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Metal–support frontier orbital interactions in single-atom catalysis

Nature volume 640, pages 668–675 (2025)Cite this article

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A Publisher Correction to this article was published on 04 June 2025

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Abstract

Single-atom catalysts (SACs) with maximized metal use and discrete energy levels hold promise for broad applications in heterogeneous catalysis, energy conversion, environmental science and biomedicine1,2,3,4,5,6,7. The activity and stability of SACs are governed by the pair of metal–adsorbate and metal–support interactions8,9,10. However, the understanding of these interactions with their catalytic performance in nature is challenging. Correlations of activity with the charge state of metal atoms have frequently reached controversial conclusions11,12,13,14,15. Here we report that the activity of palladium (Pd1) SACs exhibits a linear scaling relationship with the positions of the lowest unoccupied molecular orbital (LUMO) of oxide supports across 14 types of semiconductor. Elevation of the LUMO position by reducing the support particle size to a few nanometres boosts a record high activity along with excellent stability in the semi-hydrogenation of acetylene. We show that the elevated LUMO of support reduces its energy gap with the highest occupied molecular orbital (HOMO) of Pd1 atoms, which promotes Pd1–support orbital hybridizations for high stability and further amends the LUMO of anchored Pd1 atoms to enhance Pd1–adsorbate interactions for high activity. These findings are consistent with the frontier molecular orbital theory and provide a general descriptor for the rational selection of metal–support pairs with predictable activity.

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Fig. 1: Variation of EMSIs in Pd1/MOx SACs on support particle size.
Fig. 2: Catalytic performance of Pd1/MOx catalysts.
Fig. 3: Chemical properties of Pd1/MOx SACs.
Fig. 4: Theoretical insight into orbital coupling on activity in Pd1/ZnO SACs.

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All data generated during this study are included in this published article (and Supplementary Information) or can be obtained from the authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1502802), the Chinese Academy of Sciences (XDA29040800), the National Science Fund for Distinguished Young Scholars (22025205 and 22225301), the National Science Fund of China (22221003, 22073087, 22302200, 22321001 and 22472164), the NSFC Center for Single-Atom Catalysis (22388102), the Fundamental Research Funds for the Central Universities (WK2060000038 and 20720220009), the Strategic Priority Research Program of the CAS (XDB0450101), K. C. Wong Education (GJTD-2020-15), the CAS Project for Young Scientists in Basic Research (YSBR-022 and YSBR-004), the Dalian Institute of Chemical Physics (DICP I202107), the Innovation Program for Quantum Science and Technology (2021ZD0303302) and the National Science Foundation Graduate Research Fellowship under grant no. 2234662. Z.F. also acknowledges the support of the China Experience Fund from Oregon State University. XAS experiments were performed at the 10-ID of the Materials Research Collaborative Access Team, which is supported by the US Department of Energy (DOE) and the Materials Research Collaborative Access Team member institutions. This research used the resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We also thank J. Yang, J. Liu and L. Feng for their comments and S. Han, L. Xu and L. Cai for providing catalytic support.

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Author notes

  1. These authors contributed equally: Xianxian Shi, Zhilin Wen, Qingqing Gu

Authors and Affiliations

  1. State Key Laboratory of Precision and Intelligent Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Xianxian Shi, Long Jiao, Hai-Long Jiang, Haifeng Lv, Hengwei Wang, Jiani Ding, Yue Lin, Mei Sun, Xiaojun Wu & Junling Lu

  2. School of Chemistry and Materials Science, iChem, University of Science and Technology of China, Hefei, China

    Xianxian Shi, Zhilin Wen, Long Jiao, Hai-Long Jiang, Jiani Ding, Si Chen, Wenlong Xu, Yin Li, Xiaojun Wu & Junling Lu

  3. College of Aerospace Science and Engineering, National University of Defense Technology, Changsha, China

    Xianxian Shi

  4. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Qingqing Gu, Xiaoyan Xu, Pengfei Du, Bing Yang & Tao Zhang

  5. School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis, OR, USA

    Mason P. Lyons & Zhenxing Feng

  6. School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, OR, USA

    Alvin Chang

  7. Hefei National Laboratory, University of Science and Technology of China, Hefei, China

    Xiaojun Wu

  8. Suzhou Laboratory, Suzhou, China

    Junling Lu

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Contributions

J.L. conceived the project and designed the experiments; X.S., H.W., J.D., S.C., W.X. and Y. Li performed the catalytic performance evaluation; X.W., H.L. and Z.W. performed the theoretical calculations; Q.G., X.X., Y. Lin, P.D., T.Z. and B.Y. carried out the STEM and XPS measurements; M.S. performed the ICP measurements; X.S., L.J. and H.-L.J. conducted the Mott–Schottky curve measurements; M.P.L., A.C. and Z.F. carried out the XAS measurements; J.L., X.S., Q.G., B.Y., X.W. and Z.W. wrote the paper. All the authors contributed to the overall scientific interpretation and edited the paper.

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Correspondence to Bing Yang, Xiaojun Wu or Junling Lu.

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Shi, X., Wen, Z., Gu, Q. et al. Metal–support frontier orbital interactions in single-atom catalysis. Nature 640, 668–675 (2025). https://doi.org/10.1038/s41586-025-08747-z

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