Facet sensitivity of iron carbides in Fischer-Tropsch synthesis

Fischer-Tropsch synthesis (FTS) is a structure-sensitive reaction of which performance is strongly related to the active phase, particle size, and exposed facets. Compared with the full-pledged investigation on the active phase and particle size, the facet effect has been limited to theoretical studies or single-crystal surfaces, lacking experimental reports of practical catalysts, especially for Fe-based catalysts. Herein, we demonstrate the facet sensitivity of iron carbides in FTS. As the prerequisite, {202} and {112} facets of χ-Fe₅C₂ are fabricated as the outer shell through the conformal reconstruction of Fe₃O₄ nanocubes and octahedra, as the inner cores, respectively. During FTS, the activity and stability are highly sensitive to the exposed facet of iron carbides, whereas the facet sensitivity is not prominent for the chain growth. According to mechanistic studies, {202} χ-Fe₅C₂ surfaces follow hydrogen-assisted CO dissociation which lowers the activation energy compared with the direct CO dissociation over {112} surfaces, affording the high FTS activity.