Gas Permeation Through Single-Crystal ZIF-8 Membranes

Grain boundaries are an unavoidable microstructural feature in intergrown polycrystalline metal-organic framework (MOF) membranes. They have been suspected to be less size-selective than a MOF’s micropores, resulting in suboptimal separation performances – a speculation recently confirmed by transmission electron microscopy of MOF ZIF-8. Single-crystal membranes, without grain boundaries, should confine mass transport to micropores and reflect the intrinsic selectivity of the porous material. Here, we demonstrate the feasibility of fabricating single-crystal MOF membranes and directly measuring gas permeability through such a membrane using ZIF-8 as an exemplary MOF. Our single-crystal ZIF-8 membranes achieved ideal selectivities up to 28.9, 10.0, 40.1 and 3.6 for gas pairs CO₂/N₂, CO₂/CH₄, He/CH₄ and CH₄/N₂ respectively, much higher than or reversely selective to over 20 polycrystalline ZIF-8 membranes, unequivocally proving the non-selectivity of grain boundaries. The permeability trend obtained in single-crystal membranes aligned with a force field that had been validated against multiple empirical adsorption isotherms.