Unveiling the Activity Origin of Iron Nitride as Catalytic Material for Efficient Hydrogenation of CO2 to C2+ Hydrocarbons

Abstract Developing efficient catalytic materials and unveiling the active species are significant for selective hydrogenation of CO 2 to C 2+ hydrocarbons. Fe 2 N@C nanoparticles were reported to exhibit outstanding performance toward selective CO 2 hydrogenation to C 2+ hydrocarbons (C 2+ selectivity: 53.96 %; C 2 ‐C 4 = selectivity, 31.03 %), outperforming corresponding Fe@C. In situ X‐ray diffraction, ex situ Mössbauer and X‐ray photoelectron spectra revealed that iron nitrides were in situ converted to highly active iron carbides, which acted as the real active species. Moreover, the combined results of in situ diffuse reflectance infrared Fourier transform spectroscopy and control experiments suggested an in situ formed carbonyl iron‐mediated conversion mechanism from iron nitrides to iron carbides.