Zn-mediated modulation of Fe-Si interactions to achieve a balance between stability and selectivity in CO2 hydrogenation

doi:10.1016/S1872-2067(26)65216-3

Abstract

Abstract:

The direct hydrogenation of CO₂ to high-value olefins represents one of the most attractive pathways for large-scale CO₂ conversion. However, developing catalysts that are active, selective, and stable for olefin production remains challenging, particularly when incorporating support or binder under industrially relevant conditions. Although silica (SiO₂) is widely used as a support or binder in industrial Fe-based Fischer-Tropsch synthesis (FTS), its incorporation often leads to poor performance in CO₂ hydrogenation. In this work, we introduce a Zn promoter to modulate the detrimental Fe-Si interaction in SiO₂-containing Fe-based catalysts for CO₂ hydrogenation. The resulting catalyst achieves a single-pass C₂₊ olefin yield as high as 0.6 g·g_cat^-1·h^-1, coupled with exceptional operational stability for over 500 h at high space velocity. Multiple characterization techniques reveal that during the in-situ reaction-activation stage, Zn promotes the formation of a Zn₂SiO₄ phase, which alleviates the adverse Fe-O-Si interaction. The high content of χ-Fe₅C₂ with electron-enriched surface and abundant surface oxygen vacancies contribute to the outstanding catalytic activity and selectivity, while the presence of Zn₂SiO₄ contributes to long-term stability. These findings provide valuable insights for the rational regulation of metal-support/binder interactions in CO₂ hydrogenation catalytic systems, especially for the design of catalysts where shaping processes and long-term durability pose significant challenges.

Key words: CO₂ hydrogenation, Iron catalysts, Olefins, Fe-Si interaction, Stability, Support/binder

Yi Liu, Peng Zhang, Yijun Li, Zhihua Han, Bo Feng, Xiaowa Nie, Jingyun Chen, Ruonan He, Zhoujun Wang, Lei Shao, Shaodong Qin, Guanghui Zhang, Xinwen Guo. Zn-mediated modulation of Fe-Si interactions to achieve a balance between stability and selectivity in CO₂ hydrogenation[J]. Chinese Journal of Catalysis, 2026, 91: 122-134.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65216-3

https://www.cjcatal.com/EN/Y2026/V91/I12/122

Figures/Tables 8

Fig. 1. Catalytic properties toward CO2 hydrogenation under industrially relevant conditions. (a) The products distribution, CO2 conversion, and CO selectivity of various iron-based catalysts. (b) CO2 conversion of Fe, FeSi, and FeZnSi catalysts with time on stream of 75 h. Reaction conditions: 300 °C, 1.5 MPa, 10000 mL·g-1·h-1. (c) Kinetic studies for CO2 hydrogenation over Fe, FeSi, and FeZnSi catalysts. Reaction conditions: 260-310 °C, 1.5 MPa, 56000 mL·g-1·h-1. The reaction rate (r) is expressed as the amount of converted CO2 (mmol) per gram of catalyst per hour. (d) Long-term stability test of FeZnSi catalyst. Reaction conditions: 320 °C, 1.5 MPa, 50000 mL·g-1·h-1.

Fig. 2. Structural characterizations of fresh and activated catalysts. (a) XRD patterns of all fresh catalysts. (b-d) Results from refinement of the XRD patterns of activated Fe, FeSi, and FeZnSi catalysts. (e) MES spectra of activated Fe, FeSi, and FeZnSi catalysts. (f) Quantitative results of XRD and MES characterizations of activated catalysts. The low-content and indistinguishable Fe3O4 phase in quantitative XRD of FeZnSi sample are included in ZnFe2O4. (g) H2-TPR profiles of all iron-based catalysts. (h) Quasi-in-situ XPS Fe 2p spectra of all iron-based catalysts. (i) XPS Fe 2p spectra of all fresh catalysts.

Table 1 Mössbauer parameters of the activated catalysts after reduction at T=340 °C, P=0.1 MPa and H2/CO ratio of 1.

Catalyst	Phases	Mössbauer parameters ^a				Content (%)
Catalyst	Phases	IS (mm s^-1)	QS (mm s^-1)	Hhf (T)	Area^b (%)	Content (%)
Fe	Fe₃O₄(A)	0.25	0.17	49.2	5.9	13.1
	Fe₃O₄(B)	0.83	-0.10	46.8	7.2	13.1
	Fe₅C₂(I)	0.33	0.06	22.5	23.5	73.8
	Fe₅C₂(II)	0.38	0.13	19.6	9.5
	Fe₅C₂(III)	0.24	-0.11	11.4	23.6
	Fe₇C₃(I)	0.30	-0.00	17.3	2.2
	Fe₇C₃(II)	0.26	-0.16	19.2	15.0
	spm Fe³⁺	0.39	1.06	—	13.1	13.1
FeSi	Fe₃O₄(A)	0.36	0.02	49.2	10.2	20.5
	Fe₃O₄(B)	0.85	-0.11	45.9	10.3	20.5
	Fe₅C₂(I)	0.33	0.07	22.5	22.3	53.7
	Fe₅C₂(II)	0.40	0.17	19.3	10.7
	Fe₅C₂(III)	0.33	-0.14	9.4	9.1
	Fe₇C₃(I)	0.18	0.14	16.5	3.8
	Fe₇C₃(II)	0.25	-0.16	19.1	7.8
	spm Fe³⁺	0.49	0.93	—	25.8	25.8
FeZnSi	Fe₃O₄(A)	0.22	0.02	49.1	6.6	10.2
	Fe₃O₄(B)	0.78	-0.09	45.8	3.6	10.2
	Zn_xFe_3-_xO₄	0.54	0.67	—	89.8	89.8

Fig. 3. Structural characterizations of spent catalysts. (a) XRD patterns of all spent catalysts (TOS=75 h). (b) MES of spent Fe, FeSi, and FeZnSi catalysts (TOS=75 h). (c) Quantitative results of MES characterizations of activated and spent catalysts. (d) Results from refinement of the XRD patterns of spent FeZnSi catalyst. (e) Results from refinement of the XRD patterns of spent FeZnSi catalyst after TOS=0.5 h. (f) MES spectra of spent FeZnSi catalyst after TOS=0.5 h. (g) XANES at Fe K-edge of Fe, FeSi and FeZnSi catalysts after reaction (TOS=75 h), in comparison with references for Fe foil and Fe3O4. (h) The nonphase corrected, k3 weighted Fourier-transformed EXAFS spectra at the Fe K-edge of Fe, FeSi and FeZnSi catalysts after reaction (TOS=75 h). (i) XPS Si 2p spectra of all spent catalysts (TOS=75 h).

Table 2 Mössbauer parameters of the spent catalysts after 75 h on stream at T=300 °C, P =1.5 MPa and H2/CO2 ratio of 3.

Catalyst	Phases	Mössbauer parameters ^a				Content (%)
Catalyst	Phases	IS (mm s^-1)	QS (mm s^-1)	Hhf (T)	Area ^b (%)	Content (%)
Fe	Fe₅C₂(I)	0.30	0.01	22.5	22.6	49.2
	Fe₅C₂(II)	0.14	0.14	18.8	12.2
	Fe₅C₂(III)	0.19	0.08	11.1	14.4
	Fe₃O₄(A)	0.29	-0.20	49.8	15.5	46.3
	Fe₃O₄(B)	0.73	0.04	47.6	30.8	46.3
	spm Fe³⁺	0.20	1.15	—	4.5	4.5
FeSi	Fe₅C₂(I)	0.28	-0.03	22.2	29.6	67.9
	Fe₅C₂(II)	0.12	0.04	19.1	18.9
	Fe₅C₂(III)	0.20	-0.02	11.7	13.9
	Fe₇C₃(I)	0.22	0.01	16.7	2.3
	Fe₇C₃(II)	0.22	0.03	18.6	3.2
	spm Fe³⁺	0.30	1.08	—	32.1	32.1
FeZnSi	Fe₅C₂(I)	0.11	0.07	22.3	31.7	72.7
	Fe₅C₂(II)	0.02	0.03	18.9	21.8
	Fe₅C₂(III)	0.03	0.15	11.1	19.2
	Zn_xFe_3-_xO₄	0.26	0.89	—	27.3	27.3
FeZnSi-0.5h	Fe₅C₂(I)	0.26	0.06	22.5	9.3	21.4
	Fe₅C₂(II)	0.21	0.02	19.3	7.6
	Fe₅C₂(III)	0.24	-0.10	8.6	4.5
	Zn_xFe_3-_xO₄	0.57	0.75	—	78.6	78.6

Fig. 4. Morphology characterizations of spent Fe catalysts. (a-d) HR-TEM patterns of the spent Fe catalyst (insets: FFT patterns extracted from HR-TEM images). Original HAADF-STEM image of the spent Fe catalyst (e,i) and corresponding STEM/EDX elemental mapping (f-h, j-l) of Fe and O elements on the catalyst.

