2002 Fiscal Year Annual Research Report

水素吸蔵錯体ポリマーの創製

Research Project

Project/Area Number	13874081
Research Institution	University of Tsukuba
Principal Investigator	北川宏筑波大学, 化学系, 助教授 (90234244)
Co-Investigator(Kenkyū-buntansha)	石丸臣一筑波大学, 化学系, 講師 (10251034) 池田龍一筑波大学, 化学系, 助教授 (90022631)
Keywords	水素吸蔵 / 配位高分子 / プロトン伝導
Research Abstract	熱重量分析から、RHに応じて水分子を吸収・放出することがわかった.常温、RH〜100%においては、多量の水(ダイマー当たり3分子)を含む。水の含有量とプロトン伝導性の関連を調べる目的で、プロトン伝導率のRH依存性を複素インピーダンス法により室温下で調べた。プロトン伝導率はRH上昇に伴い5桁以上増加し、RH100%の下では、室温におけるプロトン伝導率としては極めて言い値(σp>10-4Ω-1cm-1)を示した。イオン輸率はほぼ1である。したがって、プロトン伝導率の上昇は配位高分子中に含まれる水分子の量に依存しており、本配位高分子中で発現されるプロトン伝導性は少なくともポリマー中に含まれる水分子を媒介としていると考えられ、燃料電池の固体電解質であるナフィオンにおけるプロトン伝導の機構に類似しているものと推察される。各ポリマー試料は通常微粒子(粒径<0.3μm)として得られる。微粒子の光触媒プロセスによる水の光分解と水素吸蔵の可能性を追求した。微粒子を水に分散させ、紫外・可視光を照射することによって、水の光分解を試みた。水中のプロトンは、光励起によって徴粒子内に生じた電子と結合してH・となり微粒子内に吸蔵されると考えられ、将来の環境調和型のクリーンなエネルギー源として期待される。さらに、プリンタ技術として活用されているインクジェット法を用いて、ルベアン酸系高分子錯体とRu(bpy)_3系の光触媒とを交互に並べた界面素子を作製し、昼間は光化学電池と水素吸蔵素子として利用し、夜間は燃料電池として使用可能なハイブリッド型電池システムとしての応用の可能性を探った。水素吸蔵錯体の開拓は、合金一辺倒の水素吸蔵科学の研究に、新しい展開を与えるものと期待する。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] Y.Miyazaki, Qi Wang, A.Sato, K.Saito, M.Yamamoto, H.Kitagawa, T.Mitani, M.Sorai: "Heat Capacity of Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I(dta=CH_3CS_2)"J. Phys. Chem.. 106. 197-202 (2002)
[Publications] M.Mitsumi, S.Umebayashi, Y.Ozawa, K.Toriumi, H.Kitagawa, T.Mitani: "Structural Phase Transition and Valence Fluctuation Observed in a New MMX Chain Compound, Pt_2(n-PrCS_2)_4I"Chemistry Letters. 258-259 (2002)
[Publications] Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Highly Proton-Conductive Copper Coordination Polymers"Synthetic Metals. (in press).
[Publications] M.Fujishima, Y.Nagano, R.Ikeda, S.kanda, H.Kitagawa: "Substituent Effect on the Magnetic Properties of Copper Coordination Polymers with Dithiooxamide and N,N'-bis-(hydroxyethyl)dithiooxamide"Synthetic Metals. (in press).
[Publications] M.Ohmoto, S.Maki, Y.Morita, T.Kubo, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Complementary Double Hydrogen-Bonded CT Complexes of TTF Having Uracil Moiety"Synthetic Metals. (in press).
