Active Surface Structure of SnO2 Catalysts for CO2 Reduction Revealed by Ab Initio Simulations

Tin oxide (SnO2) is an efficient catalyst for the CO2 reduction reaction (CO2RR) to formic acid; however, the understanding of the SnO2 surface structure under working electrocatalytic conditions and the nature of catalytically active sites is a current matter of debate. Here, we employ ab initio density functional theory calculations to investigate how the selectivity and reactivity of SnO2 surfaces toward the CO2RR change at varying surface stoichiometry (i.e., reduction degree). Our results show that SnO2(110) surfaces are not catalytically active for the CO2RR or hydrogen evolution reaction, but rather they reduce under an applied external bias, originating surface structures exposing few metal tin layers, which are responsible for formic acid selectivity.