Toward High‐Performance CO<sub>2</sub>‐to‐C<sub>2</sub> Electroreduction via Linker Tuning on MOF‐Derived Catalysts
Rongzhen Chen, Ling Cheng, Jinze Liu, Yating Wang, Wangxin Ge, Chuqian Xiao, Hao Jiang, Yuhang Li, Chunzhong Li
Abstract
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 CC coupling.