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Issue 10, 2016
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Thermodynamics of the structural transition in metal–organic frameworks

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Abstract

A thermodynamic study of the structural large-pore (LP) to narrow pore (NP) transition in various Metal Organic Frameworks (MOFs) is presented. First, the pressure induced transition at a constant temperature is investigated using a Tian-Calvet microcalorimeter set-up equipped with a high pressure cell. This device permits simultaneous measurements of the mechanical work and heat associated with the LP → NP transition. It is shown that MIL-53(Al) and MIL-53(Cr) have similar thermodynamic and mechanical behaviour whilst the MIL-47(V) system is characterized by much higher transition energy and mechanical work. Second, the temperature induced transition at ambient pressure is studied by means of differential scanning calorimetry (DSC) combined with X-ray absorption spectroscopy. This set-up enables one to follow simultaneously the structural changes associated with the phase transition detected by DSC. The MIL-53(Cr)-Br functionalized MOF is chosen here as a case study where both energetics and structural changes are discussed.

Graphical abstract: Thermodynamics of the structural transition in metal–organic frameworks

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Publication details

The article was received on 14 Sep 2015, accepted on 30 Oct 2015 and first published on 30 Oct 2015


Article type: Paper
DOI: 10.1039/C5DT03591K
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2016,45, 4274-4282
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    Thermodynamics of the structural transition in metal–organic frameworks

    J. Rodriguez, I. Beurroies, M.-V. Coulet, P. Fabry, T. Devic, C. Serre, R. Denoyel and P. L. Llewellyn, Dalton Trans., 2016, 45, 4274
    DOI: 10.1039/C5DT03591K

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