Strong interaction between Fe and Ti compositions for effective CO2 hydrogenation to light olefins

doi:10.1016/S1872-2067(24)60268-8

Abstract

Abstract:

Fe-based catalysts are widely used for CO₂ hydrogenation to light olefins (C_2-4⁼); however, precise regulation of active phases and the balance between intermediate reactions remain significant challenges. Herein, we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions, modulating the Fe₃O₄ and Fe₅C₂ contents. Enhanced interaction leads to an increased Fe₅C₂/Fe₃O₄ ratio, which in turn enhances the adsorption of reactants and intermediates, promoting CO hydrogenation to unsaturated alkyl groups and facilitating C-C coupling. Furthermore, the strong Fe-Ti interaction induces the preferential growth of Fe₅C₂ into prismatic structures that expose the (020), (-112), and (311) facets, forming compact active interfacial sites with Fe₃O₄ nanoparticles. These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions. The optimized 3K/FeTi catalyst with the highest Fe₅C₂/Fe₃O₄ ratio of 3.6 achieves a 52.2% CO₂ conversion rate, with 44.5% selectivity for C_2-4⁼ and 9.5% for CO, and the highest space-time yield of 412.0 mg g_cat^-1 h^-1 for C_2-4⁼.

Key words: CO₂ hydrogenation, Light olefins, Strong Fe-Ti interaction, Fe₅C₂, Active phase modulation

Hao Liang, Shunan Zhang, Ruonan Zhang, Haozhi Zhou, Lin Xia, Yuhan Sun, Hui Wang. Strong interaction between Fe and Ti compositions for effective CO₂ hydrogenation to light olefins[J]. Chinese Journal of Catalysis, 2025, 71: 146-157.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60268-8

https://www.cjcatal.com/EN/Y2025/V71/I4/146

Figures/Tables 11

Fig. 1. CO2 conversion, CO selectivity and hydrocarbon distribution over the 3K/FeTi (1/2) catalyst reduced by different atmospheres (a) and temperatures (b). (c) Impact of Fe/Ti ratio on CO2 conversion, hydrocarbon distribution, and STY of C2-4=. (d) Influence of K content for the FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 3 MPa, T = 320 °C and WHSV = 6000 mL gcat-1 h-1. (e) Pressure-dependent CO2 conversion, hydrocarbon distribution, and STY of C2-4= over the 3K/FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 2-4.5 MPa, T = 320 °C, and WHSV = 6000 mL gcat-1 h-1. (f) Temperature-dependent CO2 conversion, hydrocarbon distribution, and STY of C2-4= over the 3K/FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 3.5 MPa, T = 300-380 °C and WHSV = 6000 mL gcat-1 h-1.

Fig. 2. XRD patterns of fresh and spent 3K/FeTi catalysts: (a) Post-reduction in different atmospheres; (b) Post-reduction at different H2 reduction temperatures.

Fig. 3. (a) Phase distribution of the spent 3K/FeTi (1/2) catalyst after the reduction under different conditions. (b) The relationship between phase ratios and reaction rate in the 3K/FeTi (1/2) catalyst.

Fig. 4. XRD patterns (a), XPS spectra of Fe 2p (b), Raman spectra (c), and H2-TPR profiles (d) of fresh 3K/FeTi catalysts with different Fe/Ti ratios.

Fig. 5. In situ XRD patterns of the fresh 3K/FeTi (4/1) (a) and 3K/FeTi (5/1) (b) catalysts. (c) XRD patterns of the spent catalysts with different Fe/Ti ratios.

Fig. 6. EXAFS spectra (a) and corresponding wavelet transform plots (b-d) of the spent catalysts with different Fe/Ti ratios, corresponding wavelet transform plots of the reference materials (e).

Fig. 7. M?ssbauer spectra of the spent catalysts with different Fe/Ti ratios. (a) 3K-FeTi (1/2)-600H2-R; (b) 3K-FeTi (2/1)-600H2-R; (c) 3K-FeTi (4/1)-600H2-R; (d) 3K-FeTi (5/1)-600H2-R.

Fig. 8. (a) Phase distribution of the spent catalysts with different Fe/Ti ratios. (b) Relationship between phase ratios and reaction rates in the spent catalysts with different Fe/Ti ratios.

Fig. 9. (a) H2-TPD profiles of the spent catalysts with different Fe/Ti ratios. (b) CO2-TPD profiles of the spent catalysts with different Fe/Ti ratios. (c) CO-TPD profiles of the spent catalysts with different Fe/Ti ratios.

Fig. 10. (a,b) TEM images of the spent 3K/FeTi (4/1) catalyst. (c,d) HRTEM images of the exposed facets in the 3K/FeTi (4/1) spent catalyst. (e) Model of Fe5C2 nanoprism with triclinic prism structure. (f) HRTEM image of Fe5C2 and Fe3O4 interface.

Fig. 11. In situ DIRFTS analysis during the CO2 hydrogenation over the3K/FeTi (4/1) (a) and 3K/FeTi (5/1) (b) catalysts.

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Strong interaction between Fe and Ti compositions for effective CO₂ hydrogenation to light olefins

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