R-Fe–based catalyst. Fe/Al alloy powder (50:50 by weight, 200 mesh; Hu’nan Xingyuan Powder Co.) was added into 8 M KOH (AR, Sinopharm Chemical Reagent Co.) solution in a flask under stirring and heated to 70° ± 1°C to dissolve Al in the alloy. Afterward, K+ and AlO2 ions in the solution were washed away sequentially by deionized water (10 times) and ethanol (7 times). The Fe sample powder was transferred into a sealable quartz tube in a glove box and subsequently dried in an Ar flow at room temperature for 6 hours. As-prepared porous Fe powder was kept in a glove box with an extra seal. Before loading the sample in the in situ XRD cell, the in situ Mössbauer cell, or the FT reactor, the sample was passivated in a flow of 1% O2 in He at room temperature for 20 hours.

Fe/SiO2 catalyst. SiO2-supported Fe sample was prepared by incipient wetness impregnation method with SiO2 support (Q15, 120 mesh; Sasol) using an aqueous solution of Fe(NO3)3·9H2O (AR, Sinopharm Chemical Reagent Co.). The sample was sequentially dried at 80°C for 12 hours and 120°C for 24 hours and then calcined at 500°C for 5 hours in static air.

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