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Title: Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite (Li {sub x} Cl)LaNb{sub 2}O{sub 7}

Abstract

A two-step topotactic route is used to construct lithium halide layers within a perovskite host. Initially RbLaNb{sub 2}O{sub 7} is converted to (CuCl)LaNb{sub 2}O{sub 7} by ion exchange and then reductive intercalation with n-butyllithium is used to form (Li {sub x} Cl)LaNb{sub 2}O{sub 7}. The copper metal byproduct from the reduction step is removed by treatment with iodine. Rietveld refinement of neutron powder diffraction data revealed that an alkali-halide double layer with LiO{sub 2}Cl{sub 2} tetrahedra forms between the perovskite slabs. Compositional studies indicate that the range for x in (Li {sub x} Cl)LaNb{sub 2}O{sub 7} is 2{<=}x<4, which appears consistent with the neutron data where only one lithium site was found in the structure. - Graphical abstract: Alkali-halide layers can be constructed within a layered perovskite host via a two-step topochemical process.

Authors:
 [1];  [1];  [2]
  1. Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, LA 70148-2820 (United States)
  2. Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, LA 70148-2820 (United States), E-mail: jwiley@uno.edu
Publication Date:
OSTI Identifier:
21015687
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2006.11.014; PII: S0022-4596(06)00594-9; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER; COPPER CHLORIDES; ION EXCHANGE; LAYERS; LITHIUM CHLORIDES; NEUTRON DIFFRACTION; NIOBIUM OXIDES; PEROVSKITE

Citation Formats

Viciu, Liliana, Kodenkandath, Thomas A., and Wiley, John B.. Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite (Li {sub x} Cl)LaNb{sub 2}O{sub 7}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.11.014.
Viciu, Liliana, Kodenkandath, Thomas A., & Wiley, John B.. Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite (Li {sub x} Cl)LaNb{sub 2}O{sub 7}. United States. doi:10.1016/j.jssc.2006.11.014.
Viciu, Liliana, Kodenkandath, Thomas A., and Wiley, John B.. Thu . "Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite (Li {sub x} Cl)LaNb{sub 2}O{sub 7}". United States. doi:10.1016/j.jssc.2006.11.014.
@article{osti_21015687,
title = {Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite (Li {sub x} Cl)LaNb{sub 2}O{sub 7}},
author = {Viciu, Liliana and Kodenkandath, Thomas A. and Wiley, John B.},
abstractNote = {A two-step topotactic route is used to construct lithium halide layers within a perovskite host. Initially RbLaNb{sub 2}O{sub 7} is converted to (CuCl)LaNb{sub 2}O{sub 7} by ion exchange and then reductive intercalation with n-butyllithium is used to form (Li {sub x} Cl)LaNb{sub 2}O{sub 7}. The copper metal byproduct from the reduction step is removed by treatment with iodine. Rietveld refinement of neutron powder diffraction data revealed that an alkali-halide double layer with LiO{sub 2}Cl{sub 2} tetrahedra forms between the perovskite slabs. Compositional studies indicate that the range for x in (Li {sub x} Cl)LaNb{sub 2}O{sub 7} is 2{<=}x<4, which appears consistent with the neutron data where only one lithium site was found in the structure. - Graphical abstract: Alkali-halide layers can be constructed within a layered perovskite host via a two-step topochemical process.},
doi = {10.1016/j.jssc.2006.11.014},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 180,
place = {United States},
year = {Thu Feb 15 00:00:00 EST 2007},
month = {Thu Feb 15 00:00:00 EST 2007}
}
  • A new metastable double-layered perovskite, Rb{sub 0.04}Na{sub 0.08}Ca{sub 0.44}LaNb{sub 2}O{sub 7}, has been synthesized by a two-step ion exchange route. Initially, RbLaNb{sub 2}O{sub 7} is reacted to produce the known metastable phase NaLaNb{sub 2}O{sub 7}; then this is exchanged with calcium to yield the title compound. The product has neither the RbLaNb{sub 2}O{sub 7} nor NaLaNb{sub 2}O{sub 7} structure types, but converts to a superstructure of KLaNb{sub 2}O{sub 7} with an orthorhombic unit cell: a = 3.885(1), b = 7.725(2), and c = 20.884(4) {angstrom}. Direct calcium exchange of RbLaNb{sub 2}O{sub 7} results in poorly crystalline products with only 31%more » exchange, while exchange with KLaNb{sub 2}O{sub 7} shows little evidence of reaction. The importance of size matching in divalent-for-monovalent cation exchange is discussed.« less
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  • Single crystals of Li{sub 2}La{sub 0.833}(Nb{sub 1.5}Ti{sub 0.5})O{sub 7} and Li{sub 2}La{sub 2.25}(Nb{sub 1.25}Ti{sub 2.75})O{sub 13} were grown in the system Li{sub 2}O-La{sub 2}O{sub 3}-Nb{sub 2}O{sub 5}-TiO{sub 2}. Both these compounds crystallize in the space group P4{sub 2}/mmm (No 136), Z = 4: a = 5.5334(2), c = 18.3907(2) {angstrom} and a = 5.4915(6), and c = 33.812(4) {angstrom}, respectively. Their crystal structures, determined from single crystal X-ray diffraction data, are related to the Ruddlesden-Popper phases A{sub n+1}B{sub n}O{sub 3n+1}, which could be better written here as Li{sub 2}[A{sub x}B{sub n}O{sub 3n+1}]: Li{sub 2}La{sub 0.833}(Nb{sub 1.5}Ti{sub 0.5})O{sub 7} is anmore » n = 2 member and Li{sub 2}La{sub 2.25}(Nb{sub 1.25}Ti{sub 2.75})O{sub 13} corresponds to an n = 4 member. In both structures, Nb{sup 5+} and Ti{sub 4+} ions statistically occupy distorted B octahedral sites of the perovskite, La{sup 3+} ions partially fill the cages of the perovskite, and Li{sup +} ions are found in tetrahedral coordination between the perovskite layers.« less
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