Macroporous monoliths surface-modified with MOF using precise ligand exchange

• Project/Area Number: 18H02056
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 36010:Inorganic compounds and inorganic materials chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: Nakanishi Kazuki 名古屋大学, 未来材料・システム研究所, 教授 (00188989)
• Co-Investigator(Kenkyū-buntansha): 金森 主祥 京都大学, 理学研究科, 助教 (60452265)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2019: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2018: ¥10,660,000 (Direct Cost: ¥8,200,000、Indirect Cost: ¥2,460,000)
• Keywords: MOF / 階層的多孔構造 / 自己集合 / 相分離 / 細孔構造 / マクロ多孔材料 / 配位子交換反応 / 細孔径分布

Outline of Final Research Achievements

Hierarchically porous MOF-functionalized materials have been synthesized through two different stragegies; i) Precipitating MOFs onto the inner surfaces of macroporous metal (oxy)hydroxide by direct exchanges of coordinating ligands. ii) Sol-gel reaction accompanied by phase separation in the course of network formation between metal ions and coordinating ligands. The latter solid retained a short-range atomic order similar to those in crystallized MOFs and the crystallization was performed by post-gelation treatments. Using pulverized and classified hierarchically porous MOF particles, various physico-chemical reactions such as gas adsorption/storage and separation/purification processes was found to be accelerated compared with those using non-porous counterparts.

Academic Significance and Societal Importance of the Research Achievements

MOFのもつ整ったマイクロ孔を有効利用するために、液体の浸透が可能なマクロ孔をもつ階層的多孔材料とする合成の方法論を見出し、構造制御手法を確立するとともに、複数の金属および配位子の組合せについて、同様な材料合成が可能であることを実証した。MOFを機能発現のために幾多の挑戦が続けられてきた階層構造化への道筋が得られたことは、今後の同材料の応用を拡大してゆく上で重要な意味をもつ。階層的多孔材料は粒径を制御した粒子状に成型することにより、薬物徐放など医学分野への応用も期待され、MOFそのものの物性設計自由度の高さと相まって、社会実装可能な応用につながるものと期待される。

