Dynamic structural evolution of iron catalysts involving competitive oxidation and carburization during CO ₂ hydrogenation

Identifying the dynamic structure of heterogeneous catalysts is crucial for the rational design of new ones. In this contribution, the structural evolution of Fe(0) catalysts during CO₂ hydrogenation to hydrocarbons has been investigated by using several (quasi) in situ techniques. Upon initial reduction, Fe species are carburized to Fe₃C and then to Fe₅C₂. The by-product of CO₂ hydrogenation, H₂O, oxidizes the iron carbide to Fe₃O₄. The formation of Fe₃O₄@(Fe₅C₂+Fe₃O₄) core-shell structure was observed at steady state, and the surface composition depends on the balance of oxidation and carburization, where water plays a key role in the oxidation. The performance of CO₂ hydrogenation was also correlated with the dynamic surface structure. Theoretical calculations and controll experiments reveal the interdependence between the phase transition and reactive environment. We also suggest a practical way to tune the competitive reactions to maintain an Fe₅C₂-rich surface for a desired C₂₊ productivity.