Continuous Synthesis and Processing of Covalent Organic Frameworks in a Flow Reactor

Covalent organic frameworks (COFs) are typically prepared in the form of insoluble microcrystalline powders using batch solvothermal reactions that are energy-intensive and require long annealing periods (>120 °C, >72 h). Thus, their wide-scale adoption in a variety of potential applications is impeded by complications related to synthesis, upscaling, and processing, which also compromise their commercialization. Here we report a strategy to address both the need for scalable synthesis and processing approaches through the continuous, accelerated synthesis, and processing of imine- and hydrazone-linked COFs using a flow microreactor. The flow microreactor is capable of unprecedented COF productivities, up to 61,111 kg m^-3 day^-1, and provides control over key stages of COF formation, including nanoparticle growth, self-assembly, and precipitation. Additionally, the technique successfully yields highly crystalline and porous COFs in versatile macroscopic structures such as monoliths, membranes, prints, and packed beds. We also show that a COF synthesized using the flow microreactor acts as an excellent photocatalyst for the photocatalytic degradation of perfluorooctanoic acid (PFOA) outperforming the degradation efficiency of its batch analogue and other classical photocatalysts such as titanium dioxide (TiO₂).