Nature of Catalytic Behavior of Cobalt Oxides for CO(2) Hydrogenation

[Image: see text] Cobalt oxide (CoO(x)) catalysts are widely applied in CO(2) hydrogenation but suffer from structural evolution during the reaction. This paper describes the complicated structure–performance relationship under reaction conditions. An iterative approach was employed to simulate the reduction process with the help of neural network potential-accelerated molecular dynamics. Based on the reduced models of catalysts, a combined theoretical and experimental study has discovered that CoO(111) provides active sites to break C–O bonds for CH(4) production. The analysis of the reaction mechanism indicated that the C–O bond scission of *CH(2)O species plays a key role in producing CH(4). The nature of dissociating C–O bonds is attributed to the stabilization of *O atoms after C–O bond cleavage and the weakening of C–O bond strength by surface-transferred electrons. This work may offer a paradigm to explore the origin of performance over metal oxides in heterogeneous catalysis.