Dynamic Restructuring of Cu‐Doped SnS2 Nanoflowers for Highly Selective Electrochemical CO2 Reduction to Formate

Abstract With ever‐increasing energy consumption and continuous rise in atmospheric CO 2 concentration, electrochemical reduction of CO 2 into chemicals/fuels is becoming a promising yet challenging solution. Sn‐based materials are identified as attractive electrocatalysts for the CO 2 reduction reaction (CO 2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu‐doped SnS 2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S‐doped Cu/Sn alloy for highly selective electrochemical CO 2 RR 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 H 2 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 CO 2 RR.