Electrochemical and mechanochemical formation of solid solutions of potassium copper(II)/zinc(II) hexacyanocobaltate(III)/hexacyanoferrate(III) KCuxZn1-x[hcc]x[hcf]1-x

Widmann, Antje; Kahlert, Heike; Wulff, H.; Scholz, Fritz

doi:10.1007/s10008-004-0635-5

Cited by 16 publications

(5 citation statements)

References 44 publications

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“…This second phase would be consistent with the formation of KCu[Co(CN) 6 ] during synthesis, which is certainly feasible on chemical grounds [47,48]. A Pawley fit using this two-phase model confirms our assignment of space group symmetries and rules out the presence of any additional crystalline phases.…”

Section: Crystal Structure Of Cu 3 [Co(cn) 6 ]supporting

confidence: 77%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu 3 [Co(CN) 6 ], which we find to be isostructural to H 3 [Co(CN) 6 ] and the colossal negative thermal expansion material Ag 3 [Co(CN) 6 ]. Using synchrotron X-ray powder diffraction measurements, we find strong positive and negative thermal expansion behaviour respectively perpendicular and parallel to the trigonal crystal axis: α = 25.4(5) MK . These opposing effects collectively result in a volume expansivity α = 7.4(11) MK V −1 that is remarkably small for an anisotropic molecular framework. This thermal response is discussed in the context of the behaviour of the analogous H-and Ag-containing systems. We make use of density-functional theory with many-body dispersion interactions (DFT + MBD) to demonstrate that Cu + …Cu + metallophilic ('cuprophilic') interactions are significantly weaker in Cu 3 [Co(CN) 6 ] than Ag + …Ag + interactions in Ag 3 [Co(CN) 6 ], but that this lowering of energy scale counterintuitively translates to a more moderate-rather than enhanced-degree of structural flexibility. The same conclusion is drawn from consideration of a simple GULP model, which we also present here. Our results demonstrate that strong interactions can actually be exploited in the design of ultra-responsive materials if those interactions are set up to act in tension.

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Section: Crystal Structure Of Cu 3 [Co(cn) 6 ]supporting

confidence: 77%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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“…2a for the KM(II)Fe(III) (CN) 6 compounds show that KZnFe(CN) 6 forms a hexagonal lattice (space group R % 3c) as has been reported. 21 Whereas all the 2g e 2 g , S = 3/2). 22 In order to further determine the electron configuration, magnetic susceptibility of all products was studied.…”

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confidence: 98%

Prussian blue: a new framework of electrode materials for sodium batteries

et al. 2012

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“…The diffraction profiles of both samples are similar, indicating an identical crystal structure ( Figure 3). The diffraction patterns can be assigned to a rhombohedral structure (R-3), which is typical for Prussian Blue analogues with the interstitial sites occupied by a rich amount of Na + ions [86]. The slight broadening of the peaks of 1 frame is probably due to the lattice defects induced by etching.…”

Section: Resultsmentioning

confidence: 99%

Prussian Blue Analogue Mesoframes for Enhanced Aqueous Sodium-ion Storage

Sun

Zhang

2018

Crystals

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Mesostructure engineering is a potential avenue towards the property control of coordination polymers in addition to the traditional structure design on an atomic/molecular scale. Mesoframes, as a class of mesostructures, have short diffusion pathways for guest species and thus can be an ideal platform for fast storage of guest ions. We report a synthesis of Prussian Blue analogue mesoframes by top-down etching of cubic crystals. Scanning and transmission electron microscopy revealed that the surfaces of the cubic crystals were selectively removed by HCl, leaving the corners, edges, and the cores connected together. The mesoframes were used as a host for the reversible insertion of sodium ions with the help of electrochemistry. The electrochemical intercalation/de-intercalation of Na + ions in the mesoframes was highly reversible even at a high rate (166.7 C), suggesting that the mesoframes could be a promising cathode material for aqueous sodium ion batteries with excellent rate performance and cycling stability.

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Electrochemical and mechanochemical formation of solid solutions of potassium copper(II)/zinc(II) hexacyanocobaltate(III)/hexacyanoferrate(III) KCuxZn1-x[hcc]x[hcf]1-x

Cited by 16 publications

References 44 publications

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Prussian blue: a new framework of electrode materials for sodium batteries

Prussian Blue Analogue Mesoframes for Enhanced Aqueous Sodium-ion Storage

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