Issue 2, 2016

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

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

Article information

Article type
Paper
Submitted
08 Sept. 2015
Accepted
25 Nov. 2015
First published
26 Nov. 2015

Phys. Chem. Chem. Phys., 2016,18, 1158-1162

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements