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Title: Structure Characterization and Properties of K-Containing Copper Hexacyanoferrate

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [2];  [2];  [2];  [2];  [2];  [3];  [4];  [1]
  1. Stockholm Univ. (Sweden). Dept. of Materials and Environmental Chemistry
  2. Uppsala Univ. (Sweden). Dept. of Chemistry, Angstrom Lab.
  3. Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS). Peter Grunberg Inst. (PGI), Forschungszentrum Juelich GmbH
  4. Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS). Peter Grunberg Inst. (PGI), Forschungszentrum Juelich GmbH; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
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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 F$$m\bar{3}$$m 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. In conclusion, 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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Swedish Research Council VR
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1302943
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 12; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 87 works
Citation information provided by
Web of Science

References (62)

Copper hexacyanoferrate battery electrodes with long cycle life and high power journal November 2011
Battery Technologies for Large-Scale Stationary Energy Storage journal July 2011
Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries journal December 2011
The Effect of Insertion Species on Nanostructured Open Framework Hexacyanoferrate Battery Electrodes journal January 2012
Structural chemistry of Prussian blue analogs. Single-crystal study of manganese(II) hexacyanocobaltate(III), Mn3[Co(DcN)6]2.xH2O journal October 1970
Mössbauer Spectra of In(III) and Ga(III)Hexacyanoferrate(III) journal January 1981
X-ray Diffraction Studies on Heavy-metal Iron-cyanides journal January 1942
Structures and Formulæ of the Prussian Blues and Related Compounds journal April 1936
The structure of three cadmium hexacyanometallates(II): Cd2[Fe(CN)6]·8H2O, Cd2[Ru(CN)6]·8H2O and Cd2[Os(CN)6]·8H2O journal November 2001
Some Performance Characteristics of a Prussian Blue Battery journal January 1985
Electrochromic Switching Mechanism of Iron Hexacyanoferrates Molecular Compounds: The Role of Fe 2+ (CN) 6 Vacancies journal May 2009
The role of vacancies in the hydrogen storage properties of Prussian blue analogues journal February 2007
Catalytic reduction of hydrogen peroxide at metal hexacyanoferrate composite electrodes and applications in enzymatic analysis journal January 2007
Switching between solid-state electroactivity, coupled with ionic conductivity, and semiconducting or dielectric properties in dry mixed-metal hexacyanoferrate powders journal June 1990
Characterization of Prussian Blue analogue: nanocrystalline nickel-iron cyanide journal September 1997
Application of Electroactive Films in Corrosion Protection: II . Metal Hexacyanometalate Films on Surfaces journal July 1991
Copper hexacyanoferate(II) and (III) as trace cesium adsorbers from natural waters journal August 1987
Transparent, Superparamagnetic KCo[FeIII(CN)6]–Silica Nanocomposites with Tunable Photomagnetism journal June 2003
The Nature of Prussian Blue. journal August 1928
The crystal structure of Prussian Blue: Fe4[Fe(CN)6]3.xH2O journal November 1977
Single-crystal study of Prussian Blue: Fe4[Fe(CN)6]2, 14H2O journal January 1972
Neutron diffraction study of Prussian Blue, Fe4[Fe(CN)6]3.xH2O. Location of water molecules and long-range magnetic order journal April 1980
Structure of Fe/Co/Ni Hexacyanoferrate As Probed by Multiple Edge X-ray Absorption Spectroscopy journal June 2008
Non-Prussian Blue Structures and Magnetic Ordering of Na 2 Mn II [Mn II (CN) 6 ] and Na 2 Mn II [Mn II (CN) 6 ]·2H 2 O journal January 2012
Structure and magnetic properties of Zn-Fe cyanide journal April 2001
An atypical coordination in hexacyanometallates: Structure and properties of hexagonal zinc phases journal September 2007
Transformation of cadmium ferricyanide by heating, milling and sonication journal January 1998
Porous framework of T2[Fe(CN)6]·xH2O with T=Co, Ni, Cu, Zn, and H2 storage journal November 2008
Relationship between the Synthesis of Prussian Blue Pigments, Their Color, Physical Properties, and Their Behavior in Paint Layers journal May 2013
Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C I x Co 4 [Fe(CN) 6 ] y (C I = Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN) 6 ] Vacancies in Cesium Derivatives journal November 2001
Structural chemistry of polynuclear transition metal cyanides book January 2005
Synchrotron Structural Characterization of Electrochemically Synthesized Hexacyanoferrates Containing K + : A Revisited Analysis of Electrochemical Redox journal August 2008
