NDLI: Influence of extreme conditions on the formation and structures of caesium uranium(VI) arsenates

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Dellen, Jakob Langer, Eike M. Klepov, Vladislav V. Yu, Na Bosbach, Dirk Schlenz, Hartmut Kegler, Philip Alekseev, Evgeny V.
Description	Author Affiliation: Yu N ( Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, 52428 Jülich, Germany. e.alekseev@fz-juelich.de.)
Abstract	Four new uranyl arsenates, $Cs_{2}[(UO_{2})(As_{2}O_{7})]$ (1), $α-Cs[(UO_{2})(HAs_{2}O_{7})]$ (2), $β-Cs[(UO_{2})(HAs_{2}O_{7})]$ (3), $Cs[(UO_{2})(HAs_{2}O_{7})]·0.17H_{2}O$ (4), were synthesized by high-temperature/high pressure (HT/HP) reactions at 900 °C and 3 GPa. These phases were subsequently characterised structurally as well as chemically. We demonstrated that compound 1 can also be obtained at ambient pressure. Compounds 1, 2, and 4 are based on two-dimensional (2D) anionic layers with two different topological types. The layers possess a similar composition, $[(UO_{2})(As_{2}O_{7})]^{2−}$ in 1 and $[(UO_{2})(HAs_{2}O_{7})]^{−}$ in 2 and 4. However, the presence of hydrogen in 2 and 4 leads to a change in coordination modes of the pyroarsenate groups. There are additional 0.17 $H_{2}O$ molecules per formula unit in 4, which cause slight distortions of the layers in 4. All these layers can be simplified to a common net, which is typical of autunite-like layered compounds. Compound 3 is a polymorph of compound 2, but the structural arrangements in these two are significantly different. The structure of 3 is based upon a three-dimensional (3D) framework, in which $UO_{7}$ is coordinated by arsenate groups in order to form uranyl anion sheets, and $UO_{6}$ is located within the interlayers. Bond valance analysis proved the presence of $OH^{−}$ groups in compounds 2, 3, and 4, respectively, and water molecules in 4. The Raman analyses enabled the study of the local environments of the arsenate and the uranyl groups within the investigated phases, respectively. It turned out that the applied HT/HP synthesis method strongly affects the crystal chemistry as well as the observed structural features of all obtained compounds.
ISSN	14779226
Issue Number	47
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-12-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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