Hidden diversity of vacancy networks in Prussian blue analogues.
- Simonov A Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK.
- De Baerdemaeker T Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK.
- Boström HLB Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK.
- Ríos Gómez ML Departamento de Polímeros, Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Mexico City, Mexico.
- Gray HJ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK.
- Chernyshov D Swiss-Norwegian Beam Lines, European Synchrotron Radiation Facility, Grenoble, France.
- Bosak A European Synchrotron Radiation Facility, Grenoble, France.
- Bürgi HB Department of Chemistry, University of Zürich, Zürich, Switzerland.
- Goodwin AL Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK. andrew.goodwin@chem.ox.ac.uk.
- 2020-02-14
Published in:
- Nature. - 2020
English
Prussian blue analogues (PBAs) are a diverse family of microporous inorganic solids, known for their gas storage ability1, metal-ion immobilization2, proton conduction3, and stimuli-dependent magnetic4,5, electronic6 and optical7 properties. This family of materials includes the double-metal cyanide catalysts8,9 and the hexacyanoferrate/hexacyanomanganate battery materials10,11. Central to the various physical properties of PBAs is their ability to reversibly transport mass, a process enabled by structural vacancies. Conventionally presumed to be random12,13, vacancy arrangements are crucial because they control micropore-network characteristics, and hence the diffusivity and adsorption profiles14,15. The long-standing obstacle to characterizing the vacancy networks of PBAs is the inaccessibility of single crystals16. Here we report the growth of single crystals of various PBAs and the measurement and interpretation of their X-ray diffuse scattering patterns. We identify a diversity of non-random vacancy arrangements that is hidden from conventional crystallographic powder analysis. Moreover, we explain this unexpected phase complexity in terms of a simple microscopic model that is based on local rules of electroneutrality and centrosymmetry. The hidden phase boundaries that emerge demarcate vacancy-network polymorphs with very different micropore characteristics. Our results establish a foundation for correlated defect engineering in PBAs as a means of controlling storage capacity, anisotropy and transport efficiency.
- Language
-
- English
- Open access status
- green
- Identifiers
-
- DOI 10.1038/s41586-020-1980-y
- PMID 32051599
- Persistent URL
- https://sonar.ch/global/documents/135177
Statistics
Document views: 16
File downloads:
- Full-text: 0