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Physical properties in the bulk and nano spaces for preparing metal-supported porous coordination polymers using supercritical fluid deposition method

Research Project

Project/Area Number 21H01694
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 InstitutionHiroshima University

Principal Investigator

Ushiki Ikuo  広島大学, 先進理工系科学研究科(工), 准教授 (30734850)

Co-Investigator(Kenkyū-buntansha) 松山 清  福岡工業大学, 工学部, 教授 (40299540)
Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000)
Fiscal Year 2023: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Fiscal Year 2022: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2021: ¥11,700,000 (Direct Cost: ¥9,000,000、Indirect Cost: ¥2,700,000)
Keywords超臨界CO2 / PC-SAFT / Dubinin-Astakhov式 / ナノ空間物性 / 吸着 / 多孔性配位高分子 / バルク空間物性 / PCP / 熱力学 / 多孔質材料 / 触媒 / 超臨界二酸化炭素 / 溶解度 / 金属担持触媒 / 金属有機構造体 / MOF
Outline of Research at the Start

当研究グループではこれまで,超臨界二酸化炭素(CO2)に金属前駆体を溶解させ,これを極めて高い比表面積かつ均一なナノ細孔を有する多孔性配位高分子(PCP)に含浸させることにより,高性能の金属担持触媒を創製する方法論(超臨界含浸法)を提案してきた.本プロセスの設計へ向けては金属前駆体の超臨界CO2への溶解度(バルク空間物性)及びPCPのナノ細孔内への金属前駆体の吸着平衡(ナノ空間物性)両者に関する定量的理解が必須である.そこで本研究では,超臨界含浸法による金属担持PCP創製プロセスの設計へ向けた,超臨界CO2中における金属前駆体のバルク及びナノ空間物性に関する定量的基盤の構築を目的とする.

Outline of Final Research Achievements

In this study, we investigated the quantitative understanding of both solubility of solutes in supercritical CO2 (bulk space properties) and adsorption equilibrium of solutes in nanopores of PCP (nanospace properties) for the design of a process to prepare metal-supported PCP (porous coordination polymer) by supercritical impregnation method. The solubility and adsorption equilibria of solutes in supercritical CO2 were measured and modeled for model supports and solutes using the PC-SAFT perturbation theory equation of state and the Dubinin-Astakhov thermodynamic adsorption isotherm for model solutes. The results provide a quantitative basis for the design of a process for the creation of metal-supported PCP by the supercritical impregnation method.

Academic Significance and Societal Importance of the Research Achievements

金属資源の供給リスクや需要拡大による価格高騰を背景に、多くの反応において役立つレアメタルやレアアースを効果的に利用することが我が国の生存戦略として不可欠となっています。そのため、多孔質材料に触媒金属を埋め込む技術の重要性が増しています。本研究課題では、地球上に豊富に存在する二酸化炭素(CO2)を超臨界状態(臨界温度31℃、臨界圧力7.4 MPa以上の温度・圧力状態)にした流体を利用して、高性能な金属含浸多孔質材料を作製する方法(超臨界流体含浸法)について、そのプロセスの効率的な設計を目指して研究を行い、研究成果を得ました。

Report

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

    (21 results)

All 2024 2023 2022 2021 Other

All Journal Article (9 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 9 results,  Open Access: 3 results) Presentation (11 results) (of which Int'l Joint Research: 2 results,  Invited: 5 results) Remarks (1 results)

  • [Journal Article] Prediction of ionic liquid solubilities in supercritical CO2 + co-solvent systems using Peng?Robinson equation of state with accurate critical temperature2024

    • Author(s)
      Hiraga Yuya、Ushiki. Ikuo
    • Journal Title

      Journal of Molecular Liquids

      Volume: 398 Pages: 124324-124324

    • DOI

      10.1016/j.molliq.2024.124324

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Adsorption Equilibria of Propyl Acetate on Activated Carbon Under Supercritical CO2 Conditions2023

    • Author(s)
      Matsumoto Eisuke、Azim Mahmoud Magdy、Takishima Shigeki、Ushiki Ikuo
    • Journal Title

      Journal of Chemical Engineering of Japan

      Volume: 56 Issue: 1 Pages: 2256366-2256366

    • DOI

      10.1080/00219592.2023.2256366

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Measurement and modeling of adsorption equilibria of ketone VOCs on activated carbon in supercritical CO22023

    • Author(s)
      Tahara Yuto、Azim Mahmoud Magdy、Takishima Shigeki、Ushiki Ikuo
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 203 Pages: 106079-106079

    • DOI

      10.1016/j.supflu.2023.106079

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Modeling the Solubility of Ferrocene in Supercritical CO2 via PC-SAFT Using Solubilities Data Measured in Organic Solvents2023

    • Author(s)
      Ushiki Ikuo、Fujimitsu Ryo、Takishima Shigeki
    • Journal Title

      Journal of Chemical Engineering of Japan

      Volume: 56 Issue: 1 Pages: 2236655-2236655

    • DOI

      10.1080/00219592.2023.2236655

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] CO2 solubility and diffusivity in poly(vinyl acetate) studied using the PC-SAFT and free volume theory2023