Fig. 5. Morphology characterizations of spent FeSi catalysts. (a-e) HR-TEM and FFT patterns of the spent FeSi catalyst. Original HAADF-STEM image of the spent FeSi catalyst (f,k) and corresponding STEM/EDX elemental mapping (g-j, l-o) of Fe, Si and O elements on the catalyst.

Fig. 6. Morphology characterizations of spent FeZnSi catalysts. (a-e) HR-TEM and FFT patterns of the spent FeZnSi catalyst. Original HAADF-STEM image of the spent FeZnSi catalyst (f,g) and corresponding STEM/EDX elemental mapping (h-l) of Fe, Zn, Si and O elements on the catalyst.

References

[1]	J. Wei, R. Yao, Y. Han, Q. Ge, J. Sun, Chem. Soc. Rev., 2021, 50, 10764-10805.
[2]	J. Ye, N. Dimitratos, L. M. Rossi, N. Thonemann, A. M. Beale, R. Wojcieszak, Science, 2025, 387, eadn9388.
[3]	R.-P. Ye, J. Ding, W. Gong, M. D. Argyle, Q. Zhong, Y. Wang, C. K. Russell, Z. Xu, A. G. Russell, Q. Li, M. Fan, Y.-G. Yao, Nat. Commun., 2019, 10, 5698.
[4]	D. Wang, Z. Xie, M. D. Porosoff, J. G. Chen, Chem, 2021, 7, 2277-2311.
[5]	P. Gao, S. Li, X. Bu, S. Dang, Z. Liu, H. Wang, L. Zhong, M. Qiu, C. Yang, J. Cai, W. Wei, Y. Sun, Nat. Chem., 2017, 9, 1019-1024.
[6]	J. I. Orege, J. Wei, Y. Han, M. Yang, X. Sun, J. Zhang, C. C. Amoo, Q. Ge, J. Sun, Appl. Catal. B, 2022, 316, 121640.
[7]	L. Zhang, W. Gao, F. Wang, C. Wang, J. Liang, X. Guo, Y. He, G. Yang, N. Tsubaki, Appl. Catal. B, 2023, 328, 122535.
[8]	H. Jo, M. K. Khan, M. Irshad, M. W. Arshad, S. K. Kim, J. Kim, Appl. Catal. B, 2022, 305, 121041.
[9]	A. Fedorov, H. Lund, V. A. Kondratenko, E. V. Kondratenko, D. Linke, Appl. Catal. B, 2023, 328, 122505.
[10]	B. Yao, T. Xiao, O. A. Makgae, X. Jie, S. Gonzalez-Cortes, S. Guan,A. I. Kirkland, J. R. Dilworth, H. A. Al-Megren, S. M. Alshihri, P. J. Dobson, G. P. Owen, J. M. Thomas, P. P. Edwards, Nat. Commun., 2020, 11, 6395.
[11]	T. Numpilai, N. Chanlek, Y. Poo-Arporn, S. Wannapaiboon, C. K. Cheng, N. Siri-Nguan, T. Sornchamni, P. Kongkachuichay, M. Chareonpanich, G. Rupprechter, J. Limtrakul, T. Witoon, Appl. Surf. Sci., 2019, 483, 581-592.
[12]	Y. Liu, X. Gong, R. He, Z. Han, J. Chen, B. Feng, X. Xu, A. Xing, R. Jin, P. Ren, B. Wang, Z.-J. Wang, ACS Catal., 2024, 14, 12425-12436.
[13]	H. Suo, S. Wang, C. Zhang, J. Xu, B. Wu, Y. Yang, H. Xiang, Y.-W. Li, J. Catal., 2012, 286, 111-123.
[14]	M. Qing, Y. Yang, B. Wu, J. Xu, C. Zhang, P. Gao, Y. Li, J. Catal., 2011, 279, 111-122.
[15]	R. Zhao, J. G. Goodwin, K. Jothimurugesan, S. K. Gangwal, J. J. Spivey, Ind. Eng. Chem. Res., 2001, 40, 1065-1075.
[16]	H.-J. Wan, B.-S. Wu, Z.-C. Tao, T.-Z. Li, X. An, H.-W. Xiang, Y.-W. Li, J. Mol. Catal. A, 2006, 260, 255-263.
[17]	J. Wang, Z. You, Q. Zhang, W. Deng, Y. Wang, Catal. Today, 2013, 215, 186-193.
[18]	A. Samanta, M. V. Landau, R. Vidruk-Nehemya, M. Herskowitz, Catal. Sci. Technol., 2017, 7, 4048-4063.
