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 CO₂ electroreduction. Herein, a kind of functionalizing exfoliation agent has been selected to simultaneously modify and exfoliate bulk COFs into functional nanosheets and investigate their CO₂ 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 CO₂ 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 CO₂ electroreduction will open up the attractive possibility of developing COFs as efficient CO₂ RR electrocatalysts.