title: Explanation of the adsorption of polar vapors in the highly flexible metal organic framework MIL-53(Cr).
abstract: A comparison of the adsorption of water, methanol, and ethanol polar vapors by the flexible porous chromium(III) terephthalate MIL-53(Cr) was investigated by complementary techniques including adsorption gravimetry, ex situ X-ray powder diffraction, microcalorimetry, thermal analysis, IR spectroscopy, and molecular modeling. The breathing steps observed during adsorption strongly depend on the nature of the vapor. With water, a significant contraction of the framework is observed. For the alcohols, the initial contraction is followed by an expansion of the framework. A combination of IR analysis, X-ray diffraction, and computer modeling leads to the molecular localization of the guest molecules and to the identification of the specific guest-guest and host-guest interactions. The enthalpies of adsorption, measured by microcalorimetry, show that the strength of the interactions decreases from ethanol to water. Differential scanning calorimetry experiments on an EtOH/H(2)O mixture suggest a selective adsorption of ethanol over water.
authors.affiliation: Laboratoire Chimie Provence, UMR 6264, Universités Aix-Marseille I, II & III-CNRS, Centre de Saint Jérôme, 13397 Marseille cedex 20, France.
authors.forename: Sandrine
authors.initials: S
authors.lastname: Bourrelly
authors.forename: Béatrice
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authors.lastname: Moulin
authors.forename: Angel
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authors.lastname: Rivera
authors.forename: Guillaume
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authors.lastname: Maurin
authors.forename: Sabine
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authors.lastname: Devautour-Vinot
authors.forename: Christian
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authors.lastname: Serre
authors.forename: Thomas
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authors.lastname: Devic
authors.forename: Patricia
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authors.lastname: Horcajada
authors.forename: Alexandre
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authors.lastname: Vimont
authors.forename: Guillaume
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authors.lastname: Clet
authors.forename: Marco
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authors.lastname: Daturi
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Lavalley
authors.forename: Sandra
authors.initials: S
authors.lastname: Loera-Serna
authors.forename: Renaud
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authors.lastname: Denoyel
authors.forename: Philip L
authors.initials: PL
authors.lastname: Llewellyn
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey