Chinese Journal of Catalysis ›› 2025, Vol. 74: 4-21.DOI: 10.1016/S1872-2067(25)64738-3
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Xueqing Zhang, Wusha Jiye, Yuhua Zhang, Jinlin Li, Li Wang*()
Received:
2024-12-31
Accepted:
2025-04-18
Online:
2025-07-18
Published:
2025-07-20
Contact:
*E-mail: About author:
Li Wang (South-Central Minzu University) received his B.S. degree in 2005 from Anhui University, and his M.S. and Ph. D degrees in 2007 and 2010, respectively, from Nanjing University. From 2010 to 2012, he worked as a senior engineer at Sinopec Shanghai Research Institute of Petrochemical Technology. In 2013, he joined the faculty of South-Central Minzu University, working in the Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education. From 2016 to 2017, he was a visiting scholar at Pacific Northwest National Laboratory and Washington State University, USA. He was selected for the Young Top-notch Talent Cultivation Program of Hubei Province (2021) and was recognized as a Young Talent by the National Ethnic Affairs Commission of China (2022). His current research focuses on the Fischer-Tropsch synthesis and the application of industrial catalysts. In 2024, he was honored as an Outstanding Young Editorial Board Member by the Journal of Fuel Chemistry and Technology. He has published more than 100 peer-reviewed papers.
Supported by:
Xueqing Zhang, Wusha Jiye, Yuhua Zhang, Jinlin Li, Li Wang. Advances in iron-based Fischer-Tropsch synthesis with high carbon efficiency[J]. Chinese Journal of Catalysis, 2025, 74: 4-21.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64738-3
Fig. 2. (a) Qualitative interpretation of the ab initio atomistic thermodynamics study of the iron carbide structures. Reproduced from Ref. [42] with permission from American Chemical Society. (b) Scheme for the preparation of ε-Fe2C from the RQ Fe50Al50 alloy. Reproduced from Ref. [44] with permission from Nature Publishing Group. (c) Schematic Illustration of the Formation Mechanism of χ-Fe5C2 NPs. Reproduced from Ref. [52] with permission from American Chemical Society. (d) TEM images of the prepared single-phase θ-Fe3C sample. Reproduced from Ref. [60] with permission from Multidisciplinary Digital Publishing Institute. (e) Catalytic activity of iron carbide phases (Fe7C3, χ-Fe5C2, and ε-Fe2C) in FTS. Reproduced from Ref. [61] with permission from American Chemical Society.
Fig. 4. (a) Synthesis of the pure iron carbide phase. (b) The mechanism of Fischer-Tropsch synthesis. (c) CO conversion as a function of time over α-Fe, ε-Fe2C, Fe7C3, and χ-Fe5C2 catalysts (reaction conditions: 270 °C, 30 bar, 20 mL min-1 syngas). Reproduced from Ref. [62] with permission from Chinese Chemical Society. (d) Two typical particle growth mechanisms. Reproduced from Ref. [70] with permission from Royal Society of Chemistry. (e) The deactivation methods of iron-based catalysts during Fischer-Tropsch reaction.
Fig. 5. (a) MOFMS strategy for the Fe-based FTS catalysts: direct pyrolysis of Basolite F-300 and impregnation of the MOF precursor with a carbon source (FA) followed by pyrolysis. Reproduced from Ref. [43] with permission from Nature Publishing Group. (b) Illustration of the green and facile preparation approach of the natural magnetite-based porous Fe@C nanohybrids for FTS. Reproduced from Ref. [103] with permission from Royal Society of Chemistry.
Fig. 6. Schematic models of iron-based catalysts for Fischer-Tropsch synthesis. (a) Conventional catalysts with unconfined iron carbide (FexC) particles as the active phase. (b) Graphene layer-confined ε-Fe2C. Reproduced from Ref. [105] with permission from Nature Publishing Group.
Fig. 7. Schematic models of the armor catalyst confined by two-dimensional materials. Reproduced from Ref. [107] with permission from Royal Society of Chemistry.
Fig. 8. (a) Operando M?ssbauer spectroscopy of R-Fe catalysts. (b) FTS performance of the R-Fe catalyst as a function of time on stream. Reproduced from Ref. [121] with permission from American Association for the Advancement of Science. (c) Catalytic performance of optimized Mn-χ-Fe5C2. (d) In situ M?ssbauer spectra of the transformation of Mn-promoted Raney iron, showing as-prepared, after carburization and after Fischer-Tropsch to linear α-olefin reaction. Reproduced from Ref. [123] with permission from Springer Nature.
Fig. 9. (a) Catalytic performance of Fe2O3@SiO2-(CH3)3 catalyst. Reproduced from Ref. [126] with permission from Elsevier. (b) Catalytic performance of FeMn@Si-c catalyst. Reproduced from Ref. [124] with permission from American Association for the Advancement of Science.
Fig. 10. (a) Catalytic performance of FeNa@SiO2-c, FeNa@SiO2-c+HZSM-5 catalysts. Reproduced from Ref. [127] with permission from Wiley-VCH. (b) Catalytic performance of modified Fe/ZSM-5 catalyst. Reproduced from Ref. [129] with permission from Elsevier. (c) Catalytic performance of Fe3O4@SiO2-PFTS catalyst. Reproduced from Ref. [130] with permission from Elsevier.
Fig. 11. (a) Catalytic performance of FeK/G catalyst. Reproduced from Ref. [136] with permission from American Chemical Society. (b) Catalytic performance of N-doped graphitic carbon encapsulated iron-based catalyst. Reproduced from Ref. [137] with permission from Elsevier. (c) Catalytic performance of χ-Fe5C2 @Graphene catalyst. Reproduced from Ref. [138] with permission from National Academy of Sciences.
Fig. 12. (a) Surface-normalized carbon absorption energy (ωabs) of ε-Fe2C surfaces with and without graphene(-N) layers and the most stable structures labeled by the distances between ε-Fe2C and graphene (data in parenthesis referring to those of graphene-N). Reproduced from Ref. [105] with permission from Nature Publishing Group. (b) WGS reaction of 5Fe@C catalysts. (c) Absorption energies (Ead) of O, OH, H2O, CO, and CO/H species on pure, graphene-covered, or C-vacant-graphene-covered χ-Fe5C2 surfaces. Reproduced from Ref. [138] with permission from National Academy of Sciences.
Strategies | Catalysts | Treatment | FT condition | TOS (h) | FTY μmolCO-1 gFe-1 s-1 | CO Conv. (%) | Sel. (%) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|---|---|
CO2 | CH4 | C2-C4 | C5+ | ||||||||
Conventional catalysts | 38-Fe@C | H2; 425 °C; 3 h | 340 °C; H2/CO = 1; 2 MPa; 30000 h-1 | 10 | 380.0 | 72.0 | 46.8 | 15.0 | 28.0 | 57.0 | [ |
Fe/α-Al2O3 | H2; 350 °C; 2 h | 340 °C; H2/CO=1; 2 MPa; 1500 h-1 | 64 | 84.8 | 77.0 | 46.0 | 24.0 | 56.0 | 20.0 | [ | |
Fe-in-CNT | H2; 350 °C; 5 h | 270 °C; H2/CO=2; 5.1 MPa; 2 L h-1 gcat.-1 | 24 | — | 40.0 | 18.0 | 12.0 | 41.0 | 29.0 | [ | |
35Fe/hNCNC-3 | H2; 350 °C; 2 h | 350 °C; H2/CO=1; 0.1 MPa; 12 L h-1 gcat.-1 | 60 | — | 3.5 | 39.4 | 25.0 | 57.4 | 17.6 | [ | |
FeK2/rGO | 5%H2; 450 °C; 16 h | 340 °C; H2/CO=1; 2 MPa; 24 L h-1 gcat.-1 | 24 | 220.0 | 61.0 | 51.0 | 20.0 | 73.3 | 6.7 | [ | |
Fe/Ru/SiO2 | H2/CO = 2; 280 °C; 20 h | 260 °C; H2/CO=2; 1.5 MPa; 2000 h-1 | 73 | — | 46.1 | 21.2 | 19.7 | 44.3 | 36.0 | [ | |
Phase-pure iron carbide | θ-Fe3C | NA | 250 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 100 | — | 30.0 | 9.9 | 9.4 | 39.4 | 51.2 | [ |
ε-Fe2C/ε'-Fe2.2C | 20%H2; 280 °C; 12 h | 235 °C; H2/CO=1.5; 2.3 MPa; 18000 h-1 | 150 | — | 15.0 | 5.3 | 12.0 | 29.0 | 49.0 | [ | |
Mn-χ-Fe5C2 | H2/CO = 30; 350 °C; 6 h | 250 °C; H2/CO=1.5; 3 MPa; 5 L h-1 gcat.-1 | 1100 | — | 46.1 | 9.4 | 8.1 | 44.4 | 47.5 | [ | |
Hydrophobic modification | Fe1Mn0.3@Si-c | H2; 350 °C; 10 h; syngas; 320 °C; 5 h | 320 °C; H2/CO=2; 3 MPa; 4000 h-1 | 100 | — | 56.1 | 13.0 | 12.0 | 26.0 | 62.0 | [ |
B-Fe2O3@SiO2-(CH3)3 | H2/CO = 2; 300 °C; 4 h | 320 °C; H2/CO=2; 1.5 MPa; 3000 h-1 | 12 | — | 50.0 | 3.4 | 38.0 | 51.0 | 11.0 | [ | |
FeNa@Si-c+HZSM-5 | H2; 350 °C; 2 h | 260 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 10 | — | 49.8 | 14.3 | 7.7 | 17.0 | 75.3 | [ | |
Fe/SiO2-HP3 | H2; 150 °C; 2 h; 250 °C; 2 h; 350 °C; 16 h | 280 °C; H2/CO=1.5; 2 MPa; 2.4 L h-1 gcat.-1 | 160 | — | 19.7 | 16.0 | 18.0 | 32.0 | 50.0 | [ | |
Fe/ZSM-5@S1-24(×2) | H2/CO = 2; 300 °C; 4 h | 260 °C; H2/CO=2; 1 MPa; 6 L h-1 gcat.-1 | NA | — | 43.1 | 11.4 | 11.6 | 27.7 | 60.7 | [ | |
Fe3O4@SiO2-PFTS | H2/CO = 2; 320 °C; 1 h | 320 °C; H2/CO=2; 1.5 MPa; 3000 h-1 | 120 | — | 32.9 | 4.8 | 48.1 | 47.2 | 4.7 | [ | |
Fe@Mn@0.2Si-c | H2; 350 °C; 10 h; syngas; 320 °C; 5 h | 320 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 24 | — | 55.0 | 7.5 | 13.5 | 41.5 | 45.0 | [ | |
Graphene confinement | ε-Fe2C@graphene | H2; 350 °C; 3 h | 300 °C; H2/CO=1; 1 MPa; 64 L h-1 gcat.-1 | 400 | 582.8 | 44.6 | 20.3 | 10.3 | 23.9 | 65.8 | [ |
Fe15-G | H2; 450 °C; 5 h | 325 °C; H2/CO=2; 1.5 MPa; 2.5 L h-1 gcat.-1 | 48 | 103.0 | 51.5 | 2.0 | 1.5 | 32.0 (C2-7) | 66.5 (C8+) | [ | |
FeC-800 | H2; 400 °C; 5 h | 300 °C; H2/CO=2; 2 MPa; 12 °C L h-1 gcat.-1 | 60 | 239.4 | 47.0 | 24.0 | 18.0 | 30.0 | 52.0 | [ | |
χ-Fe5C2@Graphene | NA | 260 °C; H2/CO=1; 2 MPa; 0.25 L h-1 gcat.-1 | 180 | — | 17.2 | 4.6 | 5.9 | 11.8 | 82.3 | [ | |
Fe/PGO-380 | H2; 380 °C; 6 h | 270 °C; H2/CO=2; 3 MPa; 15 L h-1 gcat.-1 | 25 | — | 30.4 | 5.1 | 21.2 | 46.6 | 32.2 | [ |
Table 1 Summary of catalytic performance over iron-based catalysts for Fischer-Tropsch synthesis.
Strategies | Catalysts | Treatment | FT condition | TOS (h) | FTY μmolCO-1 gFe-1 s-1 | CO Conv. (%) | Sel. (%) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|---|---|
CO2 | CH4 | C2-C4 | C5+ | ||||||||
Conventional catalysts | 38-Fe@C | H2; 425 °C; 3 h | 340 °C; H2/CO = 1; 2 MPa; 30000 h-1 | 10 | 380.0 | 72.0 | 46.8 | 15.0 | 28.0 | 57.0 | [ |
Fe/α-Al2O3 | H2; 350 °C; 2 h | 340 °C; H2/CO=1; 2 MPa; 1500 h-1 | 64 | 84.8 | 77.0 | 46.0 | 24.0 | 56.0 | 20.0 | [ | |
Fe-in-CNT | H2; 350 °C; 5 h | 270 °C; H2/CO=2; 5.1 MPa; 2 L h-1 gcat.-1 | 24 | — | 40.0 | 18.0 | 12.0 | 41.0 | 29.0 | [ | |
35Fe/hNCNC-3 | H2; 350 °C; 2 h | 350 °C; H2/CO=1; 0.1 MPa; 12 L h-1 gcat.-1 | 60 | — | 3.5 | 39.4 | 25.0 | 57.4 | 17.6 | [ | |
FeK2/rGO | 5%H2; 450 °C; 16 h | 340 °C; H2/CO=1; 2 MPa; 24 L h-1 gcat.-1 | 24 | 220.0 | 61.0 | 51.0 | 20.0 | 73.3 | 6.7 | [ | |
Fe/Ru/SiO2 | H2/CO = 2; 280 °C; 20 h | 260 °C; H2/CO=2; 1.5 MPa; 2000 h-1 | 73 | — | 46.1 | 21.2 | 19.7 | 44.3 | 36.0 | [ | |
Phase-pure iron carbide | θ-Fe3C | NA | 250 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 100 | — | 30.0 | 9.9 | 9.4 | 39.4 | 51.2 | [ |
ε-Fe2C/ε'-Fe2.2C | 20%H2; 280 °C; 12 h | 235 °C; H2/CO=1.5; 2.3 MPa; 18000 h-1 | 150 | — | 15.0 | 5.3 | 12.0 | 29.0 | 49.0 | [ | |
Mn-χ-Fe5C2 | H2/CO = 30; 350 °C; 6 h | 250 °C; H2/CO=1.5; 3 MPa; 5 L h-1 gcat.-1 | 1100 | — | 46.1 | 9.4 | 8.1 | 44.4 | 47.5 | [ | |
Hydrophobic modification | Fe1Mn0.3@Si-c | H2; 350 °C; 10 h; syngas; 320 °C; 5 h | 320 °C; H2/CO=2; 3 MPa; 4000 h-1 | 100 | — | 56.1 | 13.0 | 12.0 | 26.0 | 62.0 | [ |
B-Fe2O3@SiO2-(CH3)3 | H2/CO = 2; 300 °C; 4 h | 320 °C; H2/CO=2; 1.5 MPa; 3000 h-1 | 12 | — | 50.0 | 3.4 | 38.0 | 51.0 | 11.0 | [ | |
FeNa@Si-c+HZSM-5 | H2; 350 °C; 2 h | 260 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 10 | — | 49.8 | 14.3 | 7.7 | 17.0 | 75.3 | [ | |
Fe/SiO2-HP3 | H2; 150 °C; 2 h; 250 °C; 2 h; 350 °C; 16 h | 280 °C; H2/CO=1.5; 2 MPa; 2.4 L h-1 gcat.-1 | 160 | — | 19.7 | 16.0 | 18.0 | 32.0 | 50.0 | [ | |
Fe/ZSM-5@S1-24(×2) | H2/CO = 2; 300 °C; 4 h | 260 °C; H2/CO=2; 1 MPa; 6 L h-1 gcat.-1 | NA | — | 43.1 | 11.4 | 11.6 | 27.7 | 60.7 | [ | |
Fe3O4@SiO2-PFTS | H2/CO = 2; 320 °C; 1 h | 320 °C; H2/CO=2; 1.5 MPa; 3000 h-1 | 120 | — | 32.9 | 4.8 | 48.1 | 47.2 | 4.7 | [ | |
Fe@Mn@0.2Si-c | H2; 350 °C; 10 h; syngas; 320 °C; 5 h | 320 °C; H2/CO=2; 2 MPa; 5 L h-1 gcat.-1 | 24 | — | 55.0 | 7.5 | 13.5 | 41.5 | 45.0 | [ | |
Graphene confinement | ε-Fe2C@graphene | H2; 350 °C; 3 h | 300 °C; H2/CO=1; 1 MPa; 64 L h-1 gcat.-1 | 400 | 582.8 | 44.6 | 20.3 | 10.3 | 23.9 | 65.8 | [ |
Fe15-G | H2; 450 °C; 5 h | 325 °C; H2/CO=2; 1.5 MPa; 2.5 L h-1 gcat.-1 | 48 | 103.0 | 51.5 | 2.0 | 1.5 | 32.0 (C2-7) | 66.5 (C8+) | [ | |
FeC-800 | H2; 400 °C; 5 h | 300 °C; H2/CO=2; 2 MPa; 12 °C L h-1 gcat.-1 | 60 | 239.4 | 47.0 | 24.0 | 18.0 | 30.0 | 52.0 | [ | |
χ-Fe5C2@Graphene | NA | 260 °C; H2/CO=1; 2 MPa; 0.25 L h-1 gcat.-1 | 180 | — | 17.2 | 4.6 | 5.9 | 11.8 | 82.3 | [ | |
Fe/PGO-380 | H2; 380 °C; 6 h | 270 °C; H2/CO=2; 3 MPa; 15 L h-1 gcat.-1 | 25 | — | 30.4 | 5.1 | 21.2 | 46.6 | 32.2 | [ |
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