Insights into the Structural Evolution Process of Na/ZnFe2O4 Spinel Catalyst in CO2 Hydrogenation

Abstract The CO 2 hydrogenation to olefins process over Fe‐based catalysts offer a promising route for the production of high‐value chemicals from non‐fossil route. Herein, we present a Na promoted ZnFe 2 O 4 spinel catalyst and their structural evolution from fresh state to reduction and to reaction period was elucidated. The clear phase segregation between Fe and Zn occurred after reduction/reaction because of crystalline phase transformation in the order of ZnFe 2 O 4 → ZnO+Fe 7 C 3 +χ‐Fe 5 C 2 →FeO+ZnO+Fe 7 C 3 +χ‐Fe 5 C 2 . The formation of iron carbide phases (Fe 7 C 3 and χ‐Fe 5 C 2 ) was enhanced dramatically by Na promoter. The adjacent Na promoter increase the electron density in Fe−Zn interfaces and enhance its ability to dissociate CO* to form adsorbed CH x * species, thus promoting the formation of olefins. This Na promoted rich electronic Fe−Zn interfaces alters the balance between iron oxides and iron carbides on the catalyst surface, which accelerate the chain growth reaction and facilitate the coupling efficiency of tandem reaction. The various catalysts were characterized by N 2 physisorption, SEM, HR‐TEM, HAADF‐STEM, ex‐situ /in situ XRD, Mössbauer spectra, ICP, in situ XPS, and operando DRIFTs.