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A general synthesis of single atom catalysts with controllable atomic and mesoporous structures

Nature Synthesis volume 1, pages 658–667 (2022)Cite this article

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Abstract

The control of single metal atomic sites has been extensively studied in the field of single atom catalysts. By contrast, the precise control of the mesoporous structure in the matrix material, which directly correlates with mass diffusions and may play a dominant role in delivering industrially relevant reaction rates, has been overlooked. Here we report a general method for the synthesis of a single atom catalyst with control of the atomic structure of the single atomic site as well as the mesoporous structure of the carbon support for optimized catalytic performance. Various combinations of metal centres (Ni, Co, Mn, Zn, Cu, Sc and Fe) and mass diffusion channels in two dimensions and three dimensions were achieved. Using CO2 reduction to CO as an example, our Ni single atom catalyst with three-dimensional diffusion channels delivered a practical current of 350 mA cm−2 while maintaining a 93% CO Faradaic efficiency, representing a sixfold improvement in turnover frequency compared to two-dimensional counterparts.

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Fig. 1: Synthesis strategy of M-SACs.
Fig. 2: Microscopic characterizations of Ni-SACs synthesized by using different hard templates.
Fig. 3: Fine structure of Ni-SACs.
Fig. 4: Aberration-corrected MAADF/HAADF-STEM images of various SACs.
Fig. 5: Electrochemical CO2RR performance of M-SACs in a flow cell set-up using 1.0 M KHCO3 electrolyte.
Fig. 6: Electrochemical CO2RR performance of 3D-Ni-SAC in an anion MEA cell.

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The data supporting the findings of the study are available in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Welch Foundation Research Grant (C-2051-20200401, H.W.), the Roy E. Campbell Faculty Development Award and Rice University. Aberration-corrected STEM-EELS and electron tomography research conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. The XAS data were collected at SXRMB of the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), Canadian Institutes of Health Research (CIHR), Government of Saskatchewan and the University of Saskatchewan.

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Author notes

  1. These authors contributed equally: Zhen-Yu Wu, Peng Zhu.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA

    Zhen-Yu Wu, Peng Zhu, Feng-Yang Chen & Haotian Wang

  2. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    David A. Cullen & Haoran Yu

  3. Canadian Light Source Inc., University of Saskatchewan, Saskatoon, SK, Canada

    Yongfeng Hu, Mohsen Shakouri & Alisa R. Paterson

  4. Department of Chemistry, University of Science and Technology of China, Hefei, China

    Qiang-Qiang Yan, Shan-Cheng Shen & Hai-Wei Liang

  5. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Jose D. Arregui-Mena

  6. Electrification and Energy Infrastructure Division (EEID), Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Amirkoushyar Ziabari

  7. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA

    Haotian Wang

  8. Department of Chemistry, Rice University, Houston, TX, USA

    Haotian Wang

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  1. Zhen-Yu Wu
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Contributions

Z.-Y.W. and H.W. conceptualized the project. H.W. supervised the project. Z.-Y.W. developed and performed the catalyst synthesis. Z.-Y.W., P.Z., D.A.C., Y. H., Q.-Q.Y., S.-C.S, F.-Y.C., H.Y., M.S., J.D.A.-M., A.Z., A.P. and H.-W.L. carried out the materials characterization. Z.-Y.W. and P.Z. conducted the catalytic tests of catalysts and the related data processing. Z.-Y.W., P.Z. and H.W. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Haotian Wang.

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Nature Synthesis thanks Sharon Mitchell, Bert Weckhuysen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–87, Tables 1–6, Notes 1–3 and refs. 1–21.

Supplementary Video 1

Electron tomography data and reconstruction and segmented data of Ni-SAC/SBA-15.

Source data

Source Data Fig. 5

Numerical data used to generate graphs.

Source Data Fig. 6

Numerical data used to generate graphs.

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Wu, ZY., Zhu, P., Cullen, D.A. et al. A general synthesis of single atom catalysts with controllable atomic and mesoporous structures. Nat. Synth 1, 658–667 (2022). https://doi.org/10.1038/s44160-022-00129-x

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