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Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H2, TPC-CO, TPD-CO2, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites. [ABSTRACT FROM AUTHOR]

In this contribution, we examine the effect of the promoter's ionic charge and valence orbital energy on the catalytic activity of Fe-based catalysts, based on in situ synchrotron X-ray powder diffraction (SXRPD), temperature-programmed-based techniques (TPR, TPD, CO-TP carburization), and Fischer--Tropsch synthesis catalytic testing studies. We compared the promoting effects of K (a known promoter for longer-chained products) with Ba, which has a similar ionic radius but has double the ionic charge. Despite being partially "buried" in a crystalline BaCO3 phase, the carburization of the Ba-promoted catalyst was more effective than that of K; this was primarily due to its higher (2+) ionic charge. With Ba2+, higher selectivity to methane and lighter products were obtained compared to the K-promoted catalysts; this is likely due to Ba's lesser capability of suppressing H adsorption on the catalyst surface. An explanation is provided in terms of a more limited mixing between electron-filled Ba2+ 5p and partially filled Fe 3d orbitals, which are expected to be important for the chemical promotion, as they are further apart in energy compared to the K+ 3p and Fe 3d orbitals. [ABSTRACT FROM AUTHOR]