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Scalable two-step annealing method for preparing ultra-high-density single-atom catalyst libraries

Nature Nanotechnology volume 17, pages 174–181 (2022)Cite this article

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A Publisher Correction to this article was published on 04 March 2022

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Abstract

The stabilization of transition metals as isolated centres with high areal density on suitably tailored carriers is crucial for maximizing the industrial potential of single-atom heterogeneous catalysts. However, achieving single-atom dispersions at metal contents above 2 wt% remains challenging. Here we introduce a versatile approach combining impregnation and two-step annealing to synthesize ultra-high-density single-atom catalysts with metal contents up to 23 wt% for 15 metals on chemically distinct carriers. Translation to a standardized, automated protocol demonstrates the robustness of our method and provides a path to explore virtually unlimited libraries of mono- or multimetallic catalysts. At the molecular level, characterization of the synthesis mechanism through experiments and simulations shows that controlling the bonding of metal precursors with the carrier via stepwise ligand removal prevents their thermally induced aggregation into nanoparticles. The drastically enhanced reactivity with increasing metal content exemplifies the need to optimize the surface metal density for a given application. Moreover, the loading-dependent site-specific activity observed in three distinct catalytic systems reflects the well-known complexity in heterogeneous catalyst design, which now can be tackled with a library of single-atom catalysts with widely tunable metal loadings.

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Fig. 1: Synthesis of UHD-SACs.
Fig. 2: Visualization and spectroscopic characterization of UHD-SACs.
Fig. 3: Visualization of multimetallic UHD-SACs.
Fig. 4: Automated synthesis protocol.
Fig. 5: Mechanistic investigation of the synthesis of UHD-SACs.
Fig. 6: Catalytic performance of UHD-SACs.

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Data availability

All data that support the findings of this study have been included in the main text and Supplementary Information. Any additional materials and data are available from the corresponding author upon reasonable request.

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Acknowledgements

J. Lu acknowledges support from MOE grant (R-143-000-B47-114), the Ministry of Education (Singapore) through the Research Centre of Excellence program (Award EDUN C-33-18-279-V12, Institute for Functional Intelligent Materials) and the National University of Singapore Flagship Green Energy Program (R-143-000-A55-646). X.Z. acknowledges support from a Presidential Postdoctoral Fellowship, Nanyang Technological University, Singapore via grant 03INS000973C150. S.M., D.F.A., and J.P.-R. acknowledge funding from the NCCR Catalysis, a National Centre of Competence in Research funded by the Swiss National Science Foundation. Jun Li acknowledges financial support by the National Natural Science Foundation of China (grant number 22033005) and the Guangdong Provincial Key Laboratory of Catalysis (2020B121201002). Computational resources were supported by the Center for Computational Science and Engineering (SUSTech) and Tsinghua National Laboratory for Information Science and Technology. We would like to acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore, for use of their electron microscopy facilities.

Author information

Author notes

  1. These authors contributed equally: Xiao Hai, Shibo Xi, Sharon Mitchell, Karim Harrath.

Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Xiao Hai, Haomin Xu, Jing Li, Zejun Li, Tao Sun, Huimin Yang, Yige Cui & Jiong Lu

  2. Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research, Singapore, Singapore

    Shibo Xi

  3. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland

    Sharon Mitchell, Dario Faust Akl & Javier Pérez-Ramírez

  4. Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Karim Harrath & Jun Li

  5. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, China

    Karim Harrath & Jun Li

  6. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, China

    Debin Kong

  7. SZU-NUS Collaborative Center and International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology of Ministry of Education, Engineering Technology Research Center for 2D Materials Information Functional Devices and Systems of Guangdong Province, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China

    Chenliang Su

  8. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore

    Xiaoxu Zhao

  9. Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, Singapore

    Jiong Lu

  10. Institute for Functional Intelligent Materials, National University of Singapore, Singapore, Singapore

    Jiong Lu

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  1. Xiao Hai
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Contributions

X.H. and J. Lu conceived and designed the experiments. J.P.-R. conceived the automated synthesis protocol. J. Lu and J.P.-R. supervised the project and organized the collaboration. X.H. performed materials synthesis. S.M. and D.F.A performed automated synthesis. X.H. and T.S. performed the activity test. S.X. performed the XAFS measurement. X.Z., H.X. and D.K. performed the electron microscopy experiments and data analysis. C.S. helped to perform the CO-DRIFTS measurements. Jing Li performed the XPS measurements. Z.L. performed the nitrogen sorption measurements. H.Y. and Y.C. performed the X-ray diffraction measurements. K.H. and Jun Li carried out theoretical calculations. X.H., S.M., J.P.-R., Jun Li and J. Lu co-wrote the manuscript. All authors discussed and commented on the manuscript.

Corresponding authors

Correspondence to Xiaoxu Zhao, Jun Li, Javier Pérez-Ramírez or Jiong Lu.

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Peer review information Nature Nanotechnology thanks Abhaya Datye and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Hai, X., Xi, S., Mitchell, S. et al. Scalable two-step annealing method for preparing ultra-high-density single-atom catalyst libraries. Nat. Nanotechnol. 17, 174–181 (2022). https://doi.org/10.1038/s41565-021-01022-y

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