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Issue 2, 2016
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Thermodynamics of solvent interaction with the metal–organic framework MOF-5

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Abstract

The inclusion of solvent in metal–organic framework (MOF) materials is a highly specific form of guest–host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔHf) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)−1, respectively. The enthalpies of interaction (ΔHint) for DMF and DEF with MOF-5 are −82.78 ± 4.84 kJ (mol DMF)−1 and −89.28 ± 3.05 kJ (mol DEF)−1, respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

Graphical abstract: Thermodynamics of solvent interaction with the metal–organic framework MOF-5

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Article information


Submitted
08 Sep 2015
Accepted
25 Nov 2015
First published
26 Nov 2015

Phys. Chem. Chem. Phys., 2016,18, 1158-1162
Article type
Paper
Author version available

Thermodynamics of solvent interaction with the metal–organic framework MOF-5

Z. Akimbekov, D. Wu, C. K. Brozek, M. Dincă and A. Navrotsky, Phys. Chem. Chem. Phys., 2016, 18, 1158
DOI: 10.1039/C5CP05370F

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