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Issue 18, 2013
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Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit

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Abstract

Metal–organic frameworks (MOFs) with the Zr6O4(OH)4 secondary building unit (SBU) have been of particular interest for potential commercial and industrial uses because they can be easily tailored and are reported to be chemically and thermally stable. However, we show that there are significant changes in chemical and thermal stability of Zr6O4(OH)4 MOFs with the incorporation of different organic linkers. As the number of aromatic rings is increased from one to two in 1,4-benzene dicarboxylate (UiO-66, ZrMOF–BDC) and 4,4′-biphenyl dicarboxylate (UiO-67, ZrMOF–BPDC), the Zr6O4(OH)4 SBU becomes more susceptible to chemical degradation by water and hydrochloric acid. Furthermore, as the linker is replaced with 2,2′-bipyridine-5,5′-dicarboxylate (ZrMOF–BIPY) the chemical stability decreases further as the MOF is susceptible to chemical breakdown by protic chemicals such as methanol and isopropanol. The results reported here bring into question the superior structural stability of the UiO-67 analogs as reported by others. Furthermore, the degradation mechanisms proposed here may be applied to other classes of MOFs containing aromatic dicarboxylate organic linkers, in order to predict their structural stability upon exposure to solvents.

Graphical abstract: Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit

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Publication details

The article was received on 13 Feb 2013, accepted on 15 Mar 2013 and first published on 18 Mar 2013


Article type: Paper
DOI: 10.1039/C3TA10662D
Citation: J. Mater. Chem. A, 2013,1, 5642-5650
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    Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit

    J. B. DeCoste, G. W. Peterson, H. Jasuja, T. G. Glover, Y. Huang and K. S. Walton, J. Mater. Chem. A, 2013, 1, 5642
    DOI: 10.1039/C3TA10662D

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