Mixed-valence uranium(V,VI) and uranyl oxyhydroxides synthesized under high-temperature, high-pressure hydrothermal conditions: Na5[U 5O16(OH)2] and Na5[U 5O17(OH)]

Hsin Kuang Liu, Kwang Hwa Lii

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Abstract

An unusaul mixed-valence uranium(V,VI) oxyhydroxide, Na5[U 5O16(OH)2], was synthesized via reduction of UO22+ with zinc under hydrothermal conditions at 570 C and 150 MPa. Its structure consists of extended sheets of edge-sharing U VI pentagonal bipyramids and UV square bipyramids. The overall anion topology is the same as that of the uranyl mineral sayrite, but the squares are populated by UV(OH)23+ ions. The valence state of uranium was confirmed by X-ray photoelectron spectroscopy. A hydrothermal reaction without zinc under the same reaction conditions yielded a uranyl oxyhydroxide, Na5[U5O17(OH)], with a new sheet structure. The sheet anion topology, which is closely related to that of the mixed-valence compound, contains chains of edge-sharing pentagons as well as dimers of corner-sharing squares.

Original languageEnglish
Pages (from-to)9172-9174
Number of pages3
JournalInorganic Chemistry
Volume52
Issue number16
DOIs
StatePublished - 19 Aug 2013

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