Synthesis and mechanism elucidation of porous metal complexes showing selective saturated hydrocarbon (alkane gas) adsorption

• Project/Area Number: 17H03026
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: Noro Shin-ichiro 北海道大学, 地球環境科学研究院, 教授 (70373347)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000); Fiscal Year 2019: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2018: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2017: ¥11,440,000 (Direct Cost: ¥8,800,000、Indirect Cost: ¥2,640,000)
• Keywords: 多孔性金属錯体 / 炭化水素ガス / 吸着分離 / 配位高分子 / 分離 / 多孔性配位高分子 / 多孔性材料 / 分子認識

Outline of Final Research Achievements

Development of selective alkane gas adsorption materials was carried out toward efficient hydrocarbon separation. Based on the three-dimensional porous metal complex UiO-67 constructed from Zr cations and 4,4'-biphenyldicarboxylate ligands, rigid perfluoroalkyl and flexible alkoxy groups were introduced to the ligands.Porous metal complex with perfluoroalkyl groups showed similar propane and propylene adsorption amounts. On the other hand, porous metal complex with alkoxy groups was found to show selective propane gas adsorption over propylene under low pressure condition.

Academic Significance and Societal Importance of the Research Achievements

アルケンガス、プロピレンは重要な化成品原料の一つであるが、その精製のためには特性の非常によく似たアルカンガス、プロパンを除去する必要がある。現状は高コスト分離法である蒸留法によって力づくで分離しているが、マイナー成分であるプロパンを多孔性材料による吸着法で高効率に分離できれば、分離コストの大幅な削減につながる。本研究では、これまでほとんど報告されていないアルカンガスであるプロパンを選択的に吸着する材料を見出しており、現状の高コスト分離法に代わる低コスト分離法を実現する上で極めて重要な知見となる。

Research Products

• [Int'l Joint Research] Technical University of Munich(ドイツ)
• [Int'l Joint Research] Sandia National Laboratories(米国)
• [Journal Article] Coordinated Water as New Binding Sites for the Separation of Light Hydrocarbons in Metal-Organic Frameworks with Open Metal Sites (2020)
  • Author(s): Pia Vervoorts, Andreas Schneemann, Inke Hante, Jenny Pirillo, Yuh Hijikata, Takashi Toyao, Kenichi Kon, Ken-ichi Shimizu, Takayoshi Nakamura, Shin-ichiro Noro* and Roland A. Fischer*
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 12 Issue: 8 Pages: 9448-9456
  • DOI: 10.1021/acsami.9b21261
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Dielectric and Sorption Responses of Hydrogen-Bonding Network of Amorphous C60(OH)12 and C60(OH)36 (2019)
  • Author(s): Shota Uchikawa, Ayumi Kawasaki, Norihisa Hoshino, Takashi Takeda, Shin-ichiro Noro,* Kiyonori Takahashi, Takayoshi Nakamura, Nozomi Sato, Ken Kokubo, Hidehiro Sakurai, and Tomoyuki Akutagawa*
  • Journal Title: J. Phys. Chem. C Volume: 123 Issue: 38 Pages: 23545-23553
  • DOI: 10.1021/acs.jpcc.9b06951
  • NAID: 120006887716
  • Peer Reviewed
• [Journal Article] Incorporation of Multinuclear Copper Active Sites into Nitrogen-Doped Graphene for Electrochemical Oxygen Reduction (2018)
  • Author(s): Masaru Kato, Marika Muto, Naohiro Matsubara, Yohei Uemura, Yuki Wakisaka, Tsubasa Yoneuchi, Daiju Matsumura, Tomoko Ishihara, Takashi Tokushima, Shin-ichiro Noro, Satoru Takakusagi, Kiyotaka Asakura, and Ichizo Yagi
  • Journal Title: ACS Appl. Energy Mater. Volume: 1 Issue: 5 Pages: 2358-2364
  • DOI: 10.1021/acsaem.8b00491
  • NAID: 120006887744
  • Peer Reviewed
