Sb-Doped CeO 2 Nanospheres for Selective CO 2 Electroreduction to Ethanol through Dynamic Redox Cycling of Surface Sb and Ce Sites

It is challenging to construct non-Cu catalysts toward CO 2 electroreduction (CO 2 ER) 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 CeO 2 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 CO 2 ER, which promotes *CO*OH formation and conversion to linear *CO L for further C–C coupling to produce ethanol. The optimal Sb 5.0% -CeO 2 nanospheres can convert CO 2 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 CO 2 ER to ethanol with high selectivity.