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Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1

Langmuir, ISSN: 0743-7463, Vol: 29, Issue: 25, Page: 8140-8145
2013
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Article Description

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔH) of the as-synthesized Cu-HKUST-HO ([CuTMA·3H O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔH for Zn-HKUST-DMF ([ZnTMA· 3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [CuTMA] has a ΔH of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔH for Zn-HKUST-amorph [ZnTMA·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-HO by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed HO on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology. © 2013 American Chemical Society.

Bibliographic Details

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

American Chemical Society (ACS)

Materials Science; Physics and Astronomy; Chemistry

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