Highly efficient electron-enriched Y2O3‒x-Ni interfaces boosting low-temperature CO2 methanation

doi:10.1016/S1872-2067(26)65012-7

Abstract

Abstract:

CO₂ methanation technology has shown great application prospects in carbon neutrality and hydrogen storage due to its extremely high energy efficiency and potential economic benefits. It is highly desirable but challenging to design novel catalyst and achieve efficient and stable CO₂ methanation under mild conditions. Herein, we developed a highly active electron-enriched Y₂O₃/Ni catalyst, achieving a stable operation with ~80.1% CO₂ conversion and ~100% CH₄ selectivity for 400 h at 0.1 MPa and 220 °C, which was a 100 °C lower than the conventional supported Ni-based catalysts. Structural characterizations confirmed that the Y₂O₃/Ni catalyst maintained dynamic redox changes and formed electron-enriched Y₂O_3‒_x-Ni interfaces under reaction conditions. Mechanism studies proved that the Y₂O_3‒_x-Ni interfaces obviously lowered the energy barrier of *HCO dissociation, and shifted the rate-determining step from *HCO dissociation to *CO hydrogenation. Furthermore, profited by the moderate CO_x adsorption ability and higher H₂ coverage at the Y₂O_3‒_x-Ni interfaces, the *CO hydrogenation reaction was kinetically promoted. The above factors accounted for the excellent low-temperature CO₂ methanation activity of the Y₂O₃/Ni catalyst.

Key words: Electron enrichment, Y₂O_3?x-Ni interfaces, Reaction mechanism, Low-temperature CO₂ methanation

Haifeng Fan, Di Xu, Ting Zeng, Guoqiang Hou, Yangyang Li, Siyi Huang, Yanfei Xu, Zheng Wang, Xinhua Gao, Xiang-Kui Gu, Mingyue Ding. Highly efficient electron-enriched Y₂O_3‒_x-Ni interfaces boosting low-temperature CO₂ methanation[J]. Chinese Journal of Catalysis, 2026, 84: 200-213.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65012-7

https://www.cjcatal.com/EN/Y2026/V84/I5/200

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Fig. 1. Low-temperature CO2 methanation performance. (a) CO2 conversion and CH4 selectivity; (b) Ea; (c) performance comparison with reported catalysts at atmospheric pressure; (d) 400 h time-on-stream (TOS) test at 220 °C. Reaction conditions: H2/CO2 = 4, 0.1 MPa, 160?340 °C, 15000 mL gcat-1 h-1.

Fig. 2. Structural characterizations of Y2O3/Ni and Ni/Y2O3 catalysts. HRTEM (a), TEM images and corresponding particle size statistics (b), and EDS mapping (c). In-situ XRD patterns of Y2O3/Ni (d,e) and Ni/Y2O3 (g,h) during H2 reduction (d,g) and CO2 hydrogenation (e,h) at different temperatures. (f) Enlarged view of (e). (i) Peak area percent of Ni and NiO after splitting peaks.

Fig. 3. Electronic properties of Y2O3-Ni interfaces. Quasi in-situ XPS of Ni 2p (a) and Y 3d (b) after different treatments. (c) Calculated oxygen vacancy formation energy. (d) Two dimension of charge density difference for interfacial OH on Y4O6H6/Ni(111) and Ni/Y2O3-OH(111). (e) Average Charge of Y atoms on Y4O6H6/Ni(111) and Y4O5H5/Ni(111), Nickel (green), Yttrium (light blue), Oxygen (red), and Hydrogen (white).

Fig. 4. Adsorption properties of Y2O3/Ni and Ni/Y2O3 catalysts. Reaction orders of CO2 (a) and H2 (b), CO2-TPD-MS (c), H2-TPD-MS (d), and corresponding adsorption capacities (e). (f) Illustration of the CO2/CO/H2 adsorption on Y2O3/Ni inverse catalyst and Ni/Y2O3 conventional catalyst.

Fig. 5. Reaction mechanism study of CO2 methanation on Y2O3/Ni catalyst. (a) In-situ DRIFTS with feed gas switching from CO2/H2 to H2. (b) Comparison of CO2-preadsorbed Y2O3/Ni under Ar and H2 atmosphere. (c) Lin-*CO intensity change on CO2-preadsorbed Y2O3/Ni and Ni/Y2O3 under Ar and H2 atmosphere. (d) Intensity changes of various species on CO2 pre-adsorbed Y2O3/Ni under H2 atmospheres. Experiment conditions: 0.1 MPa, 220 °C.

Fig. 6. Theoretical perspective of CO2 methanation mechanism on Y2O3/Ni interfaces. CO2 adsorption energies, charge difference (a) and COHP analysis (b) towards C=O bond of adsorbed CO2 on Ni(111) and Y4O5H5/Ni(111). (c) Free energy diagrams of direct CO2 dissociation and CO hydrogenation route of CO2 methanation on Y4O5H5/Ni(111) at 220 °C and 0.1 MPa. (d) Energies of key reactions on Ni(111). Nickel (green), Yttrium (light blue), Oxygen (red or pink), Carbon (black), and Hydrogen (white).

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Highly efficient electron-enriched Y₂O_3‒_x-Ni interfaces boosting low-temperature CO₂ methanation

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