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Advances in heterogeneous single-cluster catalysis

Nature Reviews Chemistry volume 7, pages 754–767 (2023)Cite this article

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Abstract

Heterogeneous single-cluster catalysts (SCCs) comprising atomically precise and isolated metal clusters stabilized on appropriately chosen supports offer exciting prospects for enabling novel chemical reactions owing to their broad structural diversity with unparalled opportunities for engineering their properties. Although the pioneering work revealed intriguing performance trends of size-selected metal clusters deposited on supports, synthetic and analytical challenges hindered a thorough understanding of surface chemistry under realistic conditions. This Review underscores the importance of considering the cluster environment in SCCs, encompassing the development of robust metal–support interactions, precise control over the ligand sphere, the influence of reaction media and dynamic behaviour, to uncover new reactivities. Through examples, we illustrate the criticality of tailoring the entire catalytic ensemble in SCCs to achieve stable and selective performance with practically relevant metal coverages. This expansion in application scope transcends from model reactions to complex and technically relevant reactions. Furthermore, we provide a perspective on the opportunities and future directions for SCC design within this rapidly evolving field.

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Fig. 1: Defining features of single-cluster catalysts.
Fig. 2: Synthetic strategies for producing single-cluster catalysts.
Fig. 3: Properties of single-cluster catalysts.
Fig. 4: Enhancing reactivity of single-cluster catalysts.
Fig. 5: Reported property–performance relationships on single-cluster catalysts.
Fig. 6: Conceptual strategies for discovering new reactivity of single-cluster catalysts.
Fig. 7: Structural dynamics of single-cluster catalysts.
Fig. 8: Roadmap for single-cluster catalyst development.

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Acknowledgements

J.Lu acknowledges the support from National Research Foundation, CRP programme (CRP29-2022-0038) and from Agency for Science, Technology and Research (A*STAR) under its MTC IRG Grant (M22K2c0082). S.M. and J.P.-R. acknowledge NCCR Catalysis (No. 180544), a National Centre of Competence in Research funded by the Swiss National Science Foundation. X.L. acknowledges the support from the Natural Science Foundation of Shaanxi Province (No. 2023-JC-QN-0136), ‘Young Talent Support Plan’ of Xi’an Jiaotong University (No. ND6J026) and Qinchuangyuan High-Level Talent Project (No. QCYRCXM-2022-344). J.Li. acknowledges the financial support from the National Natural Science Foundation of China (Grant No. 22033005), NSFC Center for Single-Atom Catalysis, the National Key Research and Development Project (Grant Nos 2022YFA1503900 and 2022YFA1503000) and the Guangdong Provincial Key Laboratory of Catalysis (No. 2020B121201002). Y.F. acknowledges the financial support from the National Natural Science Foundation of China (No. 22005244) and Fundamental Research Funds for the Central Universities (No. D5000230127).

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  1. These authors contributed equally: Xinzhe Li, Sharon Mitchell.

Authors and Affiliations

  1. Department of Environmental Science and Engineering, School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi, China

    Xinzhe Li

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

    Xinzhe Li, Yiyun Fang & Jiong Lu

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

    Sharon Mitchell & Javier Perez-Ramirez

  4. Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing, China

    Jun Li

  5. Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen, China

    Jun Li

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X.L. and S.M. contributed equally. All authors contributed substantially to the discussion of the content and structure, investigated the literature, wrote, reviewed and edited the manuscript.

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Li, X., Mitchell, S., Fang, Y. et al. Advances in heterogeneous single-cluster catalysis. Nat Rev Chem 7, 754–767 (2023). https://doi.org/10.1038/s41570-023-00540-8

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