A New n = 4 Layered Ruddlesden-Popper Phase K2.5Bi2.5Ti4O13 Showing Stoichiometric Hydration

Inorganic Chemistry
Samuel LiuChris D Ling

Abstract

A new bismuth-containing layered perovskite of the Ruddlesden-Popper type, K2.5Bi2.5Ti4O13, has been prepared by solid-state synthesis. It has been shown to hydrate to form stoichiometric K2.5Bi2.5Ti4O13·H2O. Diffraction data show that the structure consists of a quadruple-stacked (n = 4) perovskite layer, with potassium ions occupying the rock salt layer and its next-nearest A site. The hydrated sample was shown to remove the offset between stacked perovskite layers relative to the dehydrated sample. Computational methods show that the hydrated phase consists of intact H2O molecules in a vertical "pillared" arrangement bridging across the interlayer space. Rotations of H2O molecules about the c axis were evident in molecular dynamic calculations, which increased in rotation angle with increasing temperature. In situ diffraction data for the dehydrated phase point to a broad structural phase transition from orthorhombic to tetragonal at ∼600 °C. The relative bismuth-rich composition in the perovskite block results in a higher transition temperature compared to related perovskite structures. Water makes a significant contribution to the dielectric constant, which disappears after dehydration.

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Dec 18, 2008·Chemical Society Reviews·Akihiko Kudo, Yugo Miseki
Jan 30, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Samuel LiuChris D Ling

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Citations

Jul 19, 2016·Inorganic Chemistry·Vegar ØygardenAnja O Sjåstad

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