Non-Isothermal Kinetics of Kr Adsorption by Nanoporous γ‑Mg(BH4)2 from in Situ Synchrotron Powder Diffraction

Crystalline materials with pore dimensions comparable to the kinetic diameters of the guest molecules are attractive for their potential use in adsorption and separation applications. The nanoporous γ-Mg­(BH4)2 features one-dimensional channels matching this criterion for Kr uptake, which has been probed using synchrotron powder diffraction at various pressures and temperatures. It results in two coexisting crystalline phases with the limiting composition Mg­(BH4)2·0.66Kr expecting the highest Kr content (50.7 wt % in the crystalline phase) reported for porous materials. Quasi-equilibrium isobars built from Rietveld refinements of Kr site occupancies were rationalized with a noncooperative lattice gas model, yielding the values of the thermodynamic parameters. The latter were independently confirmed from Kr fluorescence. We have also parameterized the pronounced kinetic hysteresis with a modified mean-field model adopted for the Arrhenius kinetics.