Elucidating the Nature of Fe Species during Pyrolysis of the Fe-BTC MOF into Highly Active and Stable Fischer-Tropsch Catalysts

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 (?′-Fe_2.2C, d_p = 2.5 nm), while at temperatures of 600 °C (Fe@C-600), mainly Hägg carbides are formed (?-Fe₅C₂, d_p = 6.0 nm). Extensive carburization and sintering occur above these temperatures, as at 900 °C the predominant phase is cementite (?-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 mmol_CO g_Fe^-1 s^-1, confirming the outstanding activity and stability of this family of Fe-based FTS catalysts.