Transition from isotropic positive to negative thermal expansion by local Zr₆O₈ node distortion in MOF-801

Abstract

The chemical designability and diversity of metal-organic frameworks (MOFs) endow them with plenty of anomalous properties, such as negative thermal expansion (NTE). Herein, we investigated the thermal expansion behaviors of the well-known MOF-801, which has been widely used in water adsorption and gas separation. The analyses of variable temperature powder X-ray diffraction and Rietveld refinements revealed a fascinating transition from positive thermal expansion to NTE. Further in situ Raman spectra and pair distribution function investigations shed light on the transition being attributed to the local Zr₆O₈ node distortion rather than a long-range phase transition. Our findings will enhance the comprehension of NTE and contribute to the effective utilization of MOF-801 over a broad temperature range.

Keywords

MOF-801 / negative thermal expansion (NTE) / pair distribution function (PDF) / local structure / Zr₆O₈ node distortion

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