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Ion Exchange and Structural Aging in the Layered Perovskite Phases H1–xLixLaTiO4

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WestCHEM, Department of Pure and Applied Chemistry, Thomas Graham Building, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL Scotland
*E-mail: [email protected]. Phone: +44 141 548 2797. Fax: +44 141 548 4822.
Cite this: Inorg. Chem. 2013, 52, 12, 6985–6993
Publication Date (Web):May 28, 2013
https://doi.org/10.1021/ic4004752
Copyright © 2013 American Chemical Society

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    Grinding together the solid acid HLaTiO4 with stoichiometric quantities of lithium hydroxide monohydrate gives the solid solution H1–xLixLaTiO4. The structures of these crystalline phases have been refined against neutron powder diffraction data to show that all of these compounds crystallize in the centrosymmetric space group P4/nmm. The protons and lithium cations occupy sites between the perovskite layers; the former in hydroxide groups that hydrogen-bond to adjacent layers while Li+ is in four-coordinate sites that bridge the perovskite slabs with a geometry intermediate between square-planar and tetrahedral. The reaction proceeds rapidly, but the unit cell size continues to evolve over the course of days with a gradual compression along the interlayer direction that can be modeled using a power law dependence reminiscent of an Ostwald ripening process. On heating, these materials undergo a mass loss because of dehydration but retain the layered Ruddlesden–Popper structure up to 480 °C before a substantial loss of crystallinity on further heating to 600 °C. Impedance spectroscopy studies of the dehydrated materials shows that Li+ mobility in these materials is lower than the LiLaTiO4 end member, possibly because of microstructural effects causing large intergrain resistance through the defective phases.

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    Additional X-ray powder diffraction patterns collected after heating samples at 480 and 600 °C. This material is available free of charge via the Internet at http://pubs.acs.org.

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