Free-Standing Metal-Organic Framework Membranes Made by Solvent-Free Space-Confined Conversion for Efficient H 2 /CO 2 Separation.

Metal-organic frameworks (MOFs) are promising candidates for the advanced membrane materials based on their diverse structures, modifiable pore environment, precise pore sizes, etc. Nevertheless, the use of supports and large amounts of solvents in traditional solvothermal synthesis of MOF membranes is considered inefficient, costly, and environmentally problematic, coupled with challenges in their scalable manufacturing. In this work, we report a solvent-free space-confined conversion (SFSC) approach for the fabrication of a series of free-standing MOF (ZIF-8, Zn(EtIm) 2 , and Zn 2 (BIm) 4 ) membranes. This approach excludes the employment of solvents and supports that require tedious pretreatment and, thus, makes the process more environment-friendly and highly efficient. The free-standing membranes feature a robust and unique architecture, which comprise dense surface layers and highly porous interlayer with large amounts of irregular-shaped micron-scale pore cavities, inducing satisfactory H 2 /CO 2 selectivities and exceptional H 2 permeances. The ZIF-8 membrane affords a considerable H 2 permeance of 2653.7 GPU with a competitive H 2 /CO 2 selectivity of 17.1, and the Zn(EtIm) 2 membrane exhibits a high H 2 /CO 2 selectivity of 22.1 with an excellent H 2 permeance (6268.7 GPU). The SFSC approach potentially provides a new pathway for preparing free-standing MOF membranes under solvent-free conditions, rendering it feasible for scale-up production of membrane materials for gas separation.