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Light-driven CO2 methanation over Au-grafted Ce0.95Ru0.05O2 solid-solution catalysts with activities approaching the thermodynamic limit

Nature Catalysis volume 6, pages 519–530 (2023)Cite this article

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Abstract

Photothermal CO2 methanation offers a clean and sustainable solution to store intermittent renewable energy as synthetic CH4. However, its high reaction temperature and low space-time yield hinder its industrial application. Here we report an Au/Ce0.95Ru0.05O2 solid-solution catalyst exhibiting a remarkable photothermal CO2 methanation activity approaching the thermal catalysis limit under visible–near-infrared light irradiation without external heating. Localized surface-plasmon-induced hot-electron injection created abundant oxygen vacancies near the dispersed ruthenium sites, accelerating CO2 methanation. An approximately 6- to 8-fold increase in the pre-exponential factor was evidenced using Arrhenius plot analysis under visible–near-infrared light irradiation. Using a flow reactor, a photothermal CH4 production rate of \(473\,{\mathrm{mmol}}\,{\mathrm{g}}_{\mathrm{cat}}^{-1}\,{\mathrm{h}}^{-1}\) was obtained at a gas hourly space velocity of \(80,000\,{\mathrm{ml}}\,{\mathrm{g}}_{\mathrm{cat}}^{-1}\,{\mathrm{h}}^{-1}\) with ~100% CH4 selectivity, ~75% single-pass CO2 conversion and excellent durability. Our study offers insights into plasmonic-steered photochemistry, which may open opportunities for the high-yielding synthesis of carbon-based chemicals using solar energy.

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Fig. 1: Schematic of photothermal CO2 methanation over Au/Ce0.95Ru0.05O2.
Fig. 2: Photothermal and thermal catalytic CO2 methanation model tests.
Fig. 3: Characterizations.
Fig. 4: Mechanistic studies.
Fig. 5: Isotopic trace experiments.
Fig. 6: Photothermal CO2 methanation in a flow reactor.
Fig. 7: Photothermal CO2 methanation on screen-printed catalyst thin layers.

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Data availability

All data are available in the ScienceDB repository at https://doi.org/10.57760/sciencedb.08102 or from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant numbers 22272078, 91963121), the National Key Research and Development Program of the Ministry of Science and Technology of China (number 2020YFA0406102), and the Frontiers Science Center for Critical Earth Material Cycling of Nanjing University.

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Authors and Affiliations

  1. College of Engineering and Applied Sciences, National Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, Nanjing University, Nanjing, China

    Haoyang Jiang, Linyu Wang, Le Li, Jin Zhang, Feng Zhu & Miao Zhong

  2. School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan

    Hiroaki Kaneko, Akira Yamaguchi & Masahiro Miyauchi

  3. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Rongtian Gu & Weiping Ding

  4. Department of Applied Physics, Zhejiang University of Technology, Hangzhou, China

    Guangxu Su & Fanxin Liu

  5. School of Electronic Science and Engineering, Nanjing University, Nanjing, China

    Hucheng Song & Jun Xu

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  1. Haoyang Jiang
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Contributions

M.Z. supervised the project and conceived the idea. M.Z. and H.J. designed the experiments. H.J. and L.W. performed the synthesis, characterizations and performance tests. R.G. and W.D. provided the apparatus and helped perform the isotopic tracer analysis. H.K., A.Y. and M.M. reproduced the photothermal catalytic performance and carried out operando DRIFTS measurement. H.S. provided the apparatus and helped perform the EPR and ultraviolet–visible–near-infrared DRS tests. G.S. conducted the electromagnetic simulations. G.S., L.L., J.Z., F.Z., F.L., M.M., W.D. and M.Z. discussed the experimental results. H.J., G.S., A.Y., M.M., W.D. and M.Z. wrote the manuscript. All authors discussed the results and assisted during manuscript preparation.

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Correspondence to Miao Zhong.

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Nature Catalysis thanks Agustin Bueno Lopez and Emiliano Cortés for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–15, Figs. 1–43 and Tables 1–9.

Supplementary Video 1

Reaction using Au/Ce0.95Ru0.05O2.

Supplementary Video 2

Reaction using Ce0.95Ru0.05O2.

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Jiang, H., Wang, L., Kaneko, H. et al. Light-driven CO2 methanation over Au-grafted Ce0.95Ru0.05O2 solid-solution catalysts with activities approaching the thermodynamic limit. Nat Catal 6, 519–530 (2023). https://doi.org/10.1038/s41929-023-00970-z

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