Nature of Catalytic Behavior of Cobalt Oxides for CO 2 Hydrogenation.

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.