Abstract
Single-atom catalysts (SACs) are promising for hydrogen evolution due to their maximal atomic utilization and discrete energy levels. Modulating metal-support interactions is key to tailoring their activity and stability, yet achieving precise control and mechanistic insight remains challenging and controversial. Here, we construct a rhodium single-atom catalyst model system, with Rh atoms anchored on a series of MoSxSe2-x supports (RhSA-MoSxSe2-x, 0 ≤ x ≤ 2), enabling gradient modulation of metal-support frontier orbital interactions through systematic tuning the anion composition. The elevated lowest unoccupied molecular orbital (LUMO) of MoSxSe2-x support narrows the energy gap with the highest occupied molecular orbital (HOMO) of Rh atoms, strengthening metal-support orbital hybridization to enhance stability and further amending the LUMO of Rh atoms to optimize both the hydroxide and hydrogen adsorption for high activity. The apex RhSA-MoSSe catalyst, with optimal HOMO-LUMO hybridization, achieves favorable hydrogen evolution reaction activity and stability simultaneously. This work offers fundamental insights into the metal-support frontier orbital interaction in SACs and establishes a rational design framework for high activity and stability electrocatalysis.
Similar content being viewed by others
Acknowledgements
This work was financially supported by National Natural Science Foundation of China (52231008, 22369005, 52302236, W2521028, and 52301011), the Key Research and Development Program of Hainan Province (ZDYF2024GXJS006), International Science & Technology Cooperation Program of Hainan Province (GHYF2023007).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Source data
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Jia, R., Liu, Z., Wang, Y. et al. Frontier-orbital modulation of rhodium single-atom catalysts for enhanced hydrogen evolution. Nat Commun (2026). https://doi.org/10.1038/s41467-026-73161-6
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-73161-6
