Chemphyschem
Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk, 630090, Russia.
Published: September 2020
We present a detailed solid-state NMR characterization of the molecular dynamics of tert-butyl alcohol (TBA) confined inside breathing metal-organic framework (MOF) MIL-53(Al). Al MAS NMR has demonstrated that TBA adsorption induces the iX phase of MIL-53 material with partially shrunk channels. H solid-state NMR has shown that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two axes and librations of the molecule as a whole about the axis passing through the TBA C-O bond. These librations are realized by two distinct ways: fast molecule orientation change during the translational jump diffusion along the channel with characteristic time τ of about 10 s at 300 K; slow local librations at a single coordination site, representing framework hydroxyl groups, with τ ≈10 s at 300 K. Self-diffusion coefficient of the alcohol in the MOF has been estimated: D=3.4×10 m s at 300 K. It has been inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL-53 (Al).
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