Is Carbon Heteroatom Doping the Key to Active and Stable Carbon Supported Cobalt Fischer-Tropsch Catalysts?

Carbon supports are an interesting alternative to established oxidic catalyst supports for Co-based Fischer-Tropsch synthesis (FTS) catalysts as they allow high Co reducibility and do not suffer from the formation of Co/support compounds. To optimize Co-based carbon-supported FTS catalysts, significant research has focused on doping carbon supports with heteroatoms, aiming to enhance both catalytic activity and stability. While improvements in FTS performance have been reported for N-doped carbon supports, the exact effects of heteroatom doping are still poorly understood, largely due to difficulties in directly comparing Co FTS catalysts supported on doped versus nondoped carbon materials. In this study, we synthesized a series of highly comparable N-, S-, and P-doped carbon nanofiber (CNF) model supports, which were combined with size-controlled, colloidal Co nanoparticles to create well-defined model FTS catalysts. Comprehensive characterization of these catalysts using in situ X-ray absorption spectroscopy (XAS), in situ X-ray diffraction (XRD), and in situ magnetometry revealed that the presence of dopants significantly altered the structure and properties of the catalytically active Co⁰ phase, affecting Co coordination numbers, crystal phase composition, and magnetic behavior. Challenging optimistic literature reports, our findings demonstrate that all the studied heteroatoms negatively impact either FTS activity or catalyst stability. Co on N-doped CNFs experienced rapid deactivation due to increased sintering as well as Co phase transformations, which were not observed for Co on nondoped CNFs. Co on S-doped CNF suffered from instability of carbon-bound S species in a hydrogen atmosphere, contributing to low FTS performance by S-poisoning. Finally, Co on P-doped CNFs displayed strong metal-support interactions that improved sintering stability, but FTS activity was hampered by low Co reducibility and the loss of active Co⁰ due to a complex sequence of cobalt phosphide formation and its subsequent decomposition into phosphorus oxides and cobalt oxide species under FTS conditions.