Electrocleavage Synthesis of Solution-Processed, Imine-Linked, and Crystalline Covalent Organic Framework Thin Films

Developing a general, facile, and direct strategy for synthesizing thin films of covalent organic frameworks (COFs) is a major challenge in this field. Herein, we report an unprecedented electrocleavage synthesis strategy to produce imine-linked COF films directly on electrodes from electrolyte solutions at room temperature. This strategy enables the cathodic exfoliation of the COF powders to nanosheets by electrochemical reduction and protonation, followed by nanosheets migrating to the anode and reproducing the COF structures by anodic oxidation. Our method is adaptable with most imine-linked COFs by virtue of the low redox potential of the imine bonds, whereas the COF films possess high crystallinity and hierarchical porosity. We highlight these COF films as a superb platform for promoting mass transfer by demonstrating their extraordinarily rapid iodine adsorption with record-high rate constants.