Stable niobia-supported nickel catalysts for the hydrogenation of carbon monoxide to hydrocarbons

Abstract

Stability of metal nanoparticles under reaction conditions is crucial in many catalytic processes. Nickel-based catalysts often encounter severe particle growth in the presence of carbon monoxide due to the formation and migration of nickel carbonyl. In this research, we showed that the reduction temperature of nickel oxide supported on niobia (Nb2O5) influenced the stability of the resulting nickel catalyst during subsequent carbon monoxide hydrogenation. Low reduction temperatures resulted in high initial nickel-normalized activity towards long-chain hydrocarbons (C5+), but fast deactivation throughout the experiment. High reduction temperatures led to a shift in product distribution towards shorter hydrocarbons and a decreased initial nickel-normalized activity, while during the first hours of the experiment an increase in turnover frequency and nickel-normalized activity was observed, resulting eventually in a stable catalytic performance. Electron microscopy analysis revealed extensive particle growth after catalysis when the catalyst had been reduced at low temperatures and no significant changes in particle size when reduced at high temperatures. By use of in-situ FT-IR spectroscopy, nickel subcarbonyl species which are precursors of volatile nickel tetracarbonyl were detected on Ni/Nb2O5 after low temperature reduction and exposure to CO, but not after high temperature reduction. Hence, particle growth is explained by the formation and diffusion of nickel carbonyl and subsequent Ostwald ripening, that leads to larger nickel particles with concomitant decrease in nickel-normalized activity. The stability of the catalyst reduced at high temperature was linked to the formation of niobium suboxides and their partial coverage of the nickel particles limiting the formation of nickel carbonyl and slowing down particle growth.