Toward High‐Performance CO2‐to‐C2 Electroreduction via Linker Tuning on MOF‐Derived Catalysts

Abstract Copper (Cu)‐based metal–organic frameworks (MOFs) and MOF‐derived catalysts are well studied for electroreduction of carbon dioxide (CO 2 ); however, the effects of organic linkers for the selectivity of CO 2 reduction are still unrevealed. Here, a series of Cu‐based MOF‐derived catalysts is investigated with different organic linkers appended, named X‐Cu‐BDC (BDC = 1,4‐benzenedicarboxylic acid, X = NH 2 , OH, H, F, and 2F). It is found that the linkers affect the faradaic efficiency (FE) for C 2 products with an order of NH 2  < OH < bare Cu‐BDC < F < 2F, thus tuning the FE C2 :FE C1 ratios from 0.6 to 3.8. As a result, the highest C 2 FE of ≈63% at a current density of 150 mA cm −2 on 2F‐Cu‐BDC derived catalyst is achieved. Using operando Raman measurements, it is revealed that the MOF derives to Cu 2 O during eCO 2 RR but organic linkers are stable. The fluorine group in organic linker can promote the H 2 O dissociation to *H species, further facilitating the hydrogenation of *CO to *CHO that helps CC coupling.