Unraveling the dynamic structural evolution and reaction mechanisms of catalysts from the surface to bulk phase is key to advancing the understanding of catalytic origins. Herein, we report that an in situ formed dynamic FeOx/Fe3C heterostructure serves as the catalytically active phase, enabling rapid carbon and oxygen atom exchange with reactants under the reverse water–gas shift (RWGS) reaction. On the disordered FeOx (1 ≤ x ≤ 1.5) surface, CO2 is dissociated into gaseous CO and surface O, while partial CO further decomposes into C that infiltrates into the Fe3C lattice. The C atoms from bulk Fe3C can combine with the O atoms on FeOx to form CO, allowing Fe3C to serve as a reservoir for C atom transfer. Meanwhile, H2 effectively removes residual surface oxygen to prevent overoxidation. The FeOx/Fe3C catalyst, enabled by synergistic surface-to-bulk cycling mechanism, achieves an unprecedented rate of 1.1 × 10–2 mol/gcat/s at 600 °C in the RWGS reaction, exceeding all previously reported catalysts. This study reveals mechanistic insight into simultaneous catalysis from the surface to the bulk in heterostructured solid catalysts, offering a new perspective on the origin of the exceptional activity of iron-based catalysts in the RWGS reaction.
Li et al. (Thu,) studied this question.