    • Author(s)
      Ushiki, Ikuo; Ota, Saki; Kihara, Shin-ichi; Takishima, Shigeki
    • Journal Title

      Journal of Supercritical Fluids

      Volume: 194 Pages: 105836-105836

    • DOI

      10.1016/j.supflu.2022.105836

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Modeling cobalt (III) acetylacetonate and iron (III) acetylacetonate solubilities in supercritical CO2 with PC-SAFT based on experimentally-determined solid?liquid equilibria in organic solvents2023

    • Author(s)
      Ushiki Ikuo、Miyajima Azusa、Fujimitsu Ryo、Takishima Shigeki
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 196 Pages: 105882-105882

    • DOI

      10.1016/j.supflu.2023.105882

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Modeling the solubility of non-steroidal anti-inflammatory drugs (ibuprofen and ketoprofen) in supercritical CO2 using PC-SAFT2022

    • Author(s)
      Azim Mahmoud Magdy、Ushiki Ikuo、Miyajima Azusa、Takishima Shigeki
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 186 Pages: 105626-105626

    • DOI

      10.1016/j.supflu.2022.105626

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Estimating the solubility of salsalate in supercritical CO2 via PC-SAFT modeling using its experimental solubility data in organic solvents2022

    • Author(s)
      Azim Mahmoud Magdy、Ushiki Ikuo、Miyajima Azusa、Takishima Shigeki
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 189 Pages: 105725-105725

    • DOI

      10.1016/j.supflu.2022.105725

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Adsorption equilibria of ester VOCs (ethyl and butyl acetates) on activated carbon in supercritical CO2: Measurement and modeling by the Dubinin-Astakhov equation2022

    • Author(s)
      Ushiki Ikuo、Ueno Yuji、Takishima Shigeki、Ito Yasuyuki、Inomata Hiroshi
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 189 Pages: 105719-105719

    • DOI

      10.1016/j.supflu.2022.105719

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Presentation] 機能性ポリマーに対する超臨界CO2の溶解度・拡散係数の測定及びモデリング2023

    • Author(s)
      宇敷 育男
    • Organizer
      第25回新技術交流会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] 機能性ポリマーに対する超臨界CO2溶解度の測定およびPC-SAFT状態式によるモデリング2023

    • Author(s)
      宇敷 育男
    • Organizer
      化学工学会第54回秋季大会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] 超臨界流体法によるメソポーラスシリカへの薬剤含浸プロセスの検討2023

    • Author(s)
      山本 海利,宇敷 育男
    • Organizer
      化学工学会第54回秋季大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 超臨界CO2雰囲気下におけるケトン系VOC吸着平衡の測定及びモデリング2023

    • Author(s)
      田原 悠斗,宇敷 育男
    • Organizer
      化学工学会第54回秋季大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] A novel approach to estimate the solubilities of non-steroidal anti-inflammatory drugs (NSAIDs) in supercritical carbon dioxide by PC-SAFT equation of state,2022

    • Author(s)
      Mahmoud Magdy Azim, Ikuo Ushiki, Azusa Miyajima, Shigeki Takishima
    • Organizer
      APCChE2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 超臨界CO2雰囲気下におけるエステル系VOC吸着平衡の測定及びモデリング2022

    • Author(s)
      松本 栄祐, 宇敷 育男, 木原 伸一, 滝嶌 繁樹,
    • Organizer
      化学工学会第53会秋季大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 高機能性吸着剤再生プロセスに向けた超臨界CO2雰囲気下におけるVOC吸脱着挙動の測定及び推算2022

    • Author(s)
      宇敷 育男
    • Organizer
      広島大学大学院 先進理工系科学研究科設立3周年記念行事
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Physical properties of metal precursors in the bulk and nano spaces for design of supercritical fluid deposition processes2021

    • Author(s)
      Ikuo Ushiki
    • Organizer
      Korea-Taiwan-Japan Joint Symposium on Chemical Engineering 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 高機能性活性炭再生プロセスに向けた超臨界CO2中におけるエステル系VOC吸着平衡の測定及びモデリング2021

    • Author(s)
      上野 祐治, 宇敷 育男, 木原 伸一, 滝嶌 繁樹, 伊藤 康孝, 猪股 宏,
    • Organizer
      第52回化学工学会秋季大会2021
    • Related Report
      2021 Annual Research Report
  • [Presentation] 超臨界流体含浸プロセスの設計へ向けたバルク及びナノ空間物性の定量的把握とモデリング2021

    • Author(s)
      宇敷 育男
    • Organizer
      化学工学会東北支部 第29回若手の会セミナー講演
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Predicting the solubilities of acetylacetonate-type metal precursors in supercritical CO2: Thermodynamic modeling using PC-SAFT2021

    • Author(s)
      Ikuo Ushiki, Ryo Fujimitsu, Azusa Miyajima, Shigeki Takishima
    • Organizer
      9h International Symposium on Molecular Thermodynamics and Molecular Simulation
    • Related Report
      2021 Annual Research Report
  • [Remarks] 広島大学研究者総覧

    • URL

      https://seeds.office.hiroshima-u.ac.jp/profile/ja.8a86a47bd9407b1f520e17560c007669.html

    • Related Report
      2023 Annual Research Report 2022 Annual Research Report 2021 Annual Research Report

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

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