Tuning C1/C2 Selectivity of CO2 Electrochemical Reduction over in‐Situ Evolved CuO/SnO2 Heterostructure

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO2 electrochemical reduction (CO2ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges to understanding the reaction mechanism and rationally designing catalysts. Herein, we for the first time elucidate the structural reconstruction of CuO/SnO2 under electrochemical potentials and reveal the intrinsic relationship between CO2ER product selectivity and the in situ evolved heterostructures. At −0.85 VRHE, the CuO/SnO2 evolves to Cu2O/SnO2 with high selectivity to HCOOH (Faradaic efficiency of 54.81 %). Mostly interestingly, it is reconstructed to Cu/SnO2‐x at −1.05 VRHE with significantly improved Faradaic efficiency to ethanol of 39.8 %. In situ Raman spectra and density functional theory (DFT) calculations reveal that the synergetic absorption of *COOH and *CHOCO intermediates at the interface of Cu/SnO2‐x favors the formation of *CO and decreases the energy barrier of C−C coupling, leading to high selectivity to ethanol. For the first time, we report a tuning C1/C2 selectivity of CO2 electrochemical reduction over in situ electrochemically evolved CuO/SnO2 heterostructure. Specifically, the synergetic absorption of *COOH and *CHOCO intermediates at the interface of the newly evolved Cu/SnO2‐x facilitates ethanol generation.