Butane isomers mobility and framework dynamics in UiO-66 (Zr) MOF: Impact of the hydroxyl groups in zirconia cluster

UiO-66 (Zr) is a metal-organic framework (MOF) known for its thermal and chemical stability and wide range of adsorption-based applications. This MOF exhibits high separation selectivity for butane isomers. It has been earlier inferred that the separation performance of the material depends on the hydroxylation state of the zirconia cluster. In this contribution, we apply H-2 solid-state NMR to characterize the dynamics of both the MOF organic framework itself and butane isomers in hydroxylated and dehydroxylated forms of UiO-66. It is established that the rate of pi-flipping and the amplitude of the phenylene ring plane librations in the framework are higher for the dehydroxylated form. Self-diffusion coefficients of butane isomers have been estimated for both forms of UiO-66. The diffusivity is higher for n-butane in the dehydroxylated form, whereas the diffusion of isobutane is not affected by the presence of OH groups in the zirconia cluster of the MOF. Higher diffusivity of n-butane in dehydroxylated form is accounted for by the larger effective diameter of the window between the adjacent cages in this form, which arises from faster rotation and larger amplitude of framework linker libration. This ratio-nalizes the higher efficiency of the dehydroxylated form of UiO-66(Zr) material for butane isomers separation.

Automated summary

UiO-66 (Zr) is a metal-organic framework (MOF) with thermal and chemical stability that is widely used for adsorption-based applications. In this study, H-2 solid-state NMR was used to characterize the dynamics of UiO-66 in hydroxylated and dehydroxylated forms. The results showed that the dehydroxylated form had higher pi-flipping rate and phenylene ring plane librations. The diffusivity of butane isomers was also higher in the dehydroxylated form, which can be explained by the larger effective diameter of the window between cages in this form.