Boosting Electroreduction of CO₂ over Cationic Covalent Organic Frameworks: Hydrogen Bonding Effects of Halogen Ions

We present the first example of charged imidazolium functionalized porphyrin-based covalent organic framework (Co-iBFBim-COF-X) for electrocatalytic CO₂ reduction reaction, where the free anions (e.g., F^- , Cl^- , Br^- , and I^- ) of imidazolium ions nearby the active Co sites can stabilize the key intermediate *COOH and inhibit hydrogen evolution reaction. Thus, Co-iBFBim-COF-X exhibits higher activity than the neutral Co-BFBim-COF, following the trend of F^- - - - . Particularly, the Co-iBFBim-COF-I^- showed nearly 100 % CO₂ selectivity at a low full-cell voltage of 2.3 V, and achieved a high CO₂ partial current density of 52 mA cm^-2 with a turnover frequency of 3018 h^-1 at 2.4 V in the anion membrane electrode assembly, which is 3.57 times larger than that of neutral Co-BFBim-COF. This work provides new insight into the importance of free anions in the stabilization of intermediates and decreasing the local binding energy of H₂ O with active moiety to enhance CO₂ reduction reaction.