2次元配位空間の制御

• Project/Area Number: 18033008
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Chiba University
• Principal Investigator: 加納 博文 Chiba University, 大学院・理学研究科, 准教授 (60334166)
• Project Period (FY): 2006 – 2007
• Project Status: Completed (Fiscal Year 2007)
• Budget Amount: ¥3,800,000 (Direct Cost: ¥3,800,000); Fiscal Year 2007: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 2006: ¥1,900,000 (Direct Cost: ¥1,900,000)
• Keywords: 有機金属錯体 / 気体吸着 / クラスレート / 協同効果 / 2次元格子 / ゲート吸着 / 柔軟構造 / 潜在細孔

Research Abstract

[Cu(bpy)_2(BF_4)]で与えられるLPCは特異な気体吸着現象であるゲート現象を示すことが報告されていた。本研究ではこのゲート現象の機構を解明するために、ゲート吸着前後におけるX線回折測定から、構造解析を行い、さらに、気体吸着機能を調節するために、2次元シート構造とシート間積層構造を修飾し、配位空間を制御することを試みた。さらに、LPCを構成する中心金属、対イオン、架橋リガンド分子および溶媒をそれぞれ変え、新たな配位高分子を調製するとともに、気体吸着特性と気体吸着に伴う構造変化を調べた。
昨年度は[Cu(bpy)_2(OTf)_2]_nを調製し、2D配位高分子であること、2段階の窒素吸着等温線を示すこと、その構造変化について、詳細に報告した。本年度は昨年新たに調製した[Co(bpy)_2(OTf)_2]_nの構造を決定し、2D型であること、構造も窒素吸着挙動も[Cu(bpy)_2(OTf)_2]_nのものに似通っていることを明らかにした。
また、Ni-bpy-(BF_4)系やNi-bpb-(BF_4)系(bpb=1,4-bis-(4-pyridil)benzene)の2D配位高分子を合成し、それらの気体吸着について調べた。詳細な構造は明らかではないが、気体吸着の様式や粉末X線回折の結果から、これらNi系の新規は配位高分子も2D型である可能性が示唆された。
このように新たにいくつかの異なる2D型配位高分子を調製し、特異的吸着挙動を明らかにでき、中心金属、対イオン、架橋リガンド分子および溶媒の一連の組み合わせについて、系統的な知見を得ることができた。

