Improving the mechanical stability of zirconium-based metal-organic frameworks by incorporation of acidic modulators

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 pK(a). 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.