Imparting CO2 Electroreduction Auxiliary for Integrated Morphology Tuning and Performance Boosting in a Porphyrin‐based Covalent Organic Framework

Abstract Strategies that enable simultaneous morphology‐tuning and electroreduction performance boosting are much desired for the exploration of covalent organic frameworks in efficient CO 2 electroreduction. Herein, a kind of functionalizing exfoliation agent has been selected to simultaneously modify and exfoliate bulk COFs into functional nanosheets and investigate their CO 2 electroreduction performance. The obtained nanosheets (Cu−Tph−COF−Dct) with large‐scale (≈1.0 μm) and ultrathin (≈3.8 nm) morphology enable a superior FE CH4 (≈80 %) (almost doubly enhanced than bare COF) with large current‐density (−220.0 mA cm −2 ) at −0.9 V. The boosted performance can be ascribed to the immobilized functionalizing exfoliation agent (Dct groups) with integrated amino and triazine groups that strengthen CO 2 absorption/activation, stabilize intermediates and enrich the CO concentration around the Cu active sites as revealed by DFT calculations. The point‐to‐point functionalization strategy for modularly assembling Dct‐functionalized COF catalyst for CO 2 electroreduction will open up the attractive possibility of developing COFs as efficient CO 2 RR electrocatalysts.