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Structure Characterization and Properties of K-Containing Copper Hexacyanoferrate
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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Number of Authors: 11
2016 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 12, 5924-5934 p.Article in journal (Refereed) Published
Abstract [en]

Copper hexacyanoferrate, Cu-II[Fe-III(CN)(6)](2/3)center dot nH(2)O, was synthesized, and varied amounts of IC ions were inserted via reduction by K2S2O3 (aq). Ideally, the reaction can be written as Cu-II[Fe-III(CN)(6)](2/3)-nH(2)O + 2x/3K(+) + 2x/3e(-)K(+) <-> K-2x/3 Cu-II[Fe-x(II).Fe-1-x(II),(CN)(6)](2/3)-nH(2)O. Infrared, Raman, and Mossbauer spectroscopy studies show that Fe-II is continuously reduced to Fell with increasing x, accompanied by a decrease of the a-axis of the cubic Fn (3) over barm unit cell. Elemental analysis of K by inductively coupled plasma shows that the insertion only begins when a significant fraction similar to 10% of the Fe-III, has already been reduced. Thermogravimetric analysis shows a fast exchange of water with ambient atmosphere and a total weight loss of similar to 26 wt % upon heating to 180 degrees C, above which the structure starts to decompose. The crystal structures of Cu-III[Fe-III(CN)(6)](2/3)center dot nH(2)O and K2/3Cu[Fe(CN)(6)](2/3)center dot nH(2)O 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 Cull 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.

Place, publisher, year, edition, pages
2016. Vol. 55, no 12, 5924-5934 p.
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-132403DOI: 10.1021/acs.inorgchem.6b00227ISI: 000378369900028PubMedID: 27258790OAI: oai:DiVA.org:su-132403DiVA: diva2:952563
Available from: 2016-08-15 Created: 2016-08-11 Last updated: 2017-08-29Bibliographically approved
In thesis
1. Prussian blue analogue copper hexacyanoferrate: Synthesis, structure characterization and its applications as battery electrode and CO2 adsorbent
Open this publication in new window or tab >>Prussian blue analogue copper hexacyanoferrate: Synthesis, structure characterization and its applications as battery electrode and CO2 adsorbent
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Prussian blue (PB) and Prussian blue analogues (PBAs) are compounds with potential applications in a large variety of fields such as gas storage, poison antidotes, electrochromism, electrochemistry and molecular magnets. The compounds are easy to synthesize, cheap, environmentally friendly and have been pursued for both fundamental research and industrial purposes. Despite the multifunctionality of PB and PBAs, they have complicated compositions, which are largely dependent on the synthesis methods and storage conditions. Thus, performing investigations on such compounds with defined composition, stoichiometry and crystal structure is essential.

This thesis has focused on synthesis and detailed structure characterization of copper hexacyanoferrate (CuHCF) via X-ray powder diffraction (XRPD), neutron powder diffraction (NPD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-optical emission spectroscopy (ICP-OES), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS), infrared (IR) and Raman techniques. In addition, kinetics of thermal dehydration process, CO2 adsorption and CO2 adsorption kinetics were investigated. Moreover, in operando synchrotron X-ray diffraction experiments were performed to gain insight into the structure-electrochemistry relationships in an aqueous CuHCF/Zn battery during operation.

Place, publisher, year, edition, pages
Stockholm: Materials and Environmental Chemistry, Stockholm University, 2017
Keyword
copper hexacyanoferrate, synthesis, structure refinement, thermal dehydration, CO2 adsorption, kinetic analysis, in operando synchrotron X-ray diffraction
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146335 (URN)978-91-7649-940-5 (ISBN)978-91-7649-941-2 (ISBN)
Public defence
2017-10-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius Väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, 2011:6512
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.

Available from: 2017-09-18 Created: 2017-08-29 Last updated: 2017-09-14Bibliographically approved

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