Research Products

• [Journal Article] Tunable and Well-Defined Bimodal Porous Model Electrodes for Revealing Multiscale Structural Effects in the Nonaqueous Li-O2 Electrode Process (2021)
  • Author(s): Yosuke Hara, Manai Ono, Shoichi Matsuda, Kazuki Nakanishi, Kazuyoshi Kanamori, Ken Sakaushi*
  • Journal Title: The Journal of Physical Chemistry C Volume: 125 Issue: 2 Pages: 1403-1413
  • DOI: 10.1021/acs.jpcc.0c10446
  • Peer Reviewed
• [Journal Article] Hierarchically porous monoliths based on low-valence transition metal (Cu, Co, Mn) oxides: gelation and phase separation (2020)
  • Author(s): Xuanming Lu, Kazuyoshi Kanamori, Kazuki Nakanishi
  • Journal Title: National Science Review Volume: 7 Issue: 11 Pages: 1656-1666
  • DOI: 10.1093/nsr/nwaa103
  • Peer Reviewed / Open Access
• [Journal Article] Hierarchically porous monoliths prepared via sol-gel process accompanied by spinodal decomposition (2020)
  • Author(s): Xuanming Lu, George Hasegawa, Kazuyoshi Kanamori & Kazuki Nakanishi
  • Journal Title: J Sol-Gel Science & Technology Volume: 95 Issue: 3 Pages: 530-550
  • DOI: 10.1007/s10971-020-05370-4
  • Peer Reviewed
• [Journal Article] On-site formation of small Ag nanoparticles on superhydrophobic mesoporous silica for antibacterial application (2020)
  • Author(s): Zhu Yang, Chunhua Wu, Kazuyoshi Kanamori, Toshiyuki Kamei, Toyoshi Shimada, Kazuki Nakanishi
  • Journal Title: New Journal of Chemistry Volume: 44 Issue: 32 Pages: 13553-13556
  • DOI: 10.1039/d0nj02502j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Superhydrophobic highly flexible doubly cross-linked aerogel/carbon nanotube composites as strain/pressure sensors (2020)
  • Author(s): Guoqing ZU, Xiaodong WANG, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Journal Title: Journal of Materials Chemistry B Volume: - Issue: 22 Pages: 4883-4889
  • DOI: 10.1039/c9tb02953b
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Self-assembly of metal-organic frameworks into monolithic materials with highly controlled trimodal pore structures (2019)
  • Author(s): Yosuke HARA, Kazuyoshi KANAMORI, Kazuki NAKANISHI*
  • Journal Title: Angewandte Chemie International Edition Volume: 58 Issue: 52 Pages: 19047-19053
  • DOI: 10.1002/anie.201911499
  • Peer Reviewed
• [Journal Article] Preparation of zinc oxide with three-dimensionally interconnected macroporous structure through sol-gel method accompanied by phase separation (2019)
  • Author(s): Xuanming LU, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Journal Title: New Journal of Chemistry Volume: 43 Issue: 29 Pages: 11720-11726
  • DOI: 10.1039/c9nj02373a
  • Peer Reviewed
• [Journal Article] Superhydrophobic ultraflexible triple-network graphene/polyorganosiloxane aerogels for high-performance multifunctional temperature/strain/pressure sensing array (2019)
  • Author(s): Guoqing ZU*, Kazuyoshi KANAMORI*, Kazuki NAKANISHI, Jia HUANG
  • Journal Title: Chemistry of Materials Volume: 31 Issue: 16 Pages: 6276-6285
  • DOI: 10.1021/acs.chemmater.9b02437
  • Peer Reviewed
• [Journal Article] Iron(iii) oxyhydroxide and oxide monoliths with controlled multiscale porosity: synthesis and their adsorption performance (2018)
  • Author(s): Hara Yosuke、Kanamori Kazuyoshi、Morisato Kei、Miyamoto Riichi、Nakanishi Kazuki
  • Journal Title: Journal of Materials Chemistry A Volume: 6 Issue: 19 Pages: 9041-9048
  • DOI: 10.1039/c8ta01691g
  • Peer Reviewed
• [Presentation] Macroporous monoliths with modified compositions and structures (2019)
  • Author(s): Kazuki NAKANISHI*, Kazuyoshi KANAMORI, Xuanming LU, Yosuke HARA
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies
  • Int'l Joint Research / Invited
• [Presentation] Synthetic strategies toward ordered macroporous metal-organic frameworks monoliths (2019)
  • Author(s): Yosuke HARA*, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies
  • Int'l Joint Research
• [Presentation] Preparation of hierarchically porous low valence transition metal (Mn, Co, Cu) based monoliths with 3D interconnected structures (2019)
  • Author(s): Xuanming LU*, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies
  • Int'l Joint Research
• [Presentation] Porous inorganic monoliths: Challenges in extending chemical compositions for broader applications (2019)
  • Author(s): Kazuki NAKANISHI*, Yosuke HARA, Xuanming LU, Kazuyoshi KANAMORI
  • Organizer: XX International Sol-Gel Conference
  • Int'l Joint Research / Invited
• [Presentation] Iron(iii) oxyhydroxide and oxide monoliths with controlled multiscale porosity: synthesis and their adsorption performance (2018)
  • Author(s): Yosuke HARA*, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: 30th Symposium and Annual Meeting of the International Society for Ceramics in Medicine (Bioceramics 30, Nagoya, Japan, Oct. 26-29, 2018)
  • Int'l Joint Research
• [Presentation] Synthesis of hierarchically porous MgO monoliths with a co-continuous structure (2018)
  • Author(s): Xuanming LU*, Kazuyoshi KANAMORI, Kazuki NAKANISHI
  • Organizer: 30th Symposium and Annual Meeting of the International Society for Ceramics in Medicine (Bioceramics 30, Nagoya, Japan, Oct. 26-29, 2018)
  • Int'l Joint Research