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High-purity carbon monoxide production via photothermal formic acid decomposition over fluorite ZrO2

Nature Catalysis volume 7, pages 1350–1358 (2024)Cite this article

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Abstract

High-purity carbon monoxide (CO), crucial for various high-tech industries, requires complex purification and further energy input. Here we show that pure fluorite ZrO2 can produce clean CO without purification by driving formic acid dehydration and completely shutting off the formic acid dehydrogenation pathway. An explosion method is developed for synthesizing pristine fluorite ZrO2 nanosheets that achieve a pure CO production rate of 55 mmol g−1 h−1 at 250 °C. Integrated with a homemade photothermal reactor, the fluorite ZrO2 nanosheets show a pure CO productivity of 83 mmol g−1 h−1 under 0.5 sun irradiation and a photochemical energy conversion efficiency of 12.3%. Moreover, this system generates over 1,538 l m−2 of pure CO per day under outdoor sunlight irradiation. This work charts a promising course for purification-free pure CO generation without secondary energy input.

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Fig. 1: Theoretical simulation of formic acid decomposition.
Fig. 2: The synthesis and characterization of pure fluorite ZrO2.
Fig. 3: Thermocatalytic formic acid decomposition performances of catalysts.
Fig. 4: Characterization of intermediates in formic acid decomposition.
Fig. 5: The photothermal formic acid dehydration.

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Data availability

Source data are available via figshare at https://doi.org/10.6084/m9.figshare.27300834.v1 (ref. 51) or from the corresponding author upon reasonable request.

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Acknowledgements

We thank Qingbo Meng (Institute of Physics, Chinese Academy of Sciences) for the guidance on the formic acid dehydration. We are grateful for the TEM technical support provided by the Microanalysis Center, College of Physics Science and Technology, Hebei University. We thank Jianmin Lv (Dalian Institute of Chemical Physics, Chinese Academy of Sciences), Wei Zhou (Tianjin University) and Ruqian Lian (Hebei University) for assistance with the theoretical calculations. This work is supported by the National Natural Science Foundation of China (52371220, Y.Li; U23A20139, J.Y.), Natural Science Foundation of Hebei Province (B2023204034, Y.Li; B2023201107, D.Y.; B2022201090, Y.Li; B2021201074, Y.Li; B2024201096, J.Y.; 2023HBQZYCXY001, J.Y.), Hebei Education Department (QN2022059, D.Y.), Interdisciplinary Research Program of Natural Science of Hebei University (521100311, J.Y.; DXK202109, Y.Li), the Advanced Talents Incubation Program of Hebei University (grant no. 050001-521100223213, J.Y.) and the Scientific Research Foundation of Hebei Agricultural University (YJ201939, D.Y.).

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Author notes

  1. These authors contributed equally: Yaguang Li, Bang Liu, Dachao Yuan, Haixiao Wang.

Authors and Affiliations

  1. Research Center for Solar Driven Carbon Neutrality, Engineering Research Center of Zero-carbon Energy Buildings and Measurement Techniques, Ministry of Education, The College of Physics Science and Technology, Institute of Life Science and Green Development, Hebei University, Baoding, China

    Yaguang Li, Bang Liu, Dachao Yuan, Haixiao Wang, Qixuan Wu, Yachuan Wang, Junwei Wang, Xingyuan San & Jinhua Ye

  2. College of Mechanical and Electrical Engineering, Key Laboratory Intelligent Equipment and New Energy Utilization of Livestock and Poultry Breeding, Hebei Agricultural University, Baoding, China

    Yaguang Li & Dachao Yuan

  3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Yanhong Luo

  4. International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Ibaraki, Japan

    Jinhua Ye

  5. Graduate School of Chemical Science and Engineering, Hokkaido University, Sapporo, Japan

    Jinhua Ye

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Contributions

Y. Li and J.Y. conceived the project and contributed to the design of the experiments and analysis of the data. Y. Luo, B.L. and D.Y. performed the preparation and characterizations of the catalysts. D.Y., H.W., Q.W. and J.W. performed the photothermal reactors’ characterizations. X.S. and Y.W. conducted the SEM and TEM examinations. Y. Li and J.Y. wrote the paper. All the authors discussed the results and commented on the paper.

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Correspondence to Yaguang Li, Yanhong Luo or Jinhua Ye.

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Nature Catalysis thanks Hermenegildo Garcia and Andrew Logsdail for their contribution to the peer review of this work.

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Supplementary Methods, Figs. 1–28 and References.

Supplementary Video 1

The fast-burning video of the mixture of zirconium salt and explosive.

Supplementary Video 2

The water droplets produced from thermal formic acid decomposition over F-ZrO2.

Supplementary Video 3

The working video of photothermal formic acid dehydration.

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Li, Y., Liu, B., Yuan, D. et al. High-purity carbon monoxide production via photothermal formic acid decomposition over fluorite ZrO2. Nat Catal 7, 1350–1358 (2024). https://doi.org/10.1038/s41929-024-01249-7

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