Abstract
Atomic catalytic pairs (CPs) have shown great promise in driving multi-step catalytic transformations, yet the influence of spatial arrangement and coordination asymmetry on homonuclear CPs remain poorly understood. Herein, we construct atomically dispersed homonuclear Pt1-Pt1 CPs with asymmetric Pt1C3-Pt1O1C3 coordination anchored on reduced graphene oxide. By precisely tuning the spacing between the adjacent Pt1C3-Pt1O1C3 CPs to approximately 5.3 Å, the catalyst achieves an exceptional turnover frequency of 27,218 h-1 for transfer hydrogenation of azobenzene via ammonia-borane hydrolysis, surpassing benchmarking catalysts by more than an order of magnitude. The Pt1C3-Pt1O1C3 CPs separated by 5.3 Å can facilitate co-adsorption of sterically hindered intermediates and at the same time the asymmetric Pt1C3-Pt1O1C3 coordination enables facile hydrogen shuttling and barrier-suppressed hydrogenation. These synergistic effects enhance the overall azobenzene hydrogenation efficiency. Our findings uncover a fundamental spatial design principle for atomically precise homonuclear asymmetric CPs, offering new opportunities for sustainable and efficient fine chemical synthesis.
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The data that support the findings of this study are reported within the Article and its Supplementary Information and are available from the corresponding author upon request. Source data are provided with this paper.
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Acknowledgements
The work was supported by the Natural Science Foundation of China (22471218 to Z.-Q.R.; 22305184 and 22576162 to X.Z.L.; 22204111 to C.C.), National Defense Basic Scientific Research Program of China (JCKY2022607C007 to Y.Y. F.), Natural Science Foundation of Shaanxi Province (2023-JC-QN-0136 to X.Z.L.; 2025JC-YBMS-147 to Y.Y.F.), Shaanxi Fundamental Science Research Project for Chemistry & Biology (22JHQ002 Z.-Q.R.), the Program for Young Talents of Shaanxi Province (5113190023 to Z.-Q.R.), Natural Science Basic Research Program of Shaanxi (2024JC-ZDXM-08 to Z.-Q.R.), Natural Science Foundation of Zhejiang Province(LY24B010002 to Y.Y.F.), the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University (CX2024106 to W.Z.), the City University of Hong Kong startup fund (9020003 to B.L.), ITF-RTH- Global STEM Professorship (9446006 to B.L.) and JC STEM lab of Advanced CO2 Upcycling (9228005 to B.L.). Computations were performed using the NUS High Performance Computing (HPC) facilities and the National Supercomputing Centre (NSCC) in Singapore. We also thank Shibo Xi from the Institute of Chemical and Engineering Sciences, Singapore, for conducting and analyzing the XANES and EXAFS measurements.
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Y.Y.F., Z.-Q.R., N.G., X.Z.L., and B.L. conceived the research. X.Z.L., Y.Y.F., W.Z., and Z.L.X. carried out the synthesis and materials characterization and measurements. N.G. conducted the theoretical calculation. C.C. performed the HAADF-STEM measurement. X.Z. performed the EELS and 4D-STEM measurement and analysis. C.C.C., X.C.W., S.M.Z., Q.Y.L., D.D.L., S.Q.L., and Z.H.C. assisted in the synthesis and characterization of materials. X.Z.L., B.L., Y.Y.F., W.Z., N.G., Z.-Q.R., X.Z., and Z.L.X. wrote the manuscript. All authors discussed the results and commented on the manuscript.
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Fang, Y., Zhao, W., Xing, Z. et al. Asymmetric Pt1C3-Pt1O1C3 catalytic pairs for efficient transfer hydrogenation of azobenzene. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68759-9
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DOI: https://doi.org/10.1038/s41467-026-68759-9
