Abstract
Single-atom catalysts have found widespread application in selective hydrogenation reactions partially due to their well-defined active site structures, which ensure exceptional chemical selectivity. However, the limited binding sites on single-atom catalysts hinder their application in hydrogenating larger multidentate substrates (e.g., benzonitrile). In this work, we introduced a heteronuclear Rh-Co dual-atom catalyst stabilized on the defective graphene supports (Rh1Co1/ND@G), which resolves the activity-selectivity trade-off in nitrile hydrogenation reaction. The Rh1 site primarily activates H2, whereas the Co1 site synergistically optimizes the adsorption of benzonitrile. The cooperative interaction between Rh-Co dual sites enhances the activation of the C ≡ N bond, significantly reducing the apparent activation energy compared to Rh SACs. The Rh1Co1/ND@G catalyst achieves exceptional performance under mild reaction conditions, delivering a TOF of 4068 h-1 with >98% dibenzylamine selectivity, surpassing all previous reported heterogeneous catalysts. Remarkably, the Rh1Co1/ND@G catalyst still maintains robust catalytic performance even after 12 cycles. This work not only presents a breakthrough in dual-atom catalyst design for nitrile hydrogenation, but also opens an avenue for developing high-performance industrial hydrogenation catalysts.
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Acknowledgements
This work was supported by the National Key R&D Program of China (2022YFA1504500, 2021YFA1502802), the National Natural Science Foundation of China (U21B2092, 22202213, 22072162, 22203012, and 22402210), and the International Partnership Program of the Chinese Academy of Sciences (172GJHZ2022028MI). The XAS experiments were conducted in the Beijing Synchrotron Radiation Facility (BSRF) and the Shanghai Synchrotron Radiation Facility (SSRF).
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H.L. and D.M. conceived the research. J.C. conducted material synthesis and performed catalytic performance tests. J.C. conducted the X-ray absorption fine structure spectroscopic measurements and analyzed the data. