Temperature-Swing Synthesis of Highly Crystalline Covalent Organic Framework Films for Fast and Precise Molecular Separations

Producing crystalline covalent organic framework (COF) films is intimately related to the elusive nucleation and growth processes, which is desirable for efficient molecular transport. Rational control over these processes and insights into the mechanisms are crucial to improve synthetic methodology and achieve COF films with regular channels. Here, we report the controllable synthesis of COF films via the temperature-swing strategy and explore their crystallization from monomer assemblies to film formation. A detailed time-dependent study reveals that COF crystallites preferentially coalesce at low temperature, progressing from assembled nanospheres to continuous films through lateral and vertical interactions. Moreover, appropriately elevating the synthesis temperature promotes crystal growth and eliminate the defects of weakly crystalline regions, contributing to highly crystalline and porous COF film with a surface area of 746 m² g⁻¹. The prepared COF composite membrane exhibits a methanol permeance of 79 L m⁻² h⁻¹ bar⁻¹, which is 4.5 times higher than the weakly crystalline counterpart. In addition, the molecular sieving test recognize great membrane selectivity to discriminate the antibiotic mixture with a high separation factor of 15.4. This work offers a feasible way for the rational design of the synthesis environment, enabling access to highly crystalline framework materials for targeting molecular separations.