Research Products

• [Journal Article] Coordinated NH_3-Removal-Induced Hydrogen Adsorption of Cu-Complex Crystals (2008)
  • Author(s): A. Kondo, H. Noguchi, H. Kajiro, T. Ohba, K. Kaneko, H. Kanoh
  • Journal Title: Langmuir 24 Pages: 170-174
  • Peer Reviewed
• [Journal Article] Organic-inorganic hybrid polymer-encapsulated magnetic nanobead catalysts (2008)
  • Author(s): T. Arai, T. Sato, H. Kanoh, K. Kaneko, K. Oguma, A. Yanagisawa
  • Journal Title: Chem. Eur. J. 14 Pages: 882-885
  • Peer Reviewed
• [Journal Article] Clathrate Formation Mechanism of Supercritical Hydrogen Adsorption on Copper(II) Benzoate Pyrazine (2007)
  • Author(s): Goto, M.; Furukawa, M.; Miyamoto, J.; Kanoh, H.; Kaneko, K.
  • Journal Title: Langmuir 23 Pages: 5264-5266
  • Peer Reviewed
• [Journal Article] Magnetism of Organic Radical Molecules Confined in Nanospace of Single-Wall Carbon Nanohorn (2007)
  • Author(s): T. Matsumura, H. Tanaka, K. Kaneko, M. Yudasaka, S. Iijima, H. Kanoh
  • Journal Title: J. Phys. Chem. C 111 Pages: 10213-10216
  • Peer Reviewed
• [Journal Article] Conductive and Mesoporous Single-Wall Carbon Nanohorn/Organic Aerogel Comp osites (2007)
  • Author(s): Y. Tao, D. Noguchi, C. -M. Yang, H. Kanoh, H. Tanaka, M. Yudasaka, S. Iijima, K. Kaneko
  • Journal Title: Langmuir 23 Pages: 9155-9157
  • Peer Reviewed
• [Journal Article] Double-Step Gas Sorption of a Two-Dimensional Metal-Organic Framework (2007)
  • Author(s): A. Kondo, H. Noguchi, L. Carlucci, D. M. Proserpio, G. Ciani, H. Kajiro, T. Ohba, H. Kanoh, K. Kaneko
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 12362-12363
  • Peer Reviewed
• [Journal Article] Adsorption of water on three-dimensional pillared-layer metal organic frameworks (2007)
  • Author(s): A. Kondo, T. Daimaru, H. Noguchi, T. Ohba, K. Kaneko, H. Kanoh
  • Journal Title: J. Colloid Interface Sci. 314 Pages: 422-426
  • Peer Reviewed
• [Journal Article] Effect of Nanoscale Curvature of Single-Walled Carbon Nanotubes on Adsorption of Polycyclic Aromatic Hydrocarbons (2007)
  • Author(s): S.Gotovac, H.Honda, Y.Hattori, K.Takahashi, H.Kanoh, K.Kaneko
  • Journal Title: Nano. Lett. 7(3) Pages: 583-587
• [Journal Article] Evaluation of an effective gas storage amount of latent nanoporous cu-based metal-organic framework. (2007)
  • Author(s): Noguchi, H., Kondo, A., Hattori, Y., Kajiro, H., Kanoh, H., Kaneko, K.
  • Journal Title: J. Phys. Chem. C 111(1) Pages: 248-254
• [Journal Article] RBM band shift-evidenced dispersion mechanism of single-wall carbon nanotube bundles with NaDDBS. (2007)
  • Author(s): Utsumi, S., Kanamaru, M., Honda, H., Kanoh, H., Tanaka, H., Ohkubo, T., Sakai, H., Abe, M., Kaneko, K.
  • Journal Title: J. Colloid Interface Sci. 308(1) Pages: 276-284
• [Journal Article] Novel Expansion/Shrinkage Modulation of 2D Layered MOF Triggered by Clathrate Formation with CO_2 Molecules (2006)
  • Author(s): Atsushi Kondo, Hiroshi Noguchi, Shunsuke Ohnishi, Hiroshi Kajiro, Aya Tohdoh, Yoshiyuki Hattori, Wei-Chun Xu, Hideki Tanaka, Hirofumi Kanoh, Katsumi Kaneko
  • Journal Title: Nano Lett 6,(11) Pages: 2581-2584
• [Journal Article] Efficient H_2 Adsorption by Nanopores of High-Purity Double-Walled Carbon Nanotubes (2006)
  • Author(s): Miyamoto, J., Hattori, Y., Noguchi, D., Tanaka, H., Ohba, T., Utsumi, S., Kanoh, H., Kim, Y.A., Muramatsu, H., Hayashi, T., Endo, M., Kaneko, K.
  • Journal Title: J. Am. Chem. Soc. 128(39) Pages: 12636-12637
