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@ARTICLE{Ojwang:817987,
author = {Ojwang, Dickson O. and Grins, Jekabs and Wardecki, Dariusz
and Valvo, Mario and Renman, Viktor and Häggström, Lennart
and Ericsson, Tore and Gustafsson, Torbjörn and Mahmoud,
Abdelfattah and Svensson, Gunnar and Hermann, Raphael},
title = {{S}tructure {C}haracterization and {P}roperties of
{K}-{C}ontaining {C}opper {H}exacyanoferrate},
journal = {Inorganic chemistry},
volume = {55},
number = {12},
issn = {1520-510X},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2016-04563},
pages = {5924 - 5934},
year = {2016},
abstract = {Copper hexacyanoferrate, CuII[FeIII(CN)6]2/3·nH2O, was
synthesized, and varied amounts of K+ ions were inserted via
reduction by K2S2O3 (aq). Ideally, the reaction can be
written as CuII[FeIII(CN)6]2/3·nH2O + 2x/3K+ + 2x/3e– ↔
K2x/3CuII[FeIIxFeIII1–x(CN)6]2/3·nH2O. Infrared, Raman,
and Mössbauer spectroscopy studies show that FeIII is
continuously reduced to FeII with increasing x, accompanied
by a decrease of the a-axis of the cubic Fm3̅m unit cell.
Elemental analysis of K by inductively coupled plasma shows
that the insertion only begins when a significant fraction,
$∼20\%$ of the FeIII, has already been reduced.
Thermogravimetric analysis shows a fast exchange of water
with ambient atmosphere and a total weight loss of ∼26 wt
$\%$ upon heating to 180 °C, above which the structure
starts to decompose. The crystal structures of
CuII[FeIII(CN)6]2/3·nH2O and K2/3Cu[Fe(CN)6]2/3·nH2O were
refined using synchrotron X-ray powder diffraction data. In
both, one-third of the Fe(CN)6 groups are vacant, and the
octahedron around CuII is completed by water molecules. In
the two structures, difference Fourier maps reveal three
additional zeolitic water sites (8c, 32f, and 48g) in the
center of the cavities formed by the −Cu–N–C–Fe–
framework. The K-containing compound shows an increased
electron density at two of these sites (32f and 48g),
indicating them to be the preferred positions for the K+
ions.},
cin = {JCNS-2 / PGI-4 / JARA-FIT},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-2-20110106 / I:(DE-Juel1)PGI-4-20110106 /
$I:(DE-82)080009_20140620$},
pnm = {144 - Controlling Collective States (POF3-144) / 524 -
Controlling Collective States (POF3-524) / 6212 - Quantum
Condensed Matter: Magnetism, Superconductivity (POF3-621) /
6213 - Materials and Processes for Energy and Transport
Technologies (POF3-621) / 6G4 - Jülich Centre for Neutron
Research (JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-144 / G:(DE-HGF)POF3-524 /
G:(DE-HGF)POF3-6212 / G:(DE-HGF)POF3-6213 /
G:(DE-HGF)POF3-6G4},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000378369900028},
pubmed = {pmid:27258790},
doi = {10.1021/acs.inorgchem.6b00227},
url = {https://juser.fz-juelich.de/record/817987},
}