Dynamics of Butane and 1-Butene in ZIF-8 Probed by Solid-State 2H NMR

We present a detailed ${}^2$H NMR characterization of molecular mobility of 1-butene and n-butane propagating through the microporous ZIF-8, a zeolitic imidazolate framework renowned for its outstandingly high stability and separation selectivity of various. The experimental characterization of n-butane and 1-butene diffusivity in ZIF-8 on the molecular scale is provided for the first time. With ${}^2$H NMR spin relaxation analysis we have elucidated the motional mechanism for 1-butene and n-butane guests trapped within ZIF-8 framework and derived kinetic parameters for each type of motion. The characteristic times for microscopic translational diffusion and activation barriers (E${}_{C4H10}$ = 34 kJ mol${}^{-1}$, E${}_{C4H8}$ = 32 kJ mol${}^{-1}$) for n-butane and 1-butene diffusivities have been elucidated. Finally, we show that ${}^2$H NMR technique is capable to provide reliable information on microscopic diffusivity in the ZIF-8 MOF even for molecules with slow diffusion rates (<10${}^{-14}{m}^2{s}^{-1}$).