Article (Scientific journals)
Structure Characterization and Properties of K‑Containing Copper Hexacyanoferrate
Ojwang, Dickson O.; Grins, Jekabs; Wardecki, Dariusz et al.
2016In Inorganic Chemistry, 55, p. 5924−5934
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Keywords :
batteries; Mossbauer
Abstract :
[en] 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 ∼26wt % 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.
Disciplines :
Chemistry
Author, co-author :
Ojwang, Dickson O.
Grins, Jekabs
Wardecki, Dariusz
Valvo, Mario
Renman, Viktor
Häggström, Lennart
Ericsson, Tore
Gustafsson, Torbjörn
Mahmoud, Abdelfattah  ;  Université de Liège > Département de chimie (sciences) > LCIS - GreenMAT
Hermann, Raphaël ;  Université de Liège > Département de chimie (sciences) > Département de chimie (sciences)
Svensson, Gunnar
Language :
English
Title :
Structure Characterization and Properties of K‑Containing Copper Hexacyanoferrate
Publication date :
03 June 2016
Journal title :
Inorganic Chemistry
ISSN :
0020-1669
eISSN :
1520-510X
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
55
Pages :
5924−5934
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 27 July 2016

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