Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates

Wang, S. A., Villa, E. M., Diwu, J. A., Alekseev, E. V., Depmeier, W. and Albrecht-Schmitt, T. E. (2011) Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates Inorganic Chemistry, 50 (6). pp. 2527-2533. DOI 10.1021/ic102356d.

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Supplementary data:

Abstract

U(VI), Np(VI), and Pu(VI) borates with the formula AnO(2)[B(8)O(11)(OH)(4)] (An = U, Np, Pu) have been prepared via the reactions of U(VI) nitrate, Np(VI) perchlorate, or Pu(IV) or Pu(VI) nitrate with molten boric acid. These compounds are all isotypic and consist of a linear actinyl(VI) cation, AnO(2)(2+), surrounded by BO(3) triangles and BO(4) tetrahedra to create an AnO(8) hexagonal bipyramidal environment. The actinyl bond lengths are consistent with actinide contraction across this series. The borate anions bridge between actinyl units to create sheets. Additional BO(3) triangles and BO(4) tetrahedra extend from the polyborate layers and connect these sheets together to form a three-dimensional chiral framework structure. UV-vis-NIR absorption and fluorescence spectroscopy confirms the hexavalent oxidation state in all three compounds. Bond-valence parameters are developed for Np(VI).

Document Type: Article
Keywords: fundamental building-blocks bond-valence parameters structural-characterization cationic framework crystal-structures nuclear-waste chemistry uranyl iodates stability
Research affiliation: Kiel University
DOI etc.: 10.1021/ic102356d
ISSN: 0020-1669
Date Deposited: 15 Dec 2011 05:01
Last Modified: 08 Oct 2012 09:27
URI: http://eprints.uni-kiel.de/id/eprint/15663

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