• [Journal Article] Chemo-chromism in an orthogonal dabco-based Co(ii) network assembled by methanol-coordination and hydrogen bond formation (2018)
  • Author(s): Shiga Misaki、Kawaguchi Shogo、Fujibayashi Masaru、Nishihara Sadafumi、Inoue Katsuya、Akutagawa Tomoyuki、Noro Shin-ichiro、Nakamura Takayoshi、Tsunashima Ryo
  • Journal Title: Dalton Transactions Volume: 47 Issue: 23 Pages: 7656-7662
  • DOI: 10.1039/c8dt01220b
  • Peer Reviewed
• [Journal Article] Selective MeCN/EtCN soprtion and preferential inclusion of substituted benzenes in a cage structure with arylsulfonamide-armed anthraquinones (2018)
  • Author(s): Takashi Takeda, Shin-ichiro Noro, Takayoshi Nakamura, Yasutaka Suzuki, Jun Kawamata, Tomoyuki Akutagawa
  • Journal Title: CrystEngComm Volume: 20 Issue: 1 Pages: 17-24
  • DOI: 10.1039/c7ce01752a
  • Peer Reviewed
• [Journal Article] Host-guest molecular crystals of diamino-4,4-bithiazole and dynamic molecular motions via guest sorption (2018)
  • Author(s): Hiroshi Nishiyama, Takashi Takeda, Norihisa Hoshino, Kiyonori Takahashi, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Crystal Growth & Design Volume: 18 Issue: 1 Pages: 286-296
  • DOI: 10.1021/acs.cgd.7b01236
  • Peer Reviewed
• [Journal Article] Linker Functionalization Triggers an Alternative 3D-Topology for Zn-Isophthalate-4,4′-Bipyridine Frameworks (2017)
  • Author(s): Andreas Schneemann, Robin Rudolf, Sebastian Henke, Yukiko Takahashi, Hung Banh, Inke Hante, Christian Schneider, Shin-ichiro Noro, and Roland A. Fischer
  • Journal Title: Dalton Trans. Volume: 46 Issue: 25 Pages: 8198-8203
  • DOI: 10.1039/c7dt01195d
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Fine-tuning optimal porous coordination polymers by functional alkyl groups for CH4 purification (2017)
  • Author(s): Fujun Cheng, Qianqian Li, Jingui Duan, Nobuhiko Hosono, Shin-ichiro Noro, Rajamani Krishna, Hongliang Lyu, Shinpei Kusaka, Wanqin Jin, and Susumu Kitagawa
  • Journal Title: J. Mater. Chem. A Volume: 46 Issue: 34 Pages: 17874-17880
  • DOI: 10.1039/c7ta02760e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structural diversification of light metal coordination polymers using 4-(methylsulfonyl)benzoate with a charge-polarized neutral methylsulfonyl coordination moiety (2017)
  • Author(s): Rika Ochi, Shin-ichiro Noro, Yuh Hijikata, Kazuya Kubo, Takayoshi Nakamura
  • Journal Title: European Journal of Inorganic Chemistry Volume: 34 Issue: 34 Pages: 4013-4019
  • DOI: 10.1002/ejic.201700627
  • Peer Reviewed
• [Journal Article] The emergent intramolecular hydrogen bonding effect on the electronic structures of organic electron acceptors (2017)
  • Author(s): Takashi Takeda, Yasutaka Suzuki, Jun Kawamata, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Physical Chemistry Chemical Physics Volume: 19 Issue: 35 Pages: 23905-23909
  • DOI: 10.1039/c7cp04402j
  • Peer Reviewed
• [Journal Article] Inter-cluster Distance Dependence of Electrical Properties of Single Crystals of a Mixed-valence Polyoxometalate (2017)
  • Author(s): Ryo Tsunashima, Ippei Nakamura, Rika Oue, Seiya Koga, Hirofumi Oki, Shin-ichiro Noro, Takayoshi Nakamura, and Tomoyuki Akutagawa
  • Journal Title: Dalton Trans Volume: 46 Issue: 37 Pages: 12619-12624
  • DOI: 10.1039/c7dt02623d
  • Peer Reviewed
