Eliminating lattice defects in metal–organic framework molecular-sieving membranes

Metal–organic framework (MOF) membranes are energy-efficient candidates for molecular separations, but it remains a considerable challenge to eliminate defects at the atomic scale. The enlargement of pores due to defects reduces the molecular-sieving performance in separations and hampers the wider application of MOF membranes, especially for liquid separations, owing to insufficient stability. Here we report the elimination of lattice defects in MOF membranes based on a high-probability theoretical coordination strategy that creates sufficient chemical potential to overcome the steric hindrance that occurs when completely connecting ligands to metal clusters. Lattice defect elimination is observed by real-space high-resolution transmission electron microscopy and studied with a mathematical model and density functional theory calculations. This leads to a family of high-connectivity MOF membranes that possess ångström-sized lattice apertures that realize high and stable separation performance for gases, water desalination and an organic solvent azeotrope. Our strategy could enable a platform for the regulation of nanoconfined molecular transport in MOF pores.