title: Thermodynamics of the structural transition in metal-organic frameworks.
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.
authors.affiliation: Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
authors.forename: J
authors.initials: J
authors.lastname: Rodriguez
authors.affiliation: Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
authors.forename: I
authors.initials: I
authors.lastname: Beurroies
authors.affiliation: Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
authors.forename: M-V
authors.initials: MV
authors.lastname: Coulet
authors.affiliation: Institut Lavoisier Versailles, Université de Versailles St-Quentin, 45, avenue des Etats-Unis, 78035 Versailles Cedex, France.
authors.forename: P
authors.initials: P
authors.lastname: Fabry
authors.affiliation: Institut Lavoisier Versailles, Université de Versailles St-Quentin, 45, avenue des Etats-Unis, 78035 Versailles Cedex, France.
authors.forename: T
authors.initials: T
authors.lastname: Devic
authors.affiliation: Institut Lavoisier Versailles, Université de Versailles St-Quentin, 45, avenue des Etats-Unis, 78035 Versailles Cedex, France.
authors.forename: C
authors.initials: C
authors.lastname: Serre
authors.affiliation: Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
authors.forename: R
authors.initials: R
authors.lastname: Denoyel
authors.affiliation: Aix-Marseille University, CNRS, MADIREL-UMR 7246, Campus de St. Jérôme, 13397 Marseille Cedex 20, France. philip.llewellyn@univ-amu.fr.
authors.forename: P L
authors.initials: PL
authors.lastname: Llewellyn