ChemInform Abstract: CRYSTAL STRUCTURE OF CADMIUM HEXACYANOPALLADATE(IV)

Buser, H. J.; Ron, G.; Lüdi, A.; Engel, Peter

doi:10.1002/chin.197509408

Cited by 2 publications

(2 citation statements)

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“…The simple average crystal structure belies this compositional and structural complexity as most PBAs—whether defective or alkali-metal-containing or neither—crystallize in face-centered cubic space groups. 5 − 7 Thus, a different probe is needed to fully understand these materials.…”

Section: Introductionmentioning

confidence: 99%

Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure

et al. 2021

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The vast compositional space of Prussian blue analogues (PBAs), formula A x M[M′(CN) 6 ] y · n H 2 O, allows for a diverse range of functionality. Yet, the interplay between composition and physical properties—e.g., flexibility and propensity for phase transitions—is still largely unknown, despite its fundamental and industrial relevance. Here we use variable-pressure X-ray and neutron diffraction to explore how key structural features, i.e., defects, hydration, and composition, influence the compressibility and phase behavior of PBAs. Defects enhance the flexibility, manifesting as a remarkably low bulk modulus ( B 0 ≈ 6 GPa) for defective PBAs. Interstitial water increases B 0 and enables a pressure-induced phase transition in defective systems. Conversely, hydration does not alter the compressibility of stoichiometric MnPt(CN) 6 , but changes the high-pressure phase transitions, suggesting an interplay between low-energy distortions. AMnCo(CN) 6 (A I = Rb, Cs) transition from F 4̅3 m to P 4̅ n 2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb 0.87 Mn[Co(CN) 6 ] 0.91 is further lowered to the polar space group Pn by an improper ferroelectric mechanism. These fundamental insights aim to facilitate the rational design of PBAs for applications within a wide range of fields.

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Section: Introductionmentioning

confidence: 99%

Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure

et al. 2021

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“…1(c)]. 27,28 And, finally, it is the accessibility of Fe 3+/2+ electrochemistry that informs our decision to focus on a hexacyanoferrate salt.…”

Section: Introductionmentioning

confidence: 99%

Revealing the structural complexity of Prussian blue analogues: the case of K2Cu[Fe(CN)6]

Cattermull

Sada

Hurlbutt

et al. 2022

Preprint

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We report the synthesis, crystal structure, thermal response, and electrochemical behaviour of the Prussian blue analogue (PBA) K2Cu[Fe(CN)6]. From a structural perspective, this is the most complex PBA yet characterised: its triclinic crystal structure results from an interplay of cooperative Jahn–Teller order, octahedral tilts, and a collective `slide' distortion involving K-ion displacements. These different distortions give rise to two crystallographically-distinct K-ion channels with different mobilities. Variable-temperature X-ray powder diffraction measurements show that K-ion slides are the lowest-energy distortion mechanism at play, as they are the only distortion to be switched off with increasing temperature. Electrochemically, the material operates as a K-ion cathode with a high operating voltage, and an improved initial capacity relative to higher-vacancy PBA alternatives. On charging, K+ ions are selectively removed from a single K-ion channel type and the slide distortions are again switched on and off accordingly. We discuss the functional importance of various aspects of structural complexity in this system, placing our discussion in the context of other related PBAs.

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ChemInform Abstract: CRYSTAL STRUCTURE OF CADMIUM HEXACYANOPALLADATE(IV)

Cited by 2 publications

References 1 publication

Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure

Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure

Revealing the structural complexity of Prussian blue analogues: the case of K2Cu[Fe(CN)6]

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