Shape‐Controlled Synthesis of Covalent Organic Frameworks Enabled by Polymerization‐Induced Phase Separation

Abstract The shape and morphology modulations of covalent organic frameworks (COFs) are both difficult, but are of significance to tackle to realize high‐performance and practical applications. Here, a two‐step method is reported that separates the phase separation and crystallization processes for the shape‐controlled synthesis of COFs. The insight into the polymerization‐induced phase separation (PIPS) allows for the flexible shaping of COFs into column, rod, film and others, as well as for constructing hierarchically porous structure. The as‐synthesized COF monoliths are crack‐free, no powder detaching, and show 214 MPa of compressive modulus. The resulting good permeability and mechanical flexibility enable COF films to apply for flow‐through adsorption and extraction of pollutants at high flow rates. This work successfully resolves the contradiction between PIPS and crystallization, offering a general approach for scalable production of COFs with desired shapes, sizes, and morphologies.