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Engineering MOx/Ni inverse catalysts for low-temperature CO2 activation with high methane yields

Nature Chemical Engineering volume 1, pages 638–649 (2024)Cite this article

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Abstract

Low-temperature methanation allows the near-equilibrium conversion of CO2 to methane at atmospheric pressure, promising remarkable energy efficiency and economic interests. However, it remains challenging for the efficient catalytic activation of CO2 at low temperature owing to the kinetic limitations of hydrogenation intermediates. Here we report that Ni-based inverse catalysts composed of oxide nano-islands loaded on metallic Ni support show significant activity advantages over traditional Ni/oxide with the same composition. The optimized CeZrOx/Ni catalyst realizes ~90% CO2 conversion and >99% CH4 selectivity at 200 °C and atmospheric pressure; it also exhibits excellent long-term stability and overheating/start–stop cyclic operation stability. Mechanistic studies show that the inverse interface effectively modulates H2 and CO2 coverage and alters the configuration of adsorbed oxygenates, which benefits the hydrogenation of surface intermediates. Energy and economic analyses demonstrate that the low-temperature CO2 methanation process powered by inverse catalysts potentially reduces both capital investment and methane production costs.

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Fig. 1: The catalytic performance of inverse catalysts for low-temperature CO2 hydrogenation.
Fig. 2: The catalytic performance of CeZrOx/Ni inverse catalysts.
Fig. 3: Structural characterization of the inverse 13 mol% CeZrOx/Ni catalysts.
Fig. 4: Mechanism of CO2 hydrogenation on conventional and inverse interfacial structures.
Fig. 5: Economic analysis of methanation in the low- and high-temperature processes.

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Data availability

All data are available within the Article and its Supplementary Information. The atomic coordinates of the optimized computational models are provided in Supplementary Data 1. Source data are provided with this paper.

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Acknowledgements

This work is financially supported by the Zhejiang Provincial Natural Science Foundation of China (LR22B030003, L.L.; LQ24B030016, C.S.), Natural Science Foundation of China (22278367, L.L.), China Postdoctoral Science Foundation Grant (2022M712817, C.S.), Research Fund of Department of Education of Zhejiang Province (Y202249632, L.L.), National Natural Science Foundation of China 22232001 (D.M.), National Key R&D Program of China 2021YFA1501102 (D.M.), XPLORER Prize of Tencent Foundation (D.M.), New Cornerstone Science Foundation of Tencent Foundation (D.M.), Natural Science Foundation of China (22225206, X.W.), Natural Science Foundation of China (22202224, J.L.) and the Project of National Natural Science Foundation of China (U22A20415, Z.L.).

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Author notes

  1. These authors contributed equally: Chuqiao Song, Jinjia Liu, Ruihang Wang.

Authors and Affiliations

  1. Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, China

    Chuqiao Song, Xin Tang, Haibo Li, Hanfeng Lu, Xiaonian Li & Lili Lin

  2. Zhejiang Carbon Neutral Innovation Institute and Zhejiang International Cooperation Base for Science and Technology on Carbon Emission Reduction and Monitoring, Zhejiang University of Technology, Hangzhou, China

    Chuqiao Song, Xin Tang, Haibo Li, Hanfeng Lu & Lili Lin

  3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

    Jinjia Liu & Xiao-Dong Wen

  4. National Energy Centre for Coal to Liquids, Synfuels China Co. Ltd, Beijing, China

    Jinjia Liu & Xiao-Dong Wen

  5. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China

    Ruihang Wang, Siyu Yao & Zuwei Liao

  6. Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, China

    Kun Wang & Feng Yang

  7. Beijing National Laboratory for Molecular Science, New Cornerstone Science Laboratory, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Zirui Gao, Mi Peng & Ding Ma

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Contributions

L.L., D.M. and X.L. designed the study. C.S. and X.T. performed most of the reactions. X.T. and H. Lu carried out the stability experiments. J.L. and X.-D.W. performed the DFT calculations. R.W. and Z.L. performed the energy and economy analyses. K.W., Z.G. and F.Y. performed the TEM characterization. C.S. and H. Li carried out the DRIFTS analysis. C.S., L.L., S.Y. and M.P. wrote the paper. All authors discussed and revised the paper.

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Correspondence to Zuwei Liao, Xiao-Dong Wen, Ding Ma or Lili Lin.

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Nature Chemical Engineering thanks Patricia Concepcion, Atsushi Urakawa and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–28, Discussion and Tables 1–15.

Supplementary Data 1

Atomic coordinates of the optimized computational models

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Song, C., Liu, J., Wang, R. et al. Engineering MOx/Ni inverse catalysts for low-temperature CO2 activation with high methane yields. Nat Chem Eng 1, 638–649 (2024). https://doi.org/10.1038/s44286-024-00122-5

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