• [Journal Article] Fluorine-functionalized metal-organic frameworks and porous coordination polymers (2017)
  • Author(s): Shin-ichiro Noro and Takayoshi Nakamura
  • Journal Title: NPG Asia Mater. Volume: 9 Issue: 9 Pages: e433-e433
  • DOI: 10.1038/am.2017.165
  • Peer Reviewed / Open Access
• [Journal Article] Density Gradation of Open Metal Sites in the Mesospace of Porous Coordination Polymers (2017)
  • Author(s): Jingui Duan, Masakazu Higuchi, Jiajia Zheng, Shin-ichiro Noro, I-Ya Chang, Kim Hyeon-Deuk, Simon Mathew, Shinpei Kusaka, Easan Sivaniah, Ryotaro Matsuda, Shigeyoshi Sakaki, and Susumu Kitagawa
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 33 Pages: 11576-11583
  • DOI: 10.1021/jacs.7b05702
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 環境汚染物質除去のためのアルギネートポリマーMOF複合体の合成 (2020)
  • Author(s): 谷本憂太郎、野呂真一郎
  • Organizer: 化学系学協会北海道支部2020年冬季研究発表会
• [Presentation] アルコキシ基を有する多孔性Zr錯体の合成と吸着特性 (2020)
  • Author(s): 原田健杜、大関隆志、伊藤彰則、野呂真一郎
  • Organizer: 化学系学協会北海道支部2020年冬季研究発表会
• [Presentation] Introduction of Hydroxy Groups into One-Dimensional Metal Complexes and Their Impact on Adsorption Properties (2019)
  • Author(s): AnQi Wang, Kiyonori Takahashi, Ichiro Hisaki, Takayoshi Nakamura, Shin-ichiro Noro
  • Organizer: 錯体化学会第69回討論会
• [Presentation] 室温低濃度二酸化炭素分離へ向けた柔軟性金属錯体の合成 (2019)
  • Author(s): 杉浦みのり、高橋仁徳、久木一朗、中村貴義、野呂真一郎
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Effect of Uptake/Release of Coordinated Molecules on Gate-Opening Adsorption Behavior in Coordination Polymer (2019)
  • Author(s): Xin Zheng, Kiyonori Takahashi, Ichiro Hisaki, Takayoshi Nakamura, Shin-ichiro Noro
  • Organizer: 錯体化学会第69回討論会
• [Presentation] ピペラジンを含む金属錯体の合成と二酸化炭素吸着特性 (2019)
  • Author(s): 張思、高橋仁徳、久木一朗、中村貴義、野呂真一郎
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Perfluoroalkyl基を有する多孔性Zr錯体固溶体のガス吸着特性 (2019)
  • Author(s): 伊藤彰則、大関隆志、高橋仁徳、久木一朗、中村貴義、野呂真一郎
  • Organizer: 日本化学会北海道支部2019年夏季研究発表会
• [Presentation] 光反応性4-スチリルピリジン配位子を有するウェルナークラスレートの合成と性質 (2019)
  • Author(s): 張雲雅、高橋仁徳、久木一朗、中村貴義、野呂真一郎
  • Organizer: 日本化学会北海道支部2019年夏季研究発表会
• [Presentation] 2-アミノピリミジン架橋一次元金属錯体の合成及び二酸化炭素吸着特性評価 (2019)
  • Author(s): 孟宇、鈴木和重、高橋仁徳、久木一朗、中村貴義、野呂真一郎
  • Organizer: 日本化学会北海道支部2019年夏季研究発表会
• [Presentation] 4-スチリルピリジン配位子を有するウェルナー型錯体の合成と性質 (2019)
  • Author(s): 張雲雅、高橋仁徳、中村貴義、野呂真一郎
  • Organizer: 化学系学協会北海道支部2019年冬季研究発表会
• [Presentation] Perfluoro基で修飾された多孔性Zr錯体の合成と特性評価 (2019)
  • Author(s): 伊藤彰則、大関隆志、野呂真一郎
  • Organizer: 化学系学協会北海道支部2019年冬季研究発表会
• [Presentation] Dibenzo[24]crown-8/1-ethyl-3-methylimidazolium超分子カチオンを導入した[Ni(dmit)2]アニオンラジカル炎の融解挙動と電気物性 (2019)
  • Author(s): 高橋仁徳、白川祐基、星野哲久、野呂真一郎、芥川智行、中村貴義
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] ビピリジンとジチオレン配位子誘導体からなる分極性非対称白金錯体のエレクトロクロミック特性 (2019)
  • Author(s): 堀葵、久保和也、キム ユナ、森田朝子、友田千尋、角屋智史、野呂真一郎、玉置伸之、中村貴義、山田順一
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] 糖残基を有する双頭型両親媒性分子の合成とその集合能評価 (2019)
  • Author(s): 石ヶ森あずみ、和泉雅之、高橋仁徳、野呂真一郎、中村貴義、越智里香
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] A series of copper coordination polymers constructed by bis(imidazole) ligands and bulky fluorinated anions: synthesis, structures, and physical properties (2018)
  • Author(s): Xin Zheng, Kiyonori Takahashi, Takayoshi Nakamura, Shin-ichiro Noro
