Sb-Doped CeO2 Nanospheres for Selective CO2 Electroreduction to Ethanol through Dynamic Redox Cycling of Surface Sb and Ce Sites

It is challenging to construct non-Cu catalysts toward CO2 electroreduction (CO2ER) to ethanol with high selectivity due to the difficulty in adjusting active sites for controlling the evolution of reaction intermediates. In this work, Sb-doped CeO2 nanospheres are constructed to tune the reaction intermediates on the active sites toward selective ethanol generation. The primary active sites of one Sb site and two Ce sites undergo fluctuations in the oxidation states during CO2ER, which promotes *CO*OH formation and conversion to linear *COL for further C–C coupling to produce ethanol. The optimal Sb5.0%-CeO2 nanospheres can convert CO2 to ethanol as a single liquid product with selectivity over 50% in a broad potential range from −0.5 to −1.0 V. Remarkably, it exhibits an ethanol Faradaic efficiency of 70.5 ± 1.2% at −0.7 V with stable operation for 48 h. This work provides insights into the non-Cu catalyst design for CO2ER to ethanol with high selectivity.