Mechanism of carbon monoxide dissociation on a cobalt Fischer–Tropsch catalyst

The way in which the triple bond in CO dissociates, a key reaction step in the Fischer–Tropsch (FT) reaction, is a subject of intense debate. Direct CO dissociation on a Co catalyst was probed by ¹²C¹⁶O/¹³C¹⁸O scrambling in the absence and presence of H₂. The initial scrambling rate without H₂ was significantly higher than the rate of CO consumption under CO hydrogenation conditions, which indicated that the surface contained sites sufficiently reactive to dissociate CO without the assistance of H atoms. Only a small fraction of the surface was involved in CO scrambling. The minor influence of CO scrambling and CO residence time on the partial pressure of H₂ showed that CO dissociation was not affected by the presence of H₂. The positive H₂ reaction order was correlated to the fact that the hydrogenation of adsorbed C and O atoms was slower than CO dissociation. Temperature-programmed in situ IR spectroscopy underpinned the conclusion that CO dissociation does not require H atoms.