[19]	M. Lopez Luna, J. Timoshenko, D. Kordus, C. Rettenmaier, S. W. Chee, A. S. Hoffman, S. R. Bare, S. Shaikhutdinov, B. Roldan Cuenya, ACS Catal., 2021, 11, 6175-6185.
[20]	C. Zhang, C. Cao, Y. Zhang, X. Liu, J. Xu, M. Zhu, W. Tu, Y.-F. Han, ACS Catal., 2021, 11, 2121-2133.
[21]	J. I. Orege, G. A. Kifle, Y. Yu, J. Wei, Q. Ge, J. Sun, Matter, 2023, 6, 1404-1434.
[22]	S. Bordiga, R. Buzzoni, F. Geobaldo, C. Lamberti, E. Giamello, A. Zecchina, G. Leofanti, G. Petrini, G. Tozzola, G. Vlaic, J. Catal., 1996, 158, 486-501.
[23]	P. Fabrizioli, T. Bürgi, M. Burgener, S. van Doorslaer, A. Baiker, J. Mater. Chem., 2002, 12, 619-630.
[24]	S. Bruni, F. Cariati, M. Casu, A. Lai, A. Musinu, G. Piccaluga, S. Solinas, Nanostruct. Mater., 1999, 11, 573-586.
[25]	Y. Wu, Y. Wang, D. He, M. Fu, Z. Chen, Y. Li, J. Lumin., 2010, 130, 1768-1773.
[26]	G. Essalah, G. Kadim, A. Jabar, R. Masrour, M. Ellouze, H. Guermazi, S. Guermazi, Ceram. Int., 2020, 46, 12656-12664.
[27]	X. Gong, Y. Liu, R. He, X. Xu, Z. Han, J. Chen, B. Feng, Z.-J. Wang, A. Xing, ChemCatChem, 2024, 16, e202301341.
[28]	X. Liu, T. Lin, P. Liu, L. Zhong, Appl. Catal. B, 2023, 331, 122697.
[29]	Y. Okamoto, T. Kubota, Y. Ohto, S. Nasu, J. Phys. Chem. B, 2000, 104, 8462-8470.
[30]	Y. Liu, X.-A. Pan, Z. Qiu, L. Sun, P. Zhang, R. He, Z. Han, J. Chen, S. Liu, H. Wei, X. Xu, S. Qin, Fuel, 2025, 393, 135036.
[31]	X. Han, Q. Zhao, H. Gong, C. Wei, J. Lv, Y. Wang, M.-Y. Wang, S. Huang, X. Ma, ACS Catal., 2023, 13, 6525-6535.
[32]	J. Zhu, P. Wang, X. Zhang, G. Zhang, R. Li, W. Li, T. P. Senftle, W. Liu, J. Wang, Y. Wang, A. Zhang, Q. Fu, C. Song, X. Guo, Sci. Adv., 2022, 8, eabm3629.
[33]	B. Yan, B. Zhao, S. Kattel, Q. Wu, S. Yao, D. Su, J. G. Chen, J. Catal., 2019, 374, 60-71.
[34]	C. Zhang, M. Xu, Z. Yang, M. Zhu, J. Gao, Y.-F. Han, Appl. Catal. B, 2021, 295, 120287.
[35]	S. Wang, T. Wu, J. Lin, Y. Ji, S. Yan, Y. Pei, S. Xie, B. Zong, M. Qiao, ACS Catal., 2020, 10, 6389-6401.
[36]	J. M. Gracia, F. F. Prinsloo, J. W. Niemantsverdriet, Catal. Lett., 2009, 133, 257-261.
[37]	J. Kirchner, Z. Baysal, S. Kureti, ChemCatChem, 2020, 12, 981-988.
[38]	Y. Wang, K. Wang, B. Zhang, X. Peng, X. Gao, G. Yang, H. Hu, M. Wu, N. Tsubaki, ACS Catal., 2021, 11, 11742-11753.
[39]	Y. Xu, P. Zhai, Y. Deng, J. Xie, X. Liu, S. Wang, D. Ma, Angew. Chem. Int. Ed., 2020, 59, 21736-21744.
[40]	N. Liu, J. Wei, J. Xu, Y. Yu, J. Yu, Y. Han, K. Wang, J. I. Orege, Q. Ge, J. Sun, Appl. Catal. B, 2023, 328, 122476.
[41]	K. Y. Kim, H. Lee, W. Y. Noh, J. Shin, S. J. Han, S. K. Kim, K. An, J. S. Lee, ACS Catal., 2020, 10, 8660-8671.

Zn-mediated modulation of Fe-Si interactions to achieve a balance between stability and selectivity in CO₂ hydrogenation

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