  • Organizer: 錯体化学会第68回討論会
  • Int'l Joint Research
• [Presentation] Crystal Structure, Gas Sorption and Dielectric Properties of One-Dimensional Copper(II) Coordination Polymer with 2-Thiophenecarboxylate Ligand (2018)
  • Author(s): Kiyonori Takahashi, Norihisa Hoshino, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: 43th International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] 混合原子価ポリオキソメタレートが示す分子構造相転移における結晶溶媒の影響 (2018)
  • Author(s): 藤林将、高橋仁徳、野呂真一郎、中村貴義、綱島亮
  • Organizer: 2018年日本化学会中国四国支部大会
• [Presentation] 糖脂質型両親媒性分子ライブラリの合成とその自己集合能の評価 (2018)
  • Author(s): 石ヶ森あずみ、和泉雅之、野呂真一郎、中村貴義、越智里香
  • Organizer: 2018年日本化学会中国四国支部大会
• [Presentation] Synthesis and Characterization of Sandwich-type Polyoxometalates [(PW9O34)2(H2OTb)3CO3]11- Containing Carbonate-Bridged Terbium Triangles with Organic Cations (2018)
  • Author(s): Chen Jiao、西出大輔、藤林将、高橋仁徳、久保和也、野呂真一郎、中村貴義
  • Organizer: 化学系学協会北海道支部2018年冬季研究発表会
• [Presentation] 18核ポリオキソメタレートへのアルキルホスホン酸修飾に伴う骨格構造のひずみ (2018)
  • Author(s): 藤林将、高橋仁徳、野呂真一郎、中村貴義、綱島亮
  • Organizer: 化学系学協会北海道支部2018年冬季研究発表会
• [Presentation] 複素環カチオン-ジベンゾ[24]クラウン-8超分子構造を含む[Ni(dmit)2]塩の構造 (2018)
  • Author(s): 白川祐基、高橋仁徳、野呂真一郎、芥川智行、中村貴義
  • Organizer: 化学系学協会北海道支部2018年冬季研究発表会
• [Presentation] 多孔性配位高分子によるグルコースからフルクトースへの異性化促進 (2018)
  • Author(s): 越智里香、野呂真一郎、久保和也、中村貴義
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] Gas Sorption and Dielectric Properties of One-Dimensional Copper Coordination Polymers with Heteroaromatic Ligands (2018)
  • Author(s): Kiyonori Takahashi, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] [Cu2(4-X-benzoate)4(L)]n (X=H,Me,F,Cl,Br,I/L=pyrazine, diazabicyclooctane)の構造相転移を伴う極性・無極性気体分子の吸蔵 (2017)
  • Author(s): 赤星周平、景山義之、丸田悟朗、高橋幸裕、野呂真一郎、武田定
  • Organizer: 日本化学会北海道支部2017年夏季研究発表会
• [Presentation] 誘電性スイッチングを目指した[Cu2(4-X-benzoate)4(L)]n (X=H,Me,F,Cl,Br,I/L=Pyrazine, Diazabicyclooctane)の構造相転移を伴う極性及び無極性気体分子吸蔵 (2017)
  • Author(s): 赤星周平、丸田悟朗、景山義之、高橋幸裕、野呂真一郎、武田定
  • Organizer: 第11回分子科学討論会
• [Presentation] Light Metal Coordination Polymers Using Organic Ligands with a Charge-Polarized Neutral Coordination Moiety (2017)
  • Author(s): Shin-ichiro Noro
  • Organizer: The 2nd Japan-US Bilateral Meeting on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Solid-State Phase Transition Behavior and Molecular Dynamics of Hydrogen Bonded One-Dimensional Copper Complexes with Fluorinated Benzoate Ligands (2017)
  • Author(s): Kiyonori Takahashi, Yuji Miyazaki, Shin-ichiro Noro, Motohiro Nakano, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Solid-solid, Solid-Liquid and Solid-Glass Phase Transitions of The Coordination Polymer Containing Flexible Building Blocks (2017)
  • Author(s): Xin Zheng, Shin-ichiro Noro, Kiyonori Takahashi, and Takayoshi Nakamura
  • Organizer: 錯体化学会第67回討論会
• [Presentation] N-ヘテロ環カチオン-クラウンエーテル超分子構造を含む[Ni(dmit)2]錯体結晶の構造と物性 (2017)
  • Author(s): 白川祐基、高橋仁徳、野呂真一郎、芥川智行、中村貴義
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Structures and Magnetic Properties of Tri-Nuclear Lanthanoid Complexes Sandwiched by Lacunary Keggin Polyoxometalates (2017)
  • Author(s): Jiao Chen, Daisuke Nishide, Masaru Fujibayashi, Kiyonori Takahashi, Kazuya Kubo, Shin-ichiro Noro, Ryo Tsunashima, and Takayoshi Nakamura
