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Enhanced CO2 utilization in dry reforming of methane achieved through nickel-mediated hydrogen spillover in zeolite crystals

Nature Catalysis volume 5, pages 1030–1037 (2022)Cite this article

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Abstract

Transformation of CO2 into precursors for chemicals and fuels by self-contained reducing gas contaminants (for example, CH4) is attractive from a carbon economy perspective. Reducing as much CO2 as possible using a limited amount of reducing gas would be ideal, but general dry reforming (DRM) schemes consume stoichiometric amounts of methane for CO2 reduction. Here we develop a process with high reducibility of methane relative to conventional DRM, using up to 2.9 mol of CO2 per mol of CH4. Key to this success are Ni nanoparticles, fixed within the matrix of an aluminosilicate zeolite catalyst (Ni@HZSM-5), that enhance hydrogen spillover to favour the reduction of CO2. This process achieves an energy cost for reducing CO2 of 113.6 kJ per mol CO2, which is 31.9% lower than the conventional DRM process with stoichiometric transformation of CO2 and methane. In addition, the rigid zeolite framework could minimize coke formation and prevent Ni sintering.

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Fig. 1: Structural characterization of Ni@HZSM-5.
Fig. 2: Catalytic data.
Fig. 3: Equilibrium data and kinetic study.

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Data availability

All data are available from the authors upon reasonable request.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2021YFA1500404), and the National Natural Science Foundation of China (U21B20101 and 21932006).

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Author notes

  1. These authors contributed equally: Qiuyan Zhu, Hang Zhou, Liang Wang.

Authors and Affiliations

  1. Key Lab of Applied Chemistry of Zhejiang Province and Department of Chemistry & Key Lab of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China

    Qiuyan Zhu, Hang Zhou, Liang Wang, Chengtao Wang, Hai Wang, Wei Fang & Feng-Shou Xiao

  2. State Key Laboratory of Supramolecular Structure and Materials, Department of Chemistry, Jilin University, Changchun, China

    Liang Wang

  3. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China

    Mingyuan He

  4. Department of Science and Technology Development, China National Offshore Oil Corporation, Beijing, China

    Qing Wu

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Contributions

Q.Z. performed the catalyst preparation, characterization and catalytic tests. H.Z. performed the thermodynamic and kinetic analysis. L.W. (Jilin University) performed the TEM characterization. C.W., H.W. and W.F. participated in the catalyst preparation and characterizations. M.H. and Q.W. provided helpful discussions. L.W. (Zhejiang University) and F.-S.X. designed this study, analysed the data and wrote the paper.

Corresponding authors

Correspondence to Liang Wang or Feng-Shou Xiao.

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Nature Catalysis thanks Hyun-Seog Roh, Roger Gläser, José Odriozola and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Methods, Table 1, Figs. 1–35, Notes 1–8 and references.

Supplementary Video 1

Video showing the TEM observation of the Ni@ZSM-5 catalyst.

Supplementary Video 2

Video showing the TEM observation of the Ni/ZSM-5 catalyst.

Source data

Source Data Fig. 2

Source data for the catalytic tests in Fig. 2 of the main text.

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Zhu, Q., Zhou, H., Wang, L. et al. Enhanced CO2 utilization in dry reforming of methane achieved through nickel-mediated hydrogen spillover in zeolite crystals. Nat Catal 5, 1030–1037 (2022). https://doi.org/10.1038/s41929-022-00870-8

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