Capturing the Genesis of an Active Fischer–Tropsch Synthesis Catalyst with Operando X‐ray Nanospectroscopy

A state‐of‐the‐art operando spectroscopic technique is applied to Co/TiO2 catalysts, which account for nearly half of the world's transportation fuels produced by Fischer–Tropsch catalysis. This allows determination of, at a spatial resolution of approximately 50 nm, the interdependence of formed hydrocarbon species in the inorganic catalyst. Observed trends show intra‐ and interparticular heterogeneities previously believed not to occur in particles under 200 μm. These heterogeneities are strongly dependent on changes in H2/CO ratio, but also on changes thereby induced on the Co and Ti valence states. We have captured the genesis of an active FTS particle over its propagation to steady‐state operation, in which microgradients lead to the gradual saturation of the Co/TiO2 catalyst surface with long chain hydrocarbons (i.e., organic film formation). Hydrocarbon carpet: The propagation of a Co/TiO2 catalyst system into steady‐state operation is studied by operando and in situ X‐ray nanospectroscopy. A joint understanding of inorganic and organic constituents of the catalyst, products, and reactants is achieved by mapping their respective spatiotemporal evolutions as a function of reaction time‐on‐stream.