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).
Keywords: Fischer-Tropsch synthesis; X-ray microspectroscopy; chemical imaging; heterogeneous catalysis; nanoparticles.
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