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Ordered single active sites for cascade hydrogenation and hydroformylation reactions

Nature Catalysis volume 8, pages 536–547 (2025)Cite this article

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Abstract

Metal single-atom catalysts offer improved activity and selectivity due to their unique electronic and coordination properties compared with bulk metals. However, many single-atom catalysts suffer from randomly dispersed active sites and limited electron-donating ability due to bonding with electronegative elements or less reactive metals. Here we demonstrate that Mg-rich intermetallic Mg29TM4 (TM = Pd, Rh, Ir, Pt) nanocatalysts overcome these limitations. These materials feature periodically dispersed, electron-rich single-atom sites of noble metals within a uniform chemical environment. Mg29TM4 exhibits high activity and selectivity in C2H2 semihydrogenation (Mg29Pd4) and olefin hydroformylation (Mg29Rh4), with Mg29Rh4 achieving high regioselectivity for branched aldehydes (branched:linear > 200:1). Kinetic and density functional theory studies suggest that the Mg–TM ensemble enables precise control over carbon–carbon multiple bond adsorption and activation, enhancing both activity and selectivity. Furthermore, the ternary Mg29Pd1.3Rh2.7 catalyst, with its synergistic Mg–Pd and Mg–Rh dual single-atom sites, efficiently catalyses a cascade reaction involving phenylacetylene hydrogenation followed by hydroformylation.

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Fig. 1: Evolution of atomically dispersed catalysts from disordered to ordered structures.
Fig. 2: Theoretical analysis of crystal and electronic structures.
Fig. 3: Schematic for the preparation and characterization of Mg29Pd4.
Fig. 4: Structural characterization of the Mg29Pd4 SAIMC.
Fig. 5: Elemental EDS mapping images and particle average size of representative Mg29TM4 compounds.
Fig. 6: Catalytic performance of Mg29Pd4 and Mg29Rh4 SAIMCs.
Fig. 7: Atomic cascade catalysis of the Mg29Pd1.3Rh2.7 SAIMC.

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The data that support the findings of this article are available from the corresponding authors 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 (22275121, 21931005, 22105122 and 52272265), the National Key R&D Program of China (2023YFA1506300 and 2023YFB3809101) and the Shanghai Municipal Science and Technology Major Project. We also thank the Fundamental Research Funds for the Central Universities (23X010301599, 24X010301678), the project of Jiangxi Academy of Sciences (2023YSTZX01), Liuchuang Program of Chongqing Municipality (cx2022038), Guangdong Provincial University Science and Technology Program (2023KTSCX123) from the Department of Education of Guangdong Province, and Shenzhen Fundamental Research funding (JCYJ20220530114616036). We also thank the User Experiment Assist System of the Shanghai Synchrotron Radiation Facility (SSRF).

Author information

Author notes

  1. These authors contributed equally: Xiaojun Lu, Jiazhen Wu, Xinyi He, Zichuang Li.

Authors and Affiliations

  1. Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, and Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, China

    Xiaojun Lu, Zichuang Li, Wenqian Li, Jie-Sheng Chen & Tian-Nan Ye

  2. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, China

    Jiazhen Wu & Yijia Liu

  3. MDX Research Center for Element Strategy, Institute of Integrated Research, Institute of Science Tokyo, Yokohama, Japan

    Xinyi He, Jiang Li, Toshio Kamiya & Hideo Hosono

  4. College of Materials Science and Engineering, National Engineering Research Center for Mg Alloys, National Key Laboratory of Advanced Casting Technologies, National Innovation Center for Industry-Education Integration of Energy Storage Technology, Chongqing University, Chongqing, China

    Yangfan Lu & Fusheng Pan

  5. Chongqing Institute of New Energy Storage Materials and Equipment, Chongqing, China

    Yangfan Lu & Fusheng Pan

  6. State Key Laboratory of Space Power-sources Technology, Shanghai Institute of Space Power-Sources, Shanghai, China

    Miao Xu

  7. School of Physical Science and Technology, Shanghai Tech University, Shanghai, China

    Yanpeng Qi & Qing Zhang

  8. ShanghaiTech Laboratory for Topological Physics, ShanghaiTech University, Shanghai, China

    Yanpeng Qi

  9. Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai, China

    Yanpeng Qi & Qing Zhang

  10. Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Meng Du

  11. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Meng Du

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  1. Xiaojun Lu
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Contributions

T.-N.Y. conceived the idea and supervised the project. X.L., J.W., Y. Lu, W.L., J.L., M.X., Y. Liu, F.P. and T.-N.Y. performed the synthesis, characterization and catalytic measurements. X.H., Z.L. and T.K. conducted the model construction and DFT calculations. Y.Q. and Q.Z. helped with the STEM measurements. M.D. helped with the CO-DRIFT measurements. X.L., H.H., J.-S.C. and T.-N.Y. co-wrote the paper with input from all authors.

Corresponding authors

Correspondence to Jie-Sheng Chen or Tian-Nan Ye.

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Nature Catalysis thanks Romain Réocreux and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–59, Tables 1–19, Notes 1 and 2 and references.

Supplementary Video 1

In situ TEM images.

Supplementary Data 1

Compressed zip file containing the crystal structures of Mg29Pd4, Mg29Rh4, Mg29Ir4 and Mg29Pt4.

Supplementary Data 2

Compressed zip file containing the geometric configurations of the intermediates of C2H2 hydrogenation on Mg29Pd4.

Supplementary Data 3

Compressed zip file containing the geometric configurations of the intermediates of styrene hydroformylation on Mg29Rh4.

Supplementary Data 4

Compressed zip file containing the geometric configurations for the insertion of H adatoms at the α- and β-sites of the vinyl group of styrene on Mg29Rh4.

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Lu, X., Wu, J., He, X. et al. Ordered single active sites for cascade hydrogenation and hydroformylation reactions. Nat Catal 8, 536–547 (2025). https://doi.org/10.1038/s41929-025-01346-1

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