TY - JOUR
T1 - Thermodynamics of solvent interaction with the metal-organic framework MOF-5
AU - Akimbekov, Zamirbek
AU - Wu, Di
AU - Brozek, Carl K.
AU - Dincə, Mircea
AU - Navrotsky, Alexandra
N1 - Funding Information:
Z. A., D. W., and A. N. thank S. Sahu, G. P. Nagabhushana and D. Reusser for valuable discussions. The calorimetric work in the Navrotsky lab was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Grant DE-FG02-05ER15667. Synthetic work in the Dinca lab was supported by a CAREER award from the National Science Foundation (DMR-1452612).
Publisher Copyright:
© the Owner Societies 2016.
PY - 2015/11/26
Y1 - 2015/11/26
N2 - 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.
AB - 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.
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U2 - 10.1039/c5cp05370f
DO - 10.1039/c5cp05370f
M3 - Article
AN - SCOPUS:84952661390
SN - 1463-9076
VL - 18
SP - 1158
EP - 1162
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 2
ER -