Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (440 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

In this combined in situ XAFS, DRIFTS, and Mössbauer study, we elucidate the changes in structural, electronic, and local environments of Fe during pyrolysis of the metal organic framework Fe-BTC toward highly active and stable Fischer–Tropsch synthesis (FTS) catalysts (Fe@C). Fe-BTC framework decomposition is characterized by decarboxylation of its trimesic acid linker, generating a carbon matrix around Fe nanoparticles. Pyrolysis of Fe-BTC at 400 °C (Fe@C-400) favors the formation of highly dispersed epsilon carbides (ε′-Fe2.2C, d p = 2.5 nm), while at temperatures of 600 °C (Fe@C-600), mainly Hägg carbides are formed (χ-Fe5C2, d p = 6.0 nm). Extensive carburization and sintering occur above these temperatures, as at 900 °C the predominant phase is cementite (θ-Fe3C, d p = 28.4 nm). Thus, the loading, average particle size, and degree of carburization of Fe@C catalysts can be tuned by varying the pyrolysis temperature. Performance testing in high-temperature FTS (HT-FTS) showed that the initial turnover frequency (TOF) of Fe@C catalysts does not change significantly for pyrolysis temperatures up to 600 °C. However, methane formation is minimized when higher pyrolysis temperatures are applied. The material pyrolyzed at 900 °C showed longer induction periods and did not reach steady state conversion under the conditions studied. None of the catalysts showed deactivation during 80 h time on stream, while maintaining high Fe time yield (FTY) in the range of 0.19–0.38 mmolCO gFe –1 s–1, confirming the outstanding activity and stability of this family of Fe-based FTS catalysts.

Operando infrared spectroscopy in combination with a kinetic study is used to elucidate the role of potassium on the conversion of carbon monoxide over K-promoted MoS2 catalysts. More specifically, the initial break-in transient has been studied in detail. Stabilization of reaction intermediates, and effect of promoter on the intrinsic properties of MoS2 are discussed. Adsorbed alkoxy species were found to play an important intermediate role in the syngas to alcohol route, and it was found that potassium stabilizes these species. Moreover, the electronic properties of MoS2 change upon promotion, thereby allowing for a relatively easier activation of the CO molecule and a reduced hydrogenation activity toward alkanes.

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