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Paddle-Wheel型二核銅錯体と屈曲配位型架橋配位子ピリミジンからなる一次元ジグザグ鎖状錯体の合成と構造 (2017)
  • Author(s): 鈴木和重、野呂真一郎、高橋仁徳、中村貴義
  • Organizer: 錯体化学会第67回討論会
• [Presentation] 水/2-プロパノール混合蒸気分離特性を示す柔軟な二次元層状マグネシウム配位高分子 (2017)
  • Author(s): 越智里香、野呂真一郎、神谷裕一、土方優、久保和也、中村貴義
  • Organizer: 第66回高分子討論会
• [Presentation] Basket Shaped Organic-Inorganic Hybrid Polyoxometalates Substituted with Alkyl Group (2017)
  • Author(s): Masaru Fujibayashi, Kiyonori Takahashi, Shin-ichiro Noro, Takayoshi Nakamura, Ryo Tsunashima
  • Organizer: 12th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2017)
  • Int'l Joint Research
• [Presentation] Crystal Structure and Physical Properties of Supramolecular Asssembly with In-Plane Rotator (2017)
  • Author(s): Yuki Shirakawa, Kiyonori Takahashi, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Organizer: 12th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2017)
  • Int'l Joint Research
• [Presentation] Structures and Magnetic Properties of Sandwich-Type Lanthanoid-Containing Polyoxometalates (2017)
  • Author(s): Jiao Chen, Daisuke Nishide, Masaru Fujibayashi, Kiyonori Takahashi, Kazuya Kubo, Shin-ichiro Noro, Takayoshi Nakamura
  • Organizer: 12th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2017)
  • Int'l Joint Research
• [Presentation] Correlative Molecular Motion and Dielectric Response of Solid-State Supramolecular Rotator (2017)
  • Author(s): Kiyonori Takahashi, Yuji Miyazaki, Shin-ichiro Noro, Motohiro Nakano, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: 12th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2017)
  • Int'l Joint Research
• [Presentation] CO2 gas separation using PCPs/MOFs with fluorinated anions (2017)
  • Author(s): Shin-ichiro Noro, Xin Zheng, and Takayoshi Nakamura
  • Organizer: 1st International Conference on Energy and Material Efficiency and CO2 Reduction in the Steel Industry
  • Int'l Joint Research
• [Presentation] Flexible Porous Coordination Polymers Decorated with Fluorinated Anions and Their Pelletization (2017)
  • Author(s): Xin Zheng and Shin-ichiro Noro
  • Organizer: JST ACCEL R&D Project International Symposium: The Nanospace Science of PCP for Molecular Control - Application and Development -
  • Int'l Joint Research
• [Presentation] Mutiple Rotational Dynamics in Supramolecular Crystal of (3-Fluoroadamantylammonium)(Dibenzo[18]Crown-6)[Ni(dmit)2] (2017)
  • Author(s): Kiyonori Takahashi, Yu Oshima, Kazuya Kubo, Shin-ichiro Noro, Sadamu Takeda, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: The 18th RIES-Hokudai International Symposiym 極
  • Int'l Joint Research
• [Presentation] Structures of Carbonate-Bridged Lanthanoid Triangles Sandwiched by Lacunary Keggin Polyoxometalates (2017)
  • Author(s): Jiao Chen, Daisuke Nishide, Masaru Fujibayashi, Kiyonori Takahashi, Kazuya Kubo, Shin-ichiro Noro, and Takayoshi Nakamura
  • Organizer: The 18th RIES-Hokudai International Symposiym 極
  • Int'l Joint Research
• [Presentation] Supramolecular cations of (diazinium)(dibenzo[24]crown-8) in [Ni(dmit)2] salt (2017)
  • Author(s): Yuki Shirakawa, Kiyonori Takahashi, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Organizer: The 18th RIES-Hokudai International Symposiym 極
  • Int'l Joint Research