Spectroelectrochemistry and electrochemical preparation method of Prussian blue modified electrodes journal September 1982
Observations on the composition of Prussian blue films and their electrochemistry journal March 1988
Identification of Processes Associated with Different Iron Sites in the Prussian Blue Structure by in Situ Electrochemical, Gravimetric, and Spectroscopic Techniques in the dc and ac Regimes journal January 2012
Thermally Induced Electron Transfer in a CsCoFe Prussian Blue Derivative: The Specific Role of the Alkali-Metal Ion journal July 2004
Die Struktur der Hydrate von Co 3 [Co(CN) 6 ] 2 und Cd 3 [Co(CN) 6 ] 2 journal October 1968
Prussian blues journal November 1970
Line profiles of neutron powder-diffraction peaks for structure refinement journal January 1967
Lattice contractions and expansions accompanying the electrochemical conversions of Prussian blue and the reversible and irreversible insertion of rubidium and thallium ions journal April 1996
Precise Electrochemical Control of Ferromagnetism in a Cyanide-Bridged Bimetallic Coordination Polymer journal September 2012
Electrochemical Mg2+ intercalation into a bimetallic CuFe Prussian blue analog in aqueous electrolytes journal January 2013
Ion-Induced Transformation of Magnetism in a Bimetallic CuFe Prussian Blue Analogue journal May 2011
Infrared Spectroelectrochemical Analysis of Adsorbed Hexacyanoferrate Species Formed during Potential Cycling in the Ferrocyanide/Ferricyanide Redox Couple journal November 1997
Nature of Bonding in Metal Cyanide Complexes as Related to Intensity and Frequency of Infrared Absorption Spectra journal August 1963
Structure and magnetic properties of copper(II) hexacyanoferrate(III) compound journal April 2001
Tribochemical oxidation of KBr by transition metal ferricyanides journal June 1988
Structure and Function of Ferricyanide in the Formation of Chromate Conversion Coatings on Aluminum Aircraft Alloy journal October 1999
The vibrational spectra of the cyanide ligand revisited: the ν(CN) infrared and Raman spectroscopy of Prussian blue and its analogues journal May 2011
The Vibrational Spectra of the Cyanide Ligand Revisited: Double Bridging Cyanides journal July 2010
Sodium iron hexacyanoferrate with high Na content as a Na-rich cathode material for Na-ion batteries journal October 2014
Rhombohedral Prussian White as Cathode for Rechargeable Sodium-Ion Batteries journal February 2015
High-pressure studies of the micro-Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O) journal April 2011
Redox reactions in Prussian blue containing paint layers as a result of light exposure journal January 2013
Changeover during in Situ Compositional Modulation of Hexacyanoferrate (Prussian Blue) Material journal December 2006
Structural characterization of electrodeposited copper hexacyanoferrate films by using a spectroscopic multi-technique approach journal January 2012
Thermal-Induced Changes in Molecular Magnets Based on Prussian Blue Analogues journal April 2006
Thermal Decomposition of Prussian Blue Analogues of the Type Fe[Fe(CN) 5 NO] journal August 2000
Studies of different hydrated forms of Prussian Blue
  • Ganguli, Sanjukta; Bhattacharya, Manoranjan
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 79, Issue 7 https://doi.org/10.1039/f19837901513
journal January 1983
Prussian Blue: Artists' Pigment and Chemists' Sponge journal May 2008
Single Crystal of a Prussian Blue Analog based on Rubidium Manganese Hexacyanoferrate journal July 2007
Crystal structure of trimanganese bis(hexakis(cyano)cobaltate) dodecahydrate and tricadmium bis(hexakis(cyano)cobaltate) dodecahydrate by neutron and x-ray diffraction journal November 1977

Cited By (8)

Ni Prussian Blue Analogue/Mesoporous Carbon Composite as Electrode Material for Aqueous K-Ion Energy Storage: Effect of Carbon-Framework Interaction on Its Electrochemical Behavior journal November 2018
Hidden diversity of vacancy networks in Prussian blue analogues journal February 2020
Surfactant-stabilized nano-metal hexacyanoferrates with electrocatalytic and heterogeneous catalytic applications journal March 2018
Operando XAFS and XRD Study of a Prussian Blue Analogue Cathode Material: Iron Hexacyanocobaltate journal October 2018
Removing Cs within a continuous flow set-up by an ionic exchanger material transformable into a final waste form journal March 2019
Commencing an Acidic Battery Based on a Copper Anode with Ultrafast Proton‐Regulated Kinetics and Superior Dendrite‐Free Property journal November 2019
Hidden diversity of vacancy networks in Prussian blue analogues text January 2020
A thermogravimetric study of thermal dehydration of copper hexacyanoferrate by means of model-free kinetic analysis journal March 2017

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