Synthesis and structural determination of alkali and alkaline earth metal containing bismuth vanadates Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/pg15bj438

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  • Exploratory synthesis plays an important role in the quest to discover new materials. There are very few structurally characterized alkali metal containing bismuth vanadates. Hybridization of the 6s and 6p orbitals of Bi[superscript 3+] and the resulting lone electron pair yields some very interesting stereochemistry and steric related properties. Some of those properties include ferroelectricity, ferroelasticity, electronic and ionic conduction, superconductivity, nonlinear optical capabilities and selective catalysis. Systematic exploration of the Na-Bi-V ternary system produced a new phase of NaBi[subscript 3]V[subscript 2]O[subscript 10]. This material crystallizes in the P 1 space group and the reported oxygen ion conductivity is apparently due to the presence of interstitial oxygen rather than oxygen vacancies. Stabilization of the tetragonal scheelite phase of BiVO[subscript 4] has been achieved by the substitution of a M[superscript 2+] for Bi [superscript 3+]. This has not been accomplished previously by a M[superscript 2+] cation substitution. The compound Ca[subscript o.29]Bi[subscript o.71] VO[subscript 3.855] crystallizes in the P4 space group. An investigation of the K-Bi-V ternary system resulted in the discovery of a new potassium vanadate. K[subscript io]Bi[subscript 4]V[subscript 4]O[subscript 21] crystallizes in the P6 space group with a equal to 10.205(2)A and c equal to 7.669(2)A. Other new compounds prepared, for which structures have not been determined are [alpha]-Na3BiV[subscript 2]O[subscript 8],[Beta]-(Na[subscript 3]BiV[subscript 2]O[subscript 8], K[subscript 8]Bi[subscript 5]V[subscript 5]O[subscript 24], Rb[subscript 2]BiVO[subscript 5], a rubidium compound with a 3:3:2 stoichiometric ratio of Rb:Bi:V, a rubidium compound with 2:1:1, a sodium compound with 2:1:1 and a lithium compound with a 1:1:1 stoichiometric ratio of Li:Bi:V.
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