Mechanistic study of oxide participation in the C*cycle catalysis over Fe<sub>5</sub>C<sub>2</sub>

He Fugui; Kong Xiangbin; Zhang Tong; Zheng Bing; Lu Kuan; Zhang Jianli; Zhao Tiansheng; Gao Xinhua; He Yurong

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Mechanistic study of oxide participation in the C*cycle catalysis over Fe₅C₂

Updated：2026-03-13

- Mechanistic study of oxide participation in the C*cycle catalysis over Fe₅C₂
- Chinese Journal of Chemical Engineering Vol. 89, Issue 1, Pages: 208-219(2026)
- Affiliations：
  
  State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China
  State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
- Author bio：
  
  Corresponding authors. E-mail addresses: gxh@nxu.edu.cn(X. Gao)
  hyr@nxu.edu.cn(Y. He).
- Funds：
- DOI：
  CLC：
- Received：10 April 2025，
  
  Revised：2025-08-09，
  
  Accepted：13 August 2025，
  
  Online First：19 September 2025，
  
  Published：2026-01
- Accepted：
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He Fugui, Kong Xiangbin, Zhang Tong, et al. Mechanistic study of oxide participation in the C*cycle catalysis over Fe₅C₂[J]. Chinese Journal of Chemical Engineering, 2026, 89(1): 208-219.
DOI：

He Fugui, Kong Xiangbin, Zhang Tong, et al. Mechanistic study of oxide participation in the C*cycle catalysis over Fe₅C₂[J]. Chinese Journal of Chemical Engineering, 2026, 89(1): 208-219. DOI：

摘要

Abstract

The conversion of CO

into high value added chemicals

via

the Fischer-Tropsch synthesis (FTS) reaction has attracted significant attention. The surface oxygenation environment is a significant factor influencing the performance of the catalyst. In this work

spin-polarized density-functional theory calculations have been used to investigate the adsorption and reactions of CO

and H to generate CH

and CH

OH on Fe

(100) surfaces with varying OH*coverage. On the pure Fe

(100) surface

surface C*preferentially reacts with hydrogen to form CH

exposing C*vacancy. CO

favors adsorbing on the C*vacancy to further dissociating and activating. The co-adsorption of OH*promotes the C*cycle process by facilitating the hydrogenation of C*. The Fe

surface with an oxide interface is favorable for reducing Fe

thereby maintaining the dynamic stability of the surface. Therefore

surface oxidation is inevitably involved in the entire C*cycle of the FTS reaction and regulates the relative content of iron oxides and iron carbides. Our work can contribute to the rational modulation of

the surface C* cycle

thereby enhancing catalyst performance.

关键词

Keywords

references

F. Fischer, H. Tropsch, The preparation of synthetic oil mixtures (synthol) from carbon monoxide and hydrogen, Brennstoff-Chemie. 4(1923)276—285.

C. Panzone, R. Philippe, A. Chappaz, P. Fongarland, A. Bengaouer, Power-toLiquid catalytic CO 2 valorization into fuels and chemicals: focus on the Fische r-Tropsch route, J. CO 2 Util. 38 (2020) 314—347.

F.G. He, T. Zhang, J. Liang, H.P. Li, Y.R. He, X.H. Gao, J.L. Zhang, T.S. Zhao, The application of DFT calculation in the study of iron-based catalyst for FischerTropsch synthesis, J. Fuel Chem. Technol. 51 (11) (2023) 1540—1564.

B.H.H. Goh, C.T. Chong, H.C. Ong, T. Seljak, T. Katraˇsnik, V. Jo'zsa, J.H. Ng, B. Tian, S. Karmarkar, V. Ashokkumar, Recent advancements in catalytic conversion pathways for synthetic jet fuel produced from bioresources, Energy Convers. Manag. 251 (2022) 114974.

S. Abello', D. Montane', Exploring iron-based multifunctional catalysts for Fischer-Tropsch synthesis: a review, ChemSusChem 4(11)(2011)1538—1556.

Y.F. Zhu, B.Q. Xie, R. Amal, E.C. Lovell, J. Scott, Light-enhanced conversion of CO 2 to light olefins: basis in thermal catalysis, current progress, and future prospects, Small Struct. 4 (6) (2023) 2200285.

Q.Y. Liu, C. Shang, Z.P. Liu, In situ active site for Fe-catalyzed Fischer-Tropsch synthesis: recent progress and future challenges, J. Phys. Chem. Lett. 13 (15) (2022) 3342—3352.

J.M. Gracia, F.F. Prinsloo, J.W. Niemantsverdriet, Mars-van Krevelen-like mechanism of CO hydrogenation on an iron carbide surface, Catal. Lett. 133 (3) (2009)257—261.

F.G. He, X.B. Kong, T. Zhang, Y.N. Yuan, J.L. Zhang, X.H. Gao, Y.R. He, T.S. Zhao, Mechanistic insights of surface OH*modulation on methan ol production with CO 2 hydrogenation by iron-based catalyst, Mol. Catal. 569 (2024) 114599.

M.O. Ozbek, J.W. Niemantsverdriet, Methane, formaldehyde and methanol formation pathways from carbon monoxide and hydrogen on the (0 0 1) surface of the iron carbide χ-Fe 5 C 2 , J. Catal. 325 (2015) 9—18.

M.O. Ozbek, J.W. Niemantsverdriet, Elementary reactions of CO and H 2 on Cterminated χ-Fe 5 C 2 (001) surfaces, J. Catal. 317 (2014) 158—166.

M.H. Zhang, X.Y. Guan, Y.Z. Yu, Theoretical insights into the removal pathways of adsorbed oxygen on the surface of χ-Fe 5 C 2 (510), Chem. Eng. Sci. 271 (2023) 118576.

S. Zhao, X.W. Liu, C.F. Huo, Y.W. Li, J.G. Wang, H.J. Jiao, Surface morphology of Hägg iron carbide(χ-Fe 5 C 2 )from ab initio atomistic thermodynamics, J. Catal. 294(2012)47—53.

Y.R. He, P. Zhao, J.J. Liu, W.P. Guo, Y. Yang, Y.W. Li, C.F. Huo, X.D. Wen, Suppression by Pt of CO adsorption and dissociation and methane formation on Fe 5 C 2 (100) surfaces, Phys. Chem. Chem. Phys. 20 (39) (2018) 25246—25255.

M. Ojeda, R. Nabar, A.U. Nilekar, A. Ishikawa, M. Mavrikakis, E. Iglesia, CO activation pathways and the mechanism of Fischer—Tropsch synthesis, J. Catal. 272(2)(2010)287—297.

F.G. He, X.B. Kong, T. Zhang, S. Zhang, X.H. Gao, K. Lu, Y.R. He, J.L. Zhang, T.S. Zhao, Mechanistic ins ight into accelerating of light olefin products by surface OH* group on the Fe 5 C 2 catalyst, Fuel 381 (2025) 133635.

X.Y. Guo, B. Liu, X.H. Gao, F.G. He, Q.X. Ma, S.B. Fan, T.S. Zhao, J.M. Tian, P. Reubroycharoen, J.L. Zhang, Improved olefin selectivity during CO hydrogenation on hydrophilic Fe/HAP catalysts, Catal. Today 410 (2023) 193—204.

Y.X. Zhang, X.Y. Guo, B. Liu, J.L. Zhang, X.H. Gao, Q.X. Ma, S.B. Fan, T.S. Zhao, Surface modification of g-C 3 N 4 -supported iron catalysts for CO hydrogenation: strategy for product distribution, Fuel 305 (2021) 121473.

J. Zhu, P. Wang, X.B. Zhang, G.H. Zhang, R.T. Li, W.H. Li, T.P. Senftle, W. Liu, J.Y. Wang, Y.L. Wang, A.F. Zhang, Q. Fu, C.S. Song, X.W. Guo, Dynamic structural evolution of iron catalysts involving competitive oxidation and carburization during CO 2 hydrogenation, Sci. Adv. 8(5)(2022)eabm3629.

J. Benziger, R.J. Madix, The effects of carbon, oxygen, sulfur and potassium adlayers on CO and H 2 adsorption on Fe(1 0 0), Surf. Sci. 94 (1) (1980) 119—153.

H.Z. Wang, X.W. Nie, Y. Liu, M.J. Janik, X.P. Han, Y.D. Deng, W.B. Hu, C.S. Song, X.W. Guo, Mechanistic insight into hydrocarbon synthesis via CO 2 hydrogenation on χ-Fe 5 C 2 catalysts, ACS Appl. Mater. Interfaces 14 (33) (2022) 37637—37651.

Z.Z. Zhang, B.J. Chen, L.Y. Jia, W.Q. Liu, X.H. Gao, J. Gao, B. Meng, Y.S. Tan, Y.R. He, W.F. Tu, Y.F. Han, Unraveling the role of Fe 5 C 2 in CH 4 formation during CO 2 hydrogenation over hydrophobic iron catalysts, Appl. Catal. B Environ. 327 (2023) 122449.

M. Wilke, F. Farges, P.E. Petit, G.E. Brown Jr., F. Martin, Oxidation state and coordination of Fe in minerals: an Fe K- XANES spectroscopic study, Am. Mineral. 86(5—6) (2001)714—730.

C. Wang, X.H. Gao, J.L. Zhang, Q.X. Ma, S.B. Fan, T.S. Zhao, Effects of surface groups on Fe/ZnO catalysts for CO 2 hydrogenation to olefin, Appl. Surf. Sci. 658 (2024) 159820.

W.L. Wu, J.H. Luo, J.K. Zhao, M.L. Wang, L. Luo, S.P. Hu, B.X. He, C. Ma, H.L. Li, J. Zeng, Facet sensitivity of iron carbides in Fischer-Tropsch synthesis, Nat. Commun. 15(1)(2024)6108.

Y.H. Peng, L.B. Wang, Q.Q. Luo, Y. Cao, Y.Z. Dai, Z.L. Li, H.L. Li, X.S. Zheng, W.S. Yan, J.L. Yang, J. Zeng, Molecular-level insight into how hydroxyl groups boost catalytic activity in CO 2 hydrogenation into methanol, Chem 4 (3) (2018) 613—625.

Y.J. Guo, L.Y. Jia, Z.Z. Zhang, M.Z. Gong, S.S. Dang, Y.Q. Huang, X.H. Gao, W.F. Tu, Y.F. Han, Revealing the mechanism of Ce promoter in modulating product distribution of CO 2 hydrogenation over Fe-based catalysts, Chem. Eng. J. 491 (2024) 151964.

G. Kresse, J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6(1)(1996)15—50.

G. Kress e, J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54 (16) (1996) 11169—11186.

P. Blöchl, Projector augmented-wave method, Phys. Rev. B 50 (24) (1994) 17953—17979.

G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59 (3)(1999)1758—1775.

J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (18)(1996)3865—3868.

J. Perdew, Y. Wang, Accurate and simple analytic representation of the electron-gas correlation energy, Phys. Rev. B 45 (23) (1992) 13244—13249.

M. Methfessel, A. Paxton, High-precision sampling for Brillouin-zone integration in metals, Phys. Rev. B 40 (6) (1989) 3616—3621.

H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13 (12)(1976) 5188—5192.

G. Henkelman, H. Jo'nsson, Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points, J. Chem. Phys. 113(22)(2000)9978—9985.

S. Zhao, X.W. Liu, C.F. Huo, Y.W. Li, J.G. Wang, H.J. Jiao, Determining surface structure and stability of ε-Fe 2 C, χ-Fe 5 C 2 , θ-Fe3C and Fe 4 C phases under carburization environment from combined DFT and atomistic thermodynamic studies, Catal. Struct. React. 1 (1) (2015) 44—60.

T.H. Pham, Y.Y. Qi, J. Yang, X.Z. Duan, G. Qian, X.G. Zhou, D. Chen, W.K. Yuan, Insights into Hägg iron-carbide-catalyzed Fischer—Tropsch synthesis:suppression of CH 4 formation and enhancement of C—C coupling on χ-Fe 5 C 2 (510), ACS Catal. 5 (4) (2015) 2203—2208.

Y.R. He, P. Zhao, J.Q. Yin, W.P. Guo, Y. Yang, Y.-W. Li, C.-F. Huo, X.-D. Wen, CO direct versus H-assisted dissociation on hydrogen coadsorbed χ-Fe 5 C 2 Fischer—Tropsch catalysts, J. Phys. Chem. C 122 (36) (2018) 20907—20917.

D.B. Cao, F.Q. Zhang, Y.W. Li, J.G. Wang, H.J. Jiao, Density functional theory study of hydrogen adsorption on Fe 5 C 2 (001), Fe 5 C 2 (110), and Fe 5 C 2 (100), J. Phys. Chem. B 109 (2) (2005) 833—844.

C.F. Huo, Y.W. Li, J.G. Wang, H.J. Jiao, Insight into CH 4 formation in ironcatalyzed Fischer- Tropsch synthesis, J. Am. Chem. Soc. 131 (41) (2009) 14713—14721.

Y. Bai, J.J. Liu, T. Wang, Y.F. Song, Y. Yang, Y.W. Li, X.D. Wen, Theoretical study about adsorbed oxygen reduction over χ-Fe 5 C 2 : formation of H 2 O and CO 2 , Mol. Catal. 524 (2022) 112236.

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⁰

Mechanistic study of oxide participation in the C*cycle catalysis over Fe5C2

DOI：

摘要

Abstract

关键词

Keywords

references

Mechanistic study of oxide participation in the C*cycle catalysis over Fe₅C₂