A facile synthesis of monolithic MOF single crystal for gas separation via a supersaturation strategy

•Proposed a supersaturation strategy for preparing large-area MOF single crystal.•The supersaturation strategy shortens the single crystal growth time, and the synthesis conditions are mild and environmentally friendly.•1D transmission pathway of as-prepared single crystal achieves high CO2 permeability.•The H2O molecules in the MOF pores improve the affinity and solubility of CO2.•3D connection network endows as-prepared single crystal good mechanical stability. Large-area metal–organic framework (MOF) single crystal membrane materials hold great appeal in gas separation field due to their outstanding separation selectivity and permeability. Nevertheless, it is currently difficult to prepare MOF single crystals large enough for gas separation tests owing to the limited manufacturing processes. In this work, we fabricate a self-supporting MOF single crystal (Co-btec SC) membrane with 0.3 × 0.1 cm2 dimension via a facile supersaturation synthesis strategy. Benefiting from the one-dimensional (1D) transmission pathway and three-dimensional (3D) connection network, the obtained Co-btec SC has ultra-high permeability of 47,647 Barrer. Besides, the H2O molecules firmly filled in the pore channels greatly improve the affinity and solubility for CO2, and thus Co-btec SC yields CO2 preferential permeation in CO2/H2 mixture with superior CO2/H2 selectivity of 18.79. In addition, the Co-btec SC shows dramatic high-temperature and high-humidity separation stabilities. To demonstrate the versatility of this strategy, we also successfully fabricated hydrogen-bonded organic framework single crystals (HOF SCs) with the size of about 0.4 cm. This supersaturation strategy opens a new way to fabricate the large-area MOF single crystal membranes.