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Abstract: Electrochemical carbon dioxide (CO2) reduction can produce valuable carbonaceous compounds that are in significant demand, due to its ability to decrease the accumulated atmospheric CO2 and improve the intermittent nature of renewable energy sources. Considering the sluggish kinetics of CO2 reduction reaction, the multielectron–proton transfer process, and the inevitable mixed reduction products, designing efficient and robust electrocatalysts that benefit from the structure–activity relationship is the focus to promote CO2 conversion. In this review, various metal‐based materials are first classified and discussed in terms of their structural and elemental compositions for catalytic behaviors. Afterward, the most intrinsic microstructural/electronic effects as well as the influence of compositional alteration on the catalyst activity, selectivity, and stability are summarized. Additionally, recent attempts to develop the assigned electrochemical cells are surveyed and described from a technological point of view. [ABSTRACT FROM AUTHOR]

Polynary single‐atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active‐site prototype remain elusive. Here we report isolated diatomic Ni‐Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from −0.5 to −0.9 V (98 % at −0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni‐Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO‐adsorbed moiety upon CO2 uptake. [ABSTRACT FROM AUTHOR]