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Probing the Influen...
Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure
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- Boström, Hanna (författare)
- Uppsala universitet,Oorganisk kemi,Max Planck Inst Solid State Res, D-70569 Stuttgart, Germany.;Uppsala Univ, Angstrom Lab, Dept Inorgan Chem, SE-75121 Uppsala, Sweden.;Univ Oxford, Dept Chem, Oxford OX1 3QR, England.
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- Collings, Ines E. (författare)
- EMPA Swiss Fed Labs Mat Sci & Technol, Ctr Xray Analyt, CH-8600 Dubendorf, Switzerland.
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- Daisenberger, Dominik (författare)
- Diamond Light Source Ltd, Didcot OX11 0DE, Oxon, England.
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- Ridley, Christopher J. (författare)
- Rutherford Appleton Lab, ISIS Neutron & Muon Source, Didcot OX11 0QX, Oxon, England.
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- Funnell, Nicholas P. (författare)
- Rutherford Appleton Lab, ISIS Neutron & Muon Source, Didcot OX11 0QX, Oxon, England.
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- Cairns, Andrew B. (författare)
- Imperial Coll London, Dept Mat, London SW7 2AZ, England.;Imperial Coll London, London Ctr Nanotechnol, London SW7 2AZ, England.
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(creator_code:org_t)
- 2021-02-25
- 2021
- Engelska.
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 143:9, s. 3544-3554
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Abstract
Ämnesord
Stäng
- 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.
Ämnesord
- NATURVETENSKAP -- Fysik -- Den kondenserade materiens fysik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Condensed Matter Physics (hsv//eng)
- NATURVETENSKAP -- Kemi -- Materialkemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Materials Chemistry (hsv//eng)
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