Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure
| العنوان: | Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure |
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| المؤلفون: | Boström, Hanna, Collings, Ines E., Daisenberger, Dominik, Ridley, Christopher J., Funnell, Nicholas P., Cairns, Andrew B. |
| المصدر: | Journal of the American Chemical Society. 143(9):3544-3554 |
| الوصف: | The vast compositional space of Prussian blue analogues (PBAs), formula A(x)M[M'(CN)(6)](y)center dot nH(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 approximate to 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 (4) over bar 3m to P (4) over bar n2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb0.87Mn[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. |
| وصف الملف: | electronic |
| URL الوصول: | https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-440432 https://doi.org/10.1021/jacs.0c13181 https://uu.diva-portal.org/smash/get/diva2:1545527/FULLTEXT01.pdf |
| قاعدة البيانات: | SwePub |
Find this issue from the American Chemical Society | تدمد: | 00027863 |
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| DOI: | 10.1021/jacs.0c13181 |