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With ever‐increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn‐based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu‐doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S‐doped Cu/Sn alloy for highly selective electrochemical CO2RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S‐doping and Cu‐alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2RR. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction reaction (CO2RR) to yield synthesis gas (syngas, CO and H2) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2RR activity and the CO/H2 ratio. To address this issue, nitrogen‐doped carbon supported single‐atom catalysts are designed as electrocatalysts to produce syngas from CO2RR. While Co and Ni single‐atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm−2) with CO/H2 ratios (0.23–2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single‐atom configurations for the H2 and CO evolution. The results present a useful case on how non‐precious transition metal species can maintain high CO2RR activity with tunable CO/H2 ratios. [ABSTRACT FROM AUTHOR]