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@ARTICLE{Murphy:856927,
author = {Murphy, Gabriel and Kegler, Philip and Zhang, Yingjie and
Zhang, Zhaoming and Alekseev, Evgeny and de Jonge, Martin D.
and Kennedy, Brendan J.},
title = {{H}igh-{P}ressure {S}ynthesis, {S}tructural, and
{S}pectroscopic {S}tudies of the {N}i–{U}–{O} {S}ystem},
journal = {Inorganic chemistry},
volume = {57},
number = {21},
issn = {1520-510X},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2018-06254},
pages = {13847 - 13858},
year = {2018},
abstract = {The first comprehensive structural study of the Ni–U–O
system is reported. Single crystals of α-NiUO4, β-NiUO4,
and NiU3O10 were synthesized, and their structures were
refined—using synchrotron single-crystal X-ray diffraction
data supported by X-ray absorption spectroscopic
measurements. α-NiUO4 adopts an orthorhombic structure in
space group Pbcn and is isostructural to CrUO4 containing
corrugated two-dimensional (2D) layers of corner-sharing UO6
polyhedra and edge-sharing one-dimensional (1D) zigzag
α-PbO2 rutile-like chains of NiO6 polyhedra in the [001]
direction. β-NiUO4 is isostructural to MgUO4 and has an
orthorhombic structure in space group Ibmm, which contains
alternating 1D chains of edge-sharing UO6 and NiO6 polyhedra
in the [001] direction as in regular TiO2 rutile. NiU3O10
forms a triclinic structure in space group P1̅ and is
isostructural with CuU3O10, where it forms a
three-dimensional (3D) framework structure built through a
mixture of UO6 and UO7 polyhedra in which the NiO6 polyhedra
sit isolated within the framework. X-ray absorption
near-edge structure (XANES) measurements, conducted using
XANES mapping of single crystals, support the presence of
hexavalent uranium in the three structures. The polymorphs
of NiUO4 were found to only form under high-pressure and
high-temperature conditions (≥4 GPa and 700 °C). It is
argued that this is a consequence of the relative size
difference between the Ni2+ and U6+ cations, where the Ni2+
cation is effectively too small for the Ibmm structure and
too large for the Pbcn structure to form under ambient
pressure conditions. This does not appear to be an issue for
NiU3O10, which forms under ambient pressure conditions,
where NiO6 polyhedra sit isolated within the framework of 3D
connected UO6/UO7 polyhedra. Synthesis conditions indicate
that β-NiUO4 is the preferred higher-pressure phase and
that the transformation to this occurs irreversibly at a
temperature between 950 and 1000 °C, when P = 4 GPa. The
routes toward the synthesis of the oxides and the associated
structural and spectroscopic results are described with
respect to the structural chemistry of the Ni–U–O
system, the larger AUO4 family of oxides (A = divalent or
trivalent cation), and also their relation to the
rutile-related family of oxides.},
cin = {IEK-6},
ddc = {540},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {161 - Nuclear Waste Management (POF3-161) / Helmholtz Young
Investigators Group: Energy (HGF-YIG-Energy)},
pid = {G:(DE-HGF)POF3-161 / G:(DE-HGF)HGF-YIG-Energy},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30354086},
UT = {WOS:000449576900083},
doi = {10.1021/acs.inorgchem.8b02355},
url = {https://juser.fz-juelich.de/record/856927},
}