Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]

Journal Article · Tue Jul 01 00:00:00 EDT 2014 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2014.03.017· OSTI ID:22334274

Yu, Na; Klepov, Vladislav V. ^[1]; Villa, Eric M. ^[2]; Bosbach, Dirk ^[1]; Suleimanov, Evgeny V. ^[3]; Depmeier, Wulf ^[4]

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1. Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany)
2. Department of Chemistry, Creighton University, 2500 California Plaza, Omaha NE 68178 (United States)
3. Department of Chemistry, Lobachevsky State University of Nizhny Novgorod, 603950 Nizhny Novgorod (Russian Federation)
4. Institut für Geowissenschaften, Universität zu Kiel, 24118 Kiel (Germany)

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.

• OSTI ID: 22334274
• Journal Information: Journal of Solid State Chemistry, Vol. 215; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ARSENIC
CATIONS
DEHYDRATION
HYDROTHERMAL SYNTHESIS
RUBIDIUM NITRATES
URANIUM
URANIUM DIOXIDE
URANYL NITRATES