The Key to MOF Membrane Fabrication and Application: the Trade‐off between Crystallization and Film Formation

Abstract Metal‐organic frameworks (MOFs), owing the merits of ordered and tailored channel structures in the burgeoning crystalline porous materials, have demonstrated significant promise in construction of high‐performance separation membranes. However, precisely because this crystal structure with strong molecular interaction in their lattice provides robust structural integrity and resistance to chemical and thermal degradation, crystalline MOFs typically exhibit insolubility, infusibility, stiffness and brittleness, and therefore their membrane‐processing properties are far inferior to the flexible amorphous polymers and hinder their subsequent storage, transportation, and utilization. Hence, focusing on film‐formation and crystallization is the foundation for exploring the fabrication and application of MOF membranes. In this review, the film‐forming properties of crystalline MOFs are fundamentally analyzed from their inherent characteristics and compared with those of amorphous polymers, influencing factors of polycrystalline MOF membrane formation are summarized, the trade‐off relationship between crystallization and membrane formation is discussed, and the strategy solving the film formation of crystalline MOFs in recent years are systematically reviewed, in anticipation of realizing the goal of preparing crystalline membranes with optimized processability and excellent performance.