[Publications] M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Electronic State of A Hydrogen-Doped Copper Coordination Polymer : catena-μ-N,N'-bis-(hydroxyethyl)dithiooxamidatocopper(II), (HOC_2H_4)_2dtoaCu"Mol. Cryst. Liq. Cryst.. 379. 223-228 (2002)
[Publications] Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Complex-Plane Impedance Study on A Hydrogen-Doped Copper Coordindination Polymer : N,N'-bis-(2-hydroxy ethyl)dithiooxamidatocopper(II)"Mol. Cryst. Liq. Cryst.. 379. 89-94 (2002)
[Publications] A.Kobayashi, H.Kitagawa, R.Ikeda: "Structural and Optical Properties of Pt_2(dtp)_4Br_2 (dtp=dithiopropionato) and Its Halogen-Replacement Effect"Mol. Cryst. Liq. Cryst.. 379. 315-320 (2002)
[Publications] S.Takaishi, H.Kitagawa, R.Ikeda: "Relaxation Process of CT Exciton State in a One-Dimensional MX-Chain Compound[NiBr(chxn)_2]Br_2"Mol. Cryst. Liq. Cryst.. 379. 279-284 (2002)
[Publications] R.Makiura, H.Kitagawa, R.Ikeda: "Electronic State of A Hydrogen-Bridged Mixed-Valence Binuclear Complex, Ni_2(dta)_4I"Mol. Cryst. Liq. Cryst.. 379. 309-314 (2002)
[Publications] M.Mitsumi, K.Kitamura, A.Morinaga, Y.Ozawa, M.Kobayashi, K.Toriumi, Y.Iso, H.Kitagawa, T.Mitani: "Novel Valence-Ordering Structures and Magnetic behavior of New Metallic MMX Chain Compounds"Angrew. Chem. Int. Ed.. 41. 2767-2771 (2002)
[Publications] Y.Morita, S.Maki, M.Ohmoto, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Hydrogen-Bonded Charge-Transfer Complexes of TTF Containing a Uracil Moiety : Crystal Structures and Electronic Properties of the Hydrogen Cyananilate and TCNQ Complexes"Organic Letters. 4. 2185-2188 (2002)
[Publications] G.Saito, H.Sasaki, T.Aoki, Y.Yoshida, A.Otsuka, H.Yamochi, O.Drozdova, K.Yakushi, H.Kitagawa: "Complex formation of ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability"J. Mater. Chem.. 12. 1640-1649 (2002)
[Publications] S.Takaishi, M.Kano, H.Kitagawa, Y.Furukawa, K.Kumagai, R.Ikeda: "Spin Structure and Dynnamics in a Spin 1/2 One Dimensional Antiferromagnet, [NiBr(chxn)_2]Br_2"Chem. Lett.. 856-857 (2002)
[Publications] H.Kitagawa, Y.Nagano, M.Fujishima, R.Ikeda, S.Kanda: "Highly Proton-Conductive Copper Coordination Polymer, H_2dtoaCu"Inorg. Chem. Commun.. 6. 346-348 (2003)
[Publications] M.Yamauchi, Y.Isobe, R.Ikeda, H.Kitagawa: "A Study on Hydrogen Adsorption of Polymer-Protected Pt Nanoparticles"Synth. Met.. (in press).

