Cobalt-Nickel Nanoparticles Supported on Reducible Oxides as Fischer-Tropsch Catalysts

Efficient and more sustainable production of transportation fuels is key to fulfill the ever-increasing global demand. In order to achieve this, progress in the development of highly active and selective catalysts is fundamental. The combination of bimetallic nanoparticles and reactive support materials offers unique and complex interactions that can be exploited for improved catalyst performance. Here, we report on cobalt-nickel nanoparticles on reducible metal oxides as support material for enhanced performance in the Fischer-Tropsch synthesis. For this, different cobalt to nickel ratios (Ni/(Ni + Co): 0.0, 0.25, 0.50, 0.75, or 1.0 atom/atom) supported on reducible (TiO₂ and Nb₂O₅) or nonreducible (α-Al₂O₃) oxides were studied. At 1 bar, Co-Ni nanoparticles supported on TiO₂ and Nb₂O₅ showed stable catalytic performance, high activities and remarkably high selectivities for long-chain hydrocarbons (C₅₊, ∼80 wt %). In contrast, catalysts supported on α-Al₂O₃ independently of the metal composition showed lower activities, high methane production, and considerable deactivation throughout the experiment. At 20 bar, the combination of cobalt and nickel supported on reducible oxides allowed for 25-50% cobalt substitution by nickel with increased Fischer-Tropsch activity and without sacrificing much C₅₊ selectivity. STEM-EDX and IR of adsorbed CO pointed to a cobalt enrichment of the nanoparticle's surface and a weaker adsorption of CO in Co-Ni supported on TiO₂ and Nb₂O₅ and not on α-Al₂O₃, modifying the rate-determining step and the catalytic performance. Overall, we show the strong effect and potential of reducible metal oxides as support materials for bimetallic nanoparticles for enhanced catalytic performance.