Increase of ionic conductivity in the microporous lithosilicate RUB-29 by Na-ion exchange processes |
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Authors: | S-H Park A Senyshyn C Paulmann |
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Institution: | a Section Crystallography, Earth and Environmental Sciences, Ludwig-Maximilians-Universität München, Theresienstr. 41, 80333 Munich, Germany b Material- and Earth Sciences, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany c Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Lichtenbergstr. 1, 85747 Garching, Germany d Mineralogisch-Petrographisches Institut, Universität Hamburg, Grindelallee 48, 20146 Hamburg, Germany e HASYLAB, DESY, Notkestr. 85, 22603 Hamburg, Germany |
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Abstract: | The ionic conductivity in the zeolite-like lithosilicate RUB-29 (Cs14Li24Li18Si72O172]·14H2O S.-H. Park, J.B. Parise, H. Gies, H. Liu, C.P. Grey, B.H. Toby, J. Am. Chem. Soc. 122 (2000) 11023–11024]) increases via simple ion-exchange processes, in particular when Na cations replace a part of Cs+ and Li+ of the material. The resulting ionic conductivity value of 3.2×10−3 S cm−1 at 885 K is about two orders higher than that for the original material S.-H. Park, J.B. Parise, M.E. Franke, T. Seydel, C. Paulmann, Micropor. Mesopor. Mater., in print (doi:10.1016/j.micromeso.2007.03.040 available online since April 19, 2007)]. The structural basis of a Na+-exchanged RUB-29 sample (Na-RUB-29) at 673 K could be elucidated by means of neutron powder diffraction. Rietveld refinements confirmed the replacement of Na+ for both parts of Cs and Li cations, agreeing with idealized cell content, Na8Cs8Li40Si72O172. As a result of the incorporation of Na+ in large pores, the number of Li+ vacancies in dense Li2O-layers of the structure could increase. This can be one of the main reasons for the improved conductivity in Na-RUB-29. In addition, mobile Na cations may also contribute to the conductivity in Na-RUB-29 as continuous scattering length densities were found around the sites for Na in difference Fourier map. |
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Keywords: | Ionic conductivity Lithosilicate RUB-29 Na-RUB-29 Ion-exchange Lithium Neutron diffraction Impedance Rietveld refinement |
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