Effects of initial crystal structure of Fe2O3 and Mn promoter on effective active phase for syngas to light olefins

Although it is generally acknowledged that iron carbides are the active phase in Fischer-Tropsch synthesis (FTS), adjusting the formation of active phase and catalytic performance via the initial crystal structure of iron oxides has never been studied. Herein, we take one-dimensional pure phase α-Fe2O3 and γ-Fe2O3 nonporous nanorods to explore the effects of initial crystal phase of Fe2O3 on both formation of active phase and corresponding catalytic performance, in which the influence of diffusion limitation on selectivity can be ignored. In situ characterizations uncovered that the formation of iron carbides with high selectivity of light olefins strongly depends on the initial crystal phase of iron oxide and its induced metal-promoter interaction. Responding to the morphology effect and crystallographic phase effect, Mn located on surface of γ-Fe2O3 nanorods exhibit a low oxidation state due to a strong Fe-Mn interaction. This interaction was beneficial to the formation of C-poor iron carbide species at the metal-promoter interface during carburization. Hence, outstanding selectivity for light olefins (61.2%) was achieved on 0.5 Mn/γ-Fe2O3 nanorods catalyst at a CO conversion of 55.1% under industrially relevant conditions (320 °C, 1 MPa, H2/CO ratio of 1, and W/F = 5 gcat h mol−1). This finding enriches the fundamental understanding of active phase evolution and promoter effect in STO process and may guide the design of a catalyst with high selectivity.