Explanation of the Adsorption of Polar Vapors in the Highly Flexible Metal Organic Framework MIL-53(Cr)
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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.
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