Abstract
Throughout much of condensed matter science, correlated disorder is a key to material function. While structural and compositional defects are known to exist within a variety of metal-organic frameworks (MOFs), the prevailing understanding is that these defects are only ever included in a random manner. Here we show-using a combination of diffuse scattering, electron microscopy, anomalous X-ray scattering and pair distribution function measurements-that correlations between defects can in fact be introduced and controlled within a hafnium terephthalate MOF. The nanoscale defect structures that emerge are an analogue of correlated Schottky vacancies in rocksalt-structured transition metal monoxides and have implications for storage, transport, optical and mechanical responses. Our results suggest how the diffraction behaviour of some MOFs might be reinterpreted, and establish a strategy of exploiting correlated nanoscale disorder as a targetable and desirable motif in MOF design.
Original language | English |
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Article number | 4176 |
Journal | Nature Communications |
Volume | 5 |
DOIs | |
State | Published - Jun 20 2014 |
Externally published | Yes |
Funding
M.J.C. and A.L.G. acknowledge financial support from the E.P.S.R.C. (EP/G004528/2) and the E.R.C. (Grant Ref: 279705), and are grateful to J.A.M. Paddison (Oxford) for useful discussions. X.Z. and W.W. acknowledge financial support from the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA) and the Knut and Alice Wallenberg (KAW) Foundation through the project grant 3DEM-NATUR. The EM facility is supported by the KAW Foundation. We thank Dr R. Jacobs of the Oxford Surface Analysis Facility for SEM measurements, the Oxford Materials Characterization Service for BET measurements, the Diamond Light Source for the provision of beamtime on I15 (proposal NT5052) and A. Ross (Diamond) for technical support. This work was performed using HPC resources from GENCI-IDRIS (grant i2014087069).