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@ARTICLE{Li:850015,
author = {Li, Haijian and Kegler, Philip and Bosbach, Dirk and
Alekseev, Evgeny},
title = {{H}ydrothermal {S}ynthesis, {S}tudy, and {C}lassification
of {M}icroporous {U}ranium {S}ilicates and {G}ermanates},
journal = {Inorganic chemistry},
volume = {57},
number = {8},
issn = {1520-510X},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2018-04103},
pages = {4745 - 4756},
year = {2018},
abstract = {Four novel uranyl silicates and germanates with framework
structures, K4Na2(UO2)3(Si2O7)2·3H2O,
K4Na2(UO2)3(Ge2O7)2·3H2O, H3O(UO2)2(HGe2O7)·2H2O, and
Na2(UO2)GeO4, have been synthesized by means of the
hydrothermal method. The structures of the title compounds
were refined by single-crystal X-ray diffraction and
characterized by Raman spectroscopy. We used the method of
secondary building units (SBUs) for a crystal chemical
analysis of the 3D framework and their topologies. The
framework of the K4Na2(UO2)3(T2O7)2·3H2O (T = Si, Ge)
series exhibits large 14-membered rings and smaller
8-membered rings which are built upon [UT4] pentamers. The
internal size of the largest pores is approximately 12.39 ×
3.33 Å2. H3O(UO2)2(HGe2O7)·2H2O is based on 10-membered
rings with intermediate sized pores. They are built upon
[U2Ge2] tetramers with 7-fold-coordinated U. The internal
dimension of the pores in H3O(UO2)2(HGe2O7)·2H2O is smaller
compared to the K4Na2(UO2)3(T2O7)2·3H2O (T = Si, Ge) series
with ∼5.91 × 5.33 Å2. Its topology is similar to several
uranium germanate synthetic phases and silicate minerals,
especially α- and β-uranophane which are constructed from
similar building units. A novel 3D framework type of
Na2(UO2)GeO4with 8-membered rings demonstrates the smallest
free volume in the family of porous uranium germanates. It
crystallizes in tetragonal symmetry and is built upon corner
sharing of [UGe4] pentamers. The size of the channels is
∼6.76 × 4.27 Å2. The vibrational bands in Raman spectra
were associated with pyro-(Si2O7)6-and -(Ge2O7)6-groups,
with the Ge-OH bond and with H3O+cations, confirming the
results of the X-ray crystallographic structural
characterization. We systemized existing uranyl silicates
and germanates based on their building units and chemical
composition. We found a simple structural dependence between
synthetic conditions and chemical composition.},
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:29608306},
UT = {WOS:000430437400059},
doi = {10.1021/acs.inorgchem.8b00466},
url = {https://juser.fz-juelich.de/record/850015},
}