏡を用いたソフト多孔性錯体への外力印加によるゲート物性評価2023

    • Author(s)
      有馬誉, Leilla Abylgazina, Irena Senkovska, Ilka Hermes, 平出翔太郎, Gunter K. Auernhammer, Stefan Kaskel, 渡邉哲
    • Organizer
      化学工学会第54回秋季大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] ゲート吸着材の構造転移機構解明に向けた原子間力顕微鏡による外力直接印加2023

    • Author(s)
      有馬 誉,永野拓幸,平出翔太郎,渡邉 哲
    • Organizer
      化学工学会第88年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Formation and Characterization of Spherical Superstructures Composed of ZIF-8 Particles2022

    • Author(s)
      Satoshi Watanabe, Atsushi Fujiwara, Minoru T. Miyahara
    • Organizer
      Fundamental of Adsorption 14th international conference, 5月 23 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 多孔性錯体ZIF-8粒子の超単分散化2022

    • Author(s)
      渡邉 哲,齋藤遼太郎,藤原篤史,宮原 稔
    • Organizer
      化学工学会第53回秋季大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ソフト多孔性錯体(ELM-11)の大気暴露による細孔容量の減少機構解明とコアシェル化2022

    • Author(s)
      渡邉 哲,平出翔太郎,國光隼,藤原篤史,宮原 稔
    • Organizer
      第35回日本吸着学会研究発表会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ソフト多孔性錯体(ELM-11)の大気暴露による細孔容量減少のメカニズム解明2022

    • Author(s)
      渡邉哲, 平出翔太郎, 國光隼, 藤原篤史, 宮原稔
    • Organizer
      化学工学会第87年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ソフト多孔性錯体(ELM-11)の大気暴露による細孔容量減少の原因究明と解決手法の提案2021

    • Author(s)
      渡邉哲, 國光隼, 藤原篤史, 宮原稔
    • Organizer
      第72回コロイドおよび界面化学討論会
    • Related Report
      2021 Annual Research Report
  • [Book] 吸着技術の産業応用~基礎知識・吸着剤の特性・技術応用事例~2023

    • Author(s)
      渡邉 哲(分担執筆,第5章4節)
    • Total Pages
      348
    • Publisher
      情報機構
    • ISBN
      9784865022445
    • Related Report
      2022 Annual Research Report

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Published: 2021-04-28   Modified: 2025-01-30  

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