Imparting CO<sub>2</sub> Electroreduction Auxiliary for Integrated Morphology Tuning and Performance Boosting in a Porphyrin‐based Covalent Organic Framework
Yirong Wang, Huimin Ding, Xiaoyu Ma, Ming Liu, Yi‐Lu Yang, Yifa Chen, Shun‐Li Li, Ya‐Qian Lan
Abstract
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.