• [Journal Article] Quantum Sieving Effect of Modified Activated Carbon Fibers on H_2 and D_2 Adsorption at 20 K (2006)
  • Author(s): Hattori, Y., Tanaka, H., Okino, F., Touhara, H., Nakahigashi, Y., Utsumi, S., Kanoh, H., Kaneko, K.
  • Journal Title: J. Phys. Chem. B. 110(20) Pages: 9764-9767
• [Journal Article] Effects of Gas Adsorption on the Electrical Conductivity of Single-Wall Carbon Nanohorns (2006)
  • Author(s): Urita, K., Seki, S., Utsumi, S., Noguchi, D., Kanoh, H., Tanaka, H., Hattori, Y., Ochiai, Y., Aoki, N., Yudasaka, M., Iijima, S., Kaneko, K.
  • Journal Title: Nano Lett. 6(7) Pages: 1325-1328
• [Journal Article] Direct, -hydroxylation of ketones catalyzed by organic-inorganic hybrid polymer (2006)
  • Author(s): Arai, T., Sato, T., Noguchi, H., Kanoh, H., Kaneko, K., Yanagisawa, A.
  • Journal Title: Chem. Lett. 35(10) Pages: 1094-1095
• [Journal Article] Coordination Symmetry-Dependent Structure Restoration Function of One-Dimensional MOFs by Molecular Respiration (2006)
  • Author(s): Atsushi Kondo, Hiroshi Noguchi, Hiroshi Kajiro, Lucia Carlucci, Pierluigi Mercandelli, Davide M. Proserpio, Hideki Tanaka, Katsumi Kaneko, Hirofumi Kanoh
  • Journal Title: J. Phys. Chem. B 110(51) Pages: 25565-25567
• [Journal Article] Examination of synthesis conditions for graphite-derived nanoporous carbon-silica composites (2006)
  • Author(s): Zheng-Ming Wang, Kazuyo Shishibori, Kumiko Hoshinoo, Hirofumi Kanoh, Takahiro Hirotsu
  • Journal Title: Carbon 44(10) Pages: 1884-1890
• [Journal Article] Phenanthrene Adsorption from Solution on Single Wall Carbon Nanotubes (2006)
  • Author(s): Gotovac, S., Hattori, Y., Noguchi, D., Miyamoto, J.-i., Kanamaru, M., Utsumi, S., Kanoh, H., Kaneko, K.
  • Journal Title: J. Phys. Chem. B 110(33) Pages: 16219-16224
• [Presentation] CLATHRATE FORMATION MEDIATED STEPWISE GAS ADSORPTION ON A TWO-DIMENSIONAL METAL-ORGANIC FRAMEWORK (2007)
  • Author(s): A. Kondo, H. Noguchi, L. Carlucci, D.M. Proserpio, G. Ciani, H. Kajiro, T. Ohba, H. Kanoh, K. Kaneko
  • Organizer: Third International Symposium on Chemistry of Coordin ation Space
  • Place of Presentation: Awaji, Japan
  • Year and Date: 2007-12-10
• [Presentation] A Novel Co-Coordination Polymer of Gate Adsorptivity (2007)
  • Author(s): T. Nakagawa, A. Kondo, H. Kajiro, T. Ohba, H. Kanoh, K. Kaneko
  • Organizer: Third International Symposium on Chemistry of Coordin ation Space
  • Place of Presentation: Awaji, Japan
  • Year and Date: 2007-12-10
• [Presentation] ゲート現象による効率的気体分離・貯蔵 (2007)
  • Author(s): 野口浩志・上代洋・近藤篤1藤堂あや・服部義之・田中秀樹・大場友則・金子克美・許維春・加納博文
  • Organizer: 第21回日本吸着学会研究発表会
  • Place of Presentation: 東京大学 駒場
  • Year and Date: 2007-09-28
• [Presentation] 配位高分子の協同的気体吸収現象 (2007)
  • Author(s): 加納博文・大西俊輔・野口浩志・近藤篤・上代洋・服部義之・田中秀樹・大場友則・金子克美
  • Organizer: 第60回コロイドおよび界面化学討論会
  • Place of Presentation: 信州大学 松本市
  • Year and Date: 2007-09-20
• [Presentation] Magnetism and Structures of One-dimensional Arrays of Oxygen Molecules Confined in Nanospaces (2007)
  • Author(s): H. Kanoh, T. Matsumura, H. Li, H. Noguchi, H. Tanaka, Y. Fujiyama, A. Tohdoh, T. Ohba, T. Kodaira, K. Kaneko
  • Organizer: the 9th International Conference on Fundamentals of Ads orption(FOA9)
  • Place of Presentation: Giardini Naxos, Sicily, Italy
  • Year and Date: 2007-05-20
• [Book] 炭素材料の新展開 (2007)
  • Author(s): 加納博文、金子克美
  • Total Pages: 9
  • Publisher: 学振第117委員会
• [Book] ナノカーボンハンドブック (2007)
  • Author(s): 加納博文、金子克美
  • Total Pages: 6
  • Publisher: エヌ・ティー・エス
• [Remarks]
  • URL: http://pchem2.s.chiba-u.ac.jp/jpn/index.html