The Interplay between Structure and Product Selectivity of CO2 Hydrogenation.

Identification of the active structure under reaction conditions is of great importance for the rational design of heterogeneous catalysts. However, this is often hampered by their structural complexity. The interplay between the surface structure of Co3 O4 and the CO2 hydrogenation is described. Co3 O4 with morphology-dependent crystallographic surfaces presents different reducibility and formation energy of oxygen vacancies, thus resulting in distinct steady-state composition and product selectivity. Co3 O4 -0 h rhombic dodecahedra were completely reduced to Co0 and CoO, which presents circa 85 % CH4 selectivity. In contrast, Co3 O4 -2 h nanorods were partially reduced to CoO, which exhibits a circa 95 % CO selectivity. The crucial role of the Co3 O4 structure in determining the catalytic performance for higher alcohol synthesis over CuCo-based catalysts is demonstrated. As expected, Cu/Co3 O4 -2 h shows nine-fold higher ethanol yield than Cu/Co3 O4 -0 h owing to the inhibition for methanation.