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Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Thermodynamics of the structural transition in metal-organic frameworks
J Rodriguez1, I Beurroies1, M-V Coulet1
1Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
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.
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