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

作者：Wezendonk Tim A; Santos Vera P; Nasalevich Maxim A; Warringa Quirinus S E; Dugulan A Iulian; Chojecki Adam; Koeken Ard C J; Ruitenbeek Matthijs; Meima Garry; Islam Husn Ubayda; Sankar Gopinathan; Makkee Michiel; Kapteijn Freek^*; Gascon Jorge^*

来源：ACS Catalysis, 2016, 6(5): 3236-3247.

DOI：10.1021/acscatal.6b00426

• Fischer-Tropsch synthesis
• iron
• metal organic framework
• MOF mediated synthesis
• pyrolysis
• structure-activity relations
• iron carbide phases
• dispersion

In this combined in situ XAFS, DRIFTS, and Mossbauer 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 degrees C (Fe@C-400) favors the formation of highly dispersed epsilon carbides (epsilon'-Fe2.2C, d(p) = 2.5 nm), while at temperatures of 600 degrees C (Fe@C-600), mainly Hagg carbides are formed (chi-Fe5C2, d(p) = 6.0 nm). Extensive carburization and sintering occur above these temperatures, as at 900 degrees C the predominant phase is cementite (theta-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 degrees C. However, methane formation is minimized when higher pyrolysis temperatures are applied. The material pyrolyzed at 900 degrees C showed longer induction periods and did not reach steady state conversion under the conditions studied. None of the catalysts showed s(-1), confirming the outstanding activity and stability of this family of Fe-based FTS catalysts. 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)

• 出版日期2016-5