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Structure manufacturing of proton-conducting organic–inorganic hybrid silicophosphite membranes by solventless synthesis

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Abstract

We have developed a new class of proton-conducting organic–inorganic hybrid silicophosphite membranes, produced by ethanol condensation of organically modified alkoxysilanes and anhydrous vinylphosphonic acid under solventless, catalyst-free, low-temperature, one-pot conditions. The membranes synthesized in this study are crack-free, large, and flexible, and they exhibit good thermal stability up to intermediate temperatures (~218 °C). Structural analyses using 29Si and 31P nuclear magnetic resonance spectroscopy and infrared measurements revealed that ethanol condensation produced an inorganic alternating copolymer structure, Si–O–P, with a phosphole group, and successive polymerization between vinyl and/or methacryl groups enabled these structures to connect with each other. In this way, it is possible to achieve structure manufacturing of inorganic–organic networks. The proton conductivities of the hybrids are as high as 5.2 × 10−3 S/cm at 85 °C under 80% relative humidity.

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ACKNOWLEDGMENTS

This work was financially supported by the Joint Project of Chemical Synthesis Core Research Institutions Research and Education Funding for inter-University Research Projects, MEXT, Japan, and partially supported by a Grant-in-Aid for Scientific Research, No. 20613007, and Exploratory Research and Mission Research Project for Sustainable Humanosphere Science, Kyoto University. This work is also supported by Grant-in-Aid for Scientific Research (C), No. 20613007, MEXT. One of the authors (Y.T.) acknowledges financial support from the Murata Science Foundation.

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Authors and Affiliations

  1. Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan

    Yomei Tokuda, Satoshi Oku, Masahide Takahashi & Toshinobu Yoko

  2. Faculty of Sciences, Kyushu University, Higashi-ku Fukuoka, 812-8581, Japan

    Teppei Yamada & Hiroshi Kitagawa

  3. Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto, 606-8502, Japan

    Teppei Yamada & Hiroshi Kitagawa

  4. Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka, 599-8531, Japan

    Masahide Takahashi

  5. Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto, 611-0011, Japan

    Yoshikatsu Ueda

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  1. Yomei Tokuda
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  2. Satoshi Oku
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  3. Teppei Yamada
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  4. Masahide Takahashi
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  5. Toshinobu Yoko
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  6. Hiroshi Kitagawa
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  7. Yoshikatsu Ueda
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Correspondence to Yomei Tokuda.

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Tokuda, Y., Oku, S., Yamada, T. et al. Structure manufacturing of proton-conducting organic–inorganic hybrid silicophosphite membranes by solventless synthesis. Journal of Materials Research 26, 796–803 (2011). https://doi.org/10.1557/jmr.2010.89

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