Hostname: page-component-586b7cd67f-tf8b9 Total loading time: 0 Render date: 2024-11-28T05:18:10.187Z Has data issue: false hasContentIssue false

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

Published online by Cambridge University Press:  28 February 2011

Yomei Tokuda*
Affiliation:
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Satoshi Oku
Affiliation:
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Teppei Yamada
Affiliation:
Faculty of Sciences, Kyushu University, Higashi-ku, Fukuoka 812-8581, Japan; and Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan
Masahide Takahashi
Affiliation:
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan; and Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
Toshinobu Yoko
Affiliation:
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Hiroshi Kitagawa
Affiliation:
Faculty of Sciences, Kyushu University, Higashi-ku, Fukuoka 812-8581, Japan; and Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan
Yoshikatsu Ueda
Affiliation:
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

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.

Type
Articles
Copyright
Copyright © Materials Research Society 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Pereira, R.P., Felisberti, M.I., and Rocco, A.M.: Intermolecular interactions and formation of the hydration sphere in phosphonic acid model systems as an approach to the description of vinyl phosphonic acid based polymers. Polymer (Guildf.) 47, 1414 (2006).CrossRefGoogle Scholar
2.Sevil, F. and Bozkurt, A.: Proton conducting polymer electrolytes on the basis of poly(vinylphosphonic acid) and imidazole. J. Phys. Chem. Solids 65, 1659 (2004).CrossRefGoogle Scholar
3.Erdemi, H. and Bozkurt, A.: Synthesis and characterization of poly(vinylpyrrolidone-co-vinylphosphonic acid) copolymers. Eur. Polym. J. 40, 1925 (2004).CrossRefGoogle Scholar
4.Parvole, J. and Jannasch, P.: Polysulfones grafted with poly(vinylphosphonic acid) for highly proton conducting fuel cell membranes in the hydrated and nominally dry state. Macromolecules 41, 3893 (2008).CrossRefGoogle Scholar
5.Yamada, M. and Honma, I.: Anhydrous proton conducting polymer electrolytes based on poly(vinylphosphonic acid)-heterocycle composite material. Polymer (Guildf.) 46, 2986 (2005).CrossRefGoogle Scholar
6.Onizuka, H., Kato, M., Shimura, T., Sakamoto, W., and Yogo, T.: Synthesis of proton conductive inorganic–organic hybrid membranes through copolymerization of dimethylethoxyvinylsilane with vinylphosphonic acid. J. Sol-Gel Sci. Technol. 46, 107 (2008).CrossRefGoogle Scholar
7.Yazawa, T., Shojo, T., Mineshige, A., Yusa, S., Kobune, M., and Kuraoka, K.: Solid electrolyte membranes based on polyvinyl phosphonic acid and alkoxysilane for intermediate-temperature fuel cells. Solid State Ion 178, 1958 (2008).CrossRefGoogle Scholar
8.Brinker, C.J. and Scherer, G.W.: Sol-Gel Science (Academic Press, San Diego 1990).Google Scholar
9.Niida, H., Takahashi, M., Uchino, T., and Yoko, T.: Preparation and structure of organic–inorganic hybrid low melting phosphite glasses from phosphonic acid H3PO3. J. Mater. Res. 18, 1081 (2003).CrossRefGoogle Scholar
10.Niida, H., Takahashi, M., Uchino, T., and Yoko, T.: Preparation of organic–inorganic hybrid precursors O=P(OSiMe3) x(OH)3–x for low-melting glasses. J. Ceram. Soc. Jpn. 111, 171 (2003).CrossRefGoogle Scholar
11.Takahashi, M., Niida, H., Tokuda, Y., and Yoko, T.: Organic–inorganic hybrid phosphite low-melting glasses for photonic applications. J. Non-Cryst. Solids 326327, 524 (2003)CrossRefGoogle Scholar
12.Niida, H., Takahashi, M., Uchino, T., and Yoko, T.: Preparation and structure of organic–inorganic hybrid precursors for new type low-melting glasses. J. Non-Cryst. Solids 306, 292 (2002).CrossRefGoogle Scholar
13.Megumi, M., Takahashi, M., Tokuda, Y., and Yoko, T.: Organic–inorganic hybrid material of phenyl-modified polysilicophosphate prepared through nonaqueous acid-base reaction. Chem. Mater. 18, 2075 (2006).Google Scholar
14.Suzuki, M., Takahashi, M., Tokuda, Y., and Yoko, T.: Preparation of optically functional organic–inorganic hybrid thin films through non aqueous acid-base reaction, in 45th Symposium on Basic Science of Ceramics, Sendai, Japan, 2007.Google Scholar
15.Tokuda, Y., Tanaka, Y., Takahashi, M., Ihara, R., and Yoko, T.: Silicophosphate/silicophosphite hybrid materials prepared by solventless ethanol condensation. J. Ceram. Soc. Jpn. 117, 842 (2009).CrossRefGoogle Scholar
16.Lorenzo, C.F., Esquivias, L., Barboux, P., Maquet, J., and Taulelle, F.: Sol-gel synthesis of SiO2–P2O5 glasses. J. Non-Cryst. Solids 176, 189 (1994).CrossRefGoogle Scholar
17.Olejniczak, Z., Łączka, M., Cholewa-Kowalska, K., Wojtach, K., Rokita, M., and Mozgawa, W.: 29Si MAS NMR and FTIR study of inorganic-organic hybrid gels. J. Mol. Struct. 744747, 465 (2005).CrossRefGoogle Scholar
18.Kannan, A.G., Choudhury, N.R., and Dutta, N.K.: Synthesis and characterization of methacrylate silicophosphite hybrid for thin film applications. Polymer (Guildf.) 48, 7078 (2007).CrossRefGoogle Scholar
19.Colthup, N.B., Daly, L.H., and Wiberley, S.E.: Introduction to Infrared and Raman Spectroscopy, 3rd ed. (Academic Press, San Diego 1990).Google Scholar
20.Förner, W. and Badawi, H.M.: Study of theoretical vibrational spectra and their assignments in vinylphosphonic and vinylthiophosphonic acids. J. Theor. Comput. Chem. 7, 1251 (2008).CrossRefGoogle Scholar
21.Coloban, P. and Novak, A.: Proton transfer and superionic conductivity in solids and gels. J. Mol. Struct. 177, 277 (1988).CrossRefGoogle Scholar