Improving the mechanical stability of zirconium-based metal-organic frameworks by incorporation of acidic modulators
Van, de Voorde Ben
De, Vos Dirk
Journal of Materials Chemistry A
Royal Society of Chemistry
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Van, d. V. B., Stassen, I., Bueken, B., Vermoortele, F., De, V. D., Ameloot, R., Tan, J., & et al. (2014). Improving the mechanical stability of zirconium-based metal-organic frameworks by incorporation of acidic modulators. Journal of Materials Chemistry A, 3 1737-1742. https://doi.org/10.1039/C4TA06396A
The ability to retain structural integrity under processing conditions which involve mechanical stress, is essential if metal-organic frameworks (MOFs) are to fulfil their potential as serious candidates for use in gas sorption, separation, catalysis and energy conversion applications. A series of zirconium dicarboxylates, predicted to be amongst the more mechanically robust MOFs, have been found to undergo rapid collapse upon ball-milling, resulting in catastrophic losses of porosity. An inverse relationship between collapse time and framework porosity has been found. Addition of acidic modulator ligands (e.g. trifluoroacetic acid) to UiO-66 provided a striking increase in mechanical robustness, the degree of which is inversely related to modulator pKa. This effect, caused by an increased strength of the zirconium – carboxylate bond, provides an important concept to design microporous hybrid frameworks capable of retaining their structure under harsh processing conditions.
T.D.B. would like to thank Trinity Hall for funding, along with Professor Anthony K. Cheetham for use of lab facilities. D.D.V. is grateful to IWT (MOF Shape), KU Leuven for support in the Metusalem grant CASAS and IAP 7/05 Functional Supramolecular Systems. I.S. and B.B. thank Research Foundation – Flanders (FWO) for Ph.D. fellowships.
External DOI: https://doi.org/10.1039/C4TA06396A
This record's URL: https://www.repository.cam.ac.uk/handle/1810/247095