Pressure promoted low-temperature melting of metal–organic frameworks

abstract

Metal–organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure–temperature phase diagram. In situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF state expands substantially towards lower temperatures at intermediate, industrially achievable pressures and first-principles molecular dynamics show that softening of the framework coordination with pressure makes melting thermodynamically easier. Furthermore, the MOF glass formed by melt quenching the high-temperature liquid possesses permanent, accessible porosity. Our results thus imply a route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition on heating at ambient pressure.

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Fig. 1: Crystal structure of ZIF-62 and experimental set-up.
Fig. 2: Experimentally derived PT phase diagram for ZIF-62.
Fig. 3: Structural evolution of ZIF-62 in PT space.
Fig. 4: Potential of mean force for the Zn–N distance (r), and dynamics of Zn–N cleavages.

Data availability

Experimental and computational data supporting the findings of this work are available from the public GitHub online repository at https://github.com/fxcoudert/citable-data.

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Acknowledgements

R.N.W. acknowledges support from the EPSRC in the form of a DTG Graduate Studentship. R.N.W. and A.M.B. thank C. Hunter and his group, at the Department of Chemistry (University of Cambridge), for the use of their HPLC facilities. T.D.B. thanks the Royal Society for a University Research Fellowship and for their support (UF150021). C.Z. acknowledges the financial support of the Elite Research Travel Scholarship from the Danish Ministry of Higher Education and Science. We thank Diamond Light Source for access to beamline I15 (EE16133 and EE19046-1). This work benefitted from the financial support of ANRT (thèse CIFRE 2015/0268) and access to HPC platforms provided by a GENCI grant (A0050807069). Gas sorption on the ZIF-62 glass was supported by a grant from the National Science Foundation, Division of Chemistry under award number CHE-1661655. Synthesis of MOFs was supported by a grant from the National Science Foundation under award number CHE-1359906 (to S.M.C.). L. Friche, N. Bandata and O. T. Qasvini (Massey Unviersity) are thanked for technical assistance, alongside B. R. Pimentel (UCSD).

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T.D.B. and S.A.T.R. designed the project. R.N.W., G.I.L, S.A., S.G.M, A.K.K., M.T.W., S.F., C.Z., C.W. and T.D.B. performed the PXRD experiments. S.G.M. designed and constructed the high-P-T PXRD equipment. R.N.W. performed melting point determinations, Raman spectroscopy and microscopy, and analysed XRD and spectroscopic data. H.P. and C.Z. performed DSC measurements. A.M.B. and R.N.W. performed HPLC measurements. X.Y, S.M.C. and S.G.T. performed gas sorption measurements. R.G. and F.-X.C. designed, performed and analysed the molecular simulations. All authors participated in discussing the data. R.N.W. and T.D.B. wrote the manuscript with input from all authors.

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Correspondence to Thomas D. Bennett.

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Supplementary Information

Supplementary Methods, Supplementary Figures 1–22, Supplementary Tables 1–5, Supplementary References 1–10

Supplementary Video 1

In situ video of melting of ZIF-62 crystals at high pressure and temperature, with speed-up factor of ×8.

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Widmer, R.N., Lampronti, G.I., Anzellini, S. et al. Pressure promoted low-temperature melting of metal–organic frameworks. Nat. Mater. 18, 370–376 (2019). https://doi.org/10.1038/s41563-019-0317-4

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