Size dependent stability of cobalt nanoparticles on silica under high conversion Fischer–Tropsch environment

Abstract

Highly monodisperse cobalt crystallites, supported on Stöber silica spheres, as model catalysts for the Fischer–Tropsch synthesis were exposed to simulated high conversion environments in the presence and absence of CO utilising an in house developedin situmagnetometer. The catalyst comprising the smallest crystallites in the metallic state (average diameter of 3.2 nm) experienced pronounced oxidation whilst the ratio of H₂O to H₂was increased stepwise to simulate CO conversions from 26% up to complete conversion. Direct exposure of this freshly reduced catalyst to a high conversion Fischer–Tropsch environment resulted in almost spontaneous oxidation of 40% of the metallic cobalt. In contrast, a model catalyst with cobalt crystallites of 5.3 nm only oxidised to a small extent even when exposed to a simulated conversion of over 99%. The largest cobalt crystallites were rather stable and only experienced measurable oxidation when subjected to H₂O in the absence of H₂. This size dependency of the stability is in qualitative accordance with reported thermodynamic calculations. However, the cobalt crystallites showed an unexpected low susceptibility to oxidation,i.e.only relatively high ratios of H₂O to H₂partial pressure caused oxidation. Similar experiments in the presence of CO revealed the significance of the actual Fischer–Tropsch synthesis on the metallic surface as the dissociation of CO, an elementary step in the Fischer–Tropsch mechanism, was shown to be a prerequisite for oxidation. Direct oxidation of cobalt to CoO by H₂O seems to be kinetically hindered. Thus, H₂O may only be capable of indirect oxidation,i.e.high concentrations prevent the removal of adsorbed oxygen species on the cobalt surface leading to oxidation. However, a spontaneous direct oxidation of cobalt at the interface between the support and the crystallites by H₂O forming presumably cobalt silicate type species was observed in the presence and absence of CO. The formation of these metal–support compounds is in accordance with conducted thermodynamic predictions. None of the extreme Fischer–Tropsch conditions initiated hydrothermal sintering. Seemingly, the formation of metal–support compounds stabilised the metallic crystallites and/or higher partial pressures of CO are required to increase the concentration of mobile, cobalt oxide-type species on the metallic surface.