Regulation products selectivity on PtCo alloy catalyst in CO2 hydrogenation through enhanced CO competitive adsorption and C-C coupling

doi:10.1016/S1872-2067(26)65159-5

Abstract

Abstract:

The hydrogenation of CO₂ into high-value-added chemicals represents one of the most effective strategies for mitigating the greenhouse effect and addressing the energy crisis. In this study, the incorporation of Pt into Co-based catalysts is utilized to modulate the CO competitive adsorption capacity and reaction pathways, thereby significantly enhances the C-C coupling and the selectivity of C₂₊ hydrocarbons during CO₂ hydrogenation. The formation of PtCo alloy in the catalysts is confirmed by X-ray absorption spectroscopy, in-situ X-ray diffraction, X-ray photoelectron spectroscopy and scanning transmission electron microscopy analyses. The study reveals that the presence of PtCo alloy alters the competitive adsorption behavior of CO and CO₂ on the catalyst, and enables CO to replace CO₂ as the strongly adsorbed species on the catalyst. Density functional theory calculations demonstrate that the PtCo alloy exhibits enhanced CO adsorption energy and reduced formation energy barrier for formate compared with pure Co. This is responsible for the emergence of an additional formate pathway on the PtCo catalyst. Consequently, the 2%PtCo catalyst achieves a C₂₊ selectivity of 18.5% under conditions of 350 °C and 3 MPa, markedly higher than the 1.9% over the pure Co catalyst. PtCo catalysts possesses 83.6 mmol·g^-1·h^-1 C₂₊ yield, outperforming the Fe-based reference catalyst by a factor of 4. The study presents a novel catalyst design concept for increasing C₂₊ selectivity through regulating the competitive adsorption between intermediate and reactant.

Key words: CO₂ hydrogenation, Co-based catalysts, CO competitive adsorption, PtCo alloy, C₂₊ products

Wenhui Li, Yangbo Liu, Yilin Zhang, Qingwen Yang, Hong Yang, Xiaowa Nie, Xinwen Guo. Regulation products selectivity on PtCo alloy catalyst in CO₂ hydrogenation through enhanced CO competitive adsorption and C-C coupling[J]. Chinese Journal of Catalysis, 2026, 89: 378-389.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65159-5

https://www.cjcatal.com/EN/Y2026/V89/I10/378

Figures/Tables 11

Fig. 1. (a) Catalytic performance over Co and PtCo catalysts in CO2 hydrogenation. Arrhenius plots of CO2 and C2+ over Co (b) and 2%PtCo (c). Reaction conditions: 0.04 g catalyst, H2/CO2 = 4:1 or 1:1, GHSV = 90000 mL·g-1·h-1, T = 350 °C, and P = 3 MPa.

Fig. 2. XRD patterns taken in-situ during hydrogen reduction of the 2%PtCo catalyst from 50 to 600 °C at 50 °C intervals. Reduction conditions: pure H2 atmosphere at 0.8 MPa.

Fig. 3. HAADF-STEM images of 2%PtCo catalyst before (a-d) and after (e-i) the H2 reduction at 400 °C.

Fig. 4. Co 2p XPS spectra of the reduced 2% PtCo and Co catalysts.

Fig. 5. XANES spectra (a), RDFs from the EXAFS data taken at Pt L3 edge (b), and Wavelet transform contour plots at Pt L3 edge of 2%PtCo (c) and Pt foil (d).

Fig. 6. (a) H2-TPR curves of the PtCo catalysts with 0.1 wt%, 0.5 wt% and 2.0 wt% Pt loading. (b) H/D exchange curves of 2%PtCo and Co.

Fig. 7. (a) CO-TPD curves of Co and PtCo catalysts with 0.1 wt%, 0.5 wt% and 2.5 wt% Pt loading. (b) In-situ CO DRIFT spectra of Co and 2%PtCo. (c) CO adsorption energy on Pt (111), PtCo (101-0) and Co (101-0).

Fig. 8. Breakthrough curves (a), adsorption rate-time curves (b), and adsorption capacity-time curves (c) for the competitive CO?/CO adsorption on Co. Breakthrough curves (d), adsorption rate-time curves (e), and adsorption capacity-time curves (f) for the competitive CO?/CO adsorption on 2%PtCo. Competitive adsorption conditions: 25 °C, 0.1 bar, and CO/CO2 = 1:1.

Fig. 9. In-situ DRIFT spectra collected over wavenumber range of 3200 to 1000 cm-1 during CO2 hydrogenation on Co and 2%PtCo. Reaction conditions: H2/CO2 = 1:1, T = 50-400 °C, and P = 3 MPa.

Fig. 10. Energy diagrams of different CO2 reaction routes on Co (101-0) and PtCo (101-0).

Fig. 11. Mechanism diagram of CO2 hydrogenation to C2+ hydrocarbons on PtCo catalyst.

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Regulation products selectivity on PtCo alloy catalyst in CO₂ hydrogenation through enhanced CO competitive adsorption and C-C coupling

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