2002 Fiscal Year Annual Research Report

水素吸蔵錯体ポリマーの創製

Principal Investigator

北川 宏 筑波大学, 化学系, 助教授 (90234244)

Research Products

[Publications] Y.Miyazaki, Qi Wang, A.Sato, K.Saito, M.Yamamoto, H.Kitagawa, T.Mitani, M.Sorai: "Heat Capacity of Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I(dta=CH_3CS_2)"J. Phys. Chem.. 106. 197-202 (2002)

[Publications] M.Mitsumi, S.Umebayashi, Y.Ozawa, K.Toriumi, H.Kitagawa, T.Mitani: "Structural Phase Transition and Valence Fluctuation Observed in a New MMX Chain Compound, Pt_2(n-PrCS_2)_4I"Chemistry Letters. 258-259 (2002)

[Publications] Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Highly Proton-Conductive Copper Coordination Polymers"Synthetic Metals. (in press).

[Publications] M.Fujishima, Y.Nagano, R.Ikeda, S.kanda, H.Kitagawa: "Substituent Effect on the Magnetic Properties of Copper Coordination Polymers with Dithiooxamide and N,N'-bis-(hydroxyethyl)dithiooxamide"Synthetic Metals. (in press).

[Publications] M.Ohmoto, S.Maki, Y.Morita, T.Kubo, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Complementary Double Hydrogen-Bonded CT Complexes of TTF Having Uracil Moiety"Synthetic Metals. (in press).

[Publications] M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Electronic State of A Hydrogen-Doped Copper Coordination Polymer : catena-μ-N,N'-bis-(hydroxyethyl)dithiooxamidatocopper(II), (HOC_2H_4)_2dtoaCu"Mol. Cryst. Liq. Cryst.. 379. 223-228 (2002)

[Publications] Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Complex-Plane Impedance Study on A Hydrogen-Doped Copper Coordindination Polymer : N,N'-bis-(2-hydroxy ethyl)dithiooxamidatocopper(II)"Mol. Cryst. Liq. Cryst.. 379. 89-94 (2002)

[Publications] A.Kobayashi, H.Kitagawa, R.Ikeda: "Structural and Optical Properties of Pt_2(dtp)_4Br_2 (dtp=dithiopropionato) and Its Halogen-Replacement Effect"Mol. Cryst. Liq. Cryst.. 379. 315-320 (2002)

[Publications] S.Takaishi, H.Kitagawa, R.Ikeda: "Relaxation Process of CT Exciton State in a One-Dimensional MX-Chain Compound[NiBr(chxn)_2]Br_2"Mol. Cryst. Liq. Cryst.. 379. 279-284 (2002)

[Publications] R.Makiura, H.Kitagawa, R.Ikeda: "Electronic State of A Hydrogen-Bridged Mixed-Valence Binuclear Complex, Ni_2(dta)_4I"Mol. Cryst. Liq. Cryst.. 379. 309-314 (2002)

[Publications] M.Mitsumi, K.Kitamura, A.Morinaga, Y.Ozawa, M.Kobayashi, K.Toriumi, Y.Iso, H.Kitagawa, T.Mitani: "Novel Valence-Ordering Structures and Magnetic behavior of New Metallic MMX Chain Compounds"Angrew. Chem. Int. Ed.. 41. 2767-2771 (2002)

[Publications] Y.Morita, S.Maki, M.Ohmoto, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Hydrogen-Bonded Charge-Transfer Complexes of TTF Containing a Uracil Moiety : Crystal Structures and Electronic Properties of the Hydrogen Cyananilate and TCNQ Complexes"Organic Letters. 4. 2185-2188 (2002)

[Publications] G.Saito, H.Sasaki, T.Aoki, Y.Yoshida, A.Otsuka, H.Yamochi, O.Drozdova, K.Yakushi, H.Kitagawa: "Complex formation of ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability"J. Mater. Chem.. 12. 1640-1649 (2002)

[Publications] S.Takaishi, M.Kano, H.Kitagawa, Y.Furukawa, K.Kumagai, R.Ikeda: "Spin Structure and Dynnamics in a Spin 1/2 One Dimensional Antiferromagnet, [NiBr(chxn)_2]Br_2"Chem. Lett.. 856-857 (2002)

[Publications] H.Kitagawa, Y.Nagano, M.Fujishima, R.Ikeda, S.Kanda: "Highly Proton-Conductive Copper Coordination Polymer, H_2dtoaCu"Inorg. Chem. Commun.. 6. 346-348 (2003)

[Publications] M.Yamauchi, Y.Isobe, R.Ikeda, H.Kitagawa: "A Study on Hydrogen Adsorption of Polymer-Protected Pt Nanoparticles"Synth. Met.. (in press).

北川宏筑波大学, 化学系, 助教授 (90234244)