Mechanistic Insight into Hydrocarbon Synthesis via CO₂ Hydrogenation on χ-Fe₅C₂ Catalysts

Converting CO₂ into value-added chemicals and fuels is one of the promising approaches to alleviate CO₂ emissions, reduce the dependence on nonrenewable energy resources, and minimize the negative environmental effect of fossil fuels. This work used density functional theory (DFT) calculations combined with microkinetic modeling to provide fundamental insight into the mechanisms of CO₂ hydrogenation to hydrocarbons over the iron carbide catalyst, with a focus on understanding the energetically favorable pathways and kinetic controlling factors for selective hydrocarbon production. The crystal orbital Hamiltonian population analysis demonstrated that the transition states associated with O-H bond formation steps within the path are less stable than those of C-H bond formation, accounting for the observed higher barriers in O-H bond formation from DFT. Energetically favorable pathways for CO₂ hydrogenation to CH₄ and C₂H₄ products were identified which go through an HCOO intermediate, while the CH* species was found to be the key C₁ intermediate over χ-Fe₅C₂(510). The microkinetic modeling results showed that the relative selectivity to CH₄ is higher than C₂H₄ in CO₂ hydrogenation, but the trend is opposite under CO hydrogenation conditions. The major impact on C₂ hydrocarbon production is attributed to the high surface coverage of O* from CO₂ conversion, which occupies crucial active sites and impedes C-C couplings to C₂ species over χ-Fe₅C₂(510). The coexistence of iron oxide and carbide phases was proposed and the interfacial sites created between the two phases impact CO₂ surface chemistry. Adding potassium into the Fe₅C₂ catalyst accelerates O* removal from the carbide surface, enhances the stability of the iron carbide catalyst, thus, promotes C-C couplings to hydrocarbons.