Pressure promoted low-temperature melting of metal–organic frameworks

Widmer, Remo N. and Lampronti, Giulio I. and Anzellini, Simone and Gaillac, Romain and Farsang, Stefan and Zhou, Chao and Belenguer, Ana M. and Wilson, Craig W. and Palmer, Hannah and Kleppe, Annette K. and Wharmby, Michael T. and Yu, Xiao and Cohen, Seth M. and Telfer, Shane G. and Redfern, Simon A. T. and Coudert, François-Xavier and MacLeod, Simon G. and Bennett, Thomas D. (2019) Pressure promoted low-temperature melting of metal–organic frameworks. Nature Materials, 18 (4). pp. 370-376. ISSN 1476-1122 DOI

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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.

Item Type: Article
Uncontrolled Keywords: 2018AREP; IA75
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
08 - Green Open Access
12 - PhD
Journal or Publication Title: Nature Materials
Volume: 18
Page Range: pp. 370-376
Identification Number:
Depositing User: Sarah Humbert
Date Deposited: 29 Mar 2019 11:16
Last Modified: 29 Mar 2019 11:16

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