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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−

A hydrogen bonding strategy for achieving an excellent electrocatalytic CO2 reduction reaction performance over an imidazolium‐functionalized covalent organic framework (Co‐iBFBim‐COF‐X) is reported by Yuan‐Biao Huang and co‐workers in their Research Article (e202215687). The halogen anions can form hydrogen bonds with intermediates (*COOH) and thus lower the energy barrier to the formation of CO. Moreover, the water–anion interactions can repel the contact of water with the active centers, thus inhibiting the occurrence of HER. [ABSTRACT FROM AUTHOR]

Moreover, the water-anion interactions can repel the contact of water with the active centers, thus inhibiting the occurrence of HER. The halogen anions can form hydrogen bonds with intermediates (*COOH) and thus lower the energy barrier to the formation of CO. Keywords: CO; CO2 Electrocatalysis; Covalent Organic Framework; Hydrogen Bond; Imidazolium EN CO CO2 Electrocatalysis Covalent Organic Framework Hydrogen Bond Imidazolium 1 1 1 02/07/23 20230206 NES 230206 B A hydrogen bonding strategy b for achieving an excellent electrocatalytic CO SB 2 sb reduction reaction performance over an imidazolium-functionalized covalent organic framework (Co-iBFBim-COF-X) is reported by Yuan-Biao Huang and co-workers in their Research Article (e202215687). [Extracted from the article]