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Pressure promoted low-temperature melting of metal–organic frameworks

DOI: 10.1038/s41563-019-0317-4 DOI Help

Authors: Remo N. Widmer (University of Cambridge) , Giulio I. Lampronti (University of Cambridge) , Simone Anzellini (Diamond Light Source) , Romain Gaillac (Chimie ParisTech, PSL University, CNRS) , Stefan Farsang (University of Cambridge) , Chao Zhou (Aalborg University) , Ana M. Belenguer (University of Cambridge) , Craig Wilson (Atomic Weapons Establishment) , Hannah Palmer (University of Cambridge) , Annette K. Kleppe (Diamond Light Source) , Michael T. Wharmby (Diamond Light Source) , Xiao Yu (University of California, San Diego) , Seth M. Cohen (University of California) , Shane G. Telfer (Massey University) , Simon A. T. Redfern (University of Cambridge) , François-Xavier Coudert (Chimie ParisTech, PSL University, CNRS) , Simon Macleod (Atomic Weapons Establishment) , Thomas Bennett (University of Cambridge)
Co-authored by industrial partner: Yes

Type: Journal Paper
Journal: Nature Materials , VOL 18 , PAGES 370 - 376

State: Published (Approved)
Published: March 2019
Diamond Proposal Number(s): 16133 , 19046

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.

Journal Keywords: Metal–organic frameworks; Phase transitions and critical phenomena; Structure of solids and liquids

Subject Areas: Materials, Chemistry

Instruments: I15-Extreme Conditions

Added On: 27/03/2019 09:38

Discipline Tags:

Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction