Synthetic fuel production by means of Fischer-Tropsch synthesis (FTS) involves the catalytic hydrogenation of CO over Co-based catalysts. Often, these catalysts incorporate performance-enhancing additives known as promoters. Although not catalytically active for FTS by themselves, promoters can alter the structural and electronic properties of the active Co metal so as to improve catalyst activity, selectivity, or stability. Elements that form metal oxides have been studied for their ability to increase CO consumption rates and shift the product distribution toward higher molecular weight. Despite several decades of study of such elements, there remains limited understanding of the connections between these promotional effects and element properties. Accordingly, this dissertation focuses on clarifying the chemical basis for the effects of metal oxide promotion and making connections to periodic trends.
To understand the importance of physical contact between the promoter and the Co, the influence of Co-Mn spatial association on the magnitude of Mn promotional effects was investigated. Elemental maps obtained by STEM-EDS revealed that different catalyst pretreatment methods could control how closely associated the promoter and Co were at the nanoscale. By relating these results to catalytic reaction data, it was determined that higher extents of contact between the two elements were correlated with higher selectivities toward C5+ hydrocarbons. This work was extended to the elements Ce, Gd, La, and Zr, which are among the most commonly studied metal oxide-forming promoters. The presence of the promoter element suppressed methane formation and increased the FTS chain propagation probability, but the sensitivity of these effects toward promoter loading was different for each element. Elements that deposited preferentially onto the Co nanoparticles led to rapid shifts in the product distribution as the promoter loading increased, whereas elements that dispersed over the entire catalyst surface resulted in more gradual changes. For all promoters, the product selectivities became insensitive to loading when the loading reached a quantity nearly equivalent to that which would form a half monolayer of the promoter on the Co nanoparticle surface. These trends are characteristic of the formation of active sites along the interface between the Co and the promoter that exhibit improved product selectivity.
Structurally, the oxidation states and local coordination environments of the promoters were consistent with highly dispersed oxides. No evidence for the formation of bimetallic alloys or large promoter-containing crystallites was detected by either X-ray absorption spectroscopy or X-ray diffraction. These data suggest that small promoter oxide moieties decorate the surface of the Co metal nanoparticles so as to form metal-metal oxide interfaces. Under this model, the promotional effects increase in magnitude as the fraction of Co active sites that are adjacent to the promoter increases. When the Co surface is sufficiently covered by the promoter so that the fraction of active sites that are along the perimeter of the promoter moieties is nearly unity, the catalyst performance ceases to improve as a function of promoter loading. Guided by this reasoning, the catalytic properties of the promoted catalysts were investigated using samples in which the fraction of sites that were promoted was near unity.
Measurements of reaction kinetics were conducted to assess the impact of metal oxide promotion on the rate parameters governing FTS. The rates of CO consumption for both unpromoted and metal oxide-promoted catalysts followed a Langmuir-Hinshelwood rate law for which H-assisted CO dissociation is assumed to be the rate determining step. Each promoter increased the apparent rate constant and the CO adsorption constant that appear within the rate law. Thus, metal oxide promotion appears both to facilitate the cleavage of the C–O bond and to enhance the extent of CO adsorption onto the catalyst. This finding was reinforced by CO temperature programmed desorption experiments and an evaluation of the effects of Mn promotion on the rate of CO disproportionation. Owing to the appearance of the CO adsorption constant in the numerator and denominator of the rate law, it is possible for promoted catalysts to have both higher and lower turnover frequencies than unpromoted catalysts depending on the chosen operating pressure. As a consequence, an optimal promoter can be found for maximizing the turnover frequency at a given operating pressure. However, product selectivity, which is largely determined by the availability of adsorbed H, is invariably improved by a higher CO adsorption constant because it decreases the ratio of adsorbed H to CO on the Co surface.
Strong correlations between catalyst performance and the Lewis acidity of the promoter oxide suggest that Lewis acid-base interactions between the promoter and the adsorbed CO are the cause for the observed metal oxide promotional effects. Much of the experimental data presented in this work favors the hypothesis that CO can interact simultaneously with Co through the C atom and with the promoter cation through the O atom. These chemical interactions, in which the promoter serves as a Lewis acid, weaken the bond between C and O. Experimental evidence for this effect was observed in the lower activation barrier for CO hydrogenation over the ZrO2-promoted catalysts and the appearance of adsorbed carbonyl species on the MnO-promoted catalyst with severely redshifted C–O stretching frequencies measured by in situ infrared spectroscopy. These results provide insight into the chemical mechanism by which metal oxides affect the reaction and identify Lewis acidity of the promoter as the relevant descriptor for quantitatively predicting metal oxide-based promotional effects over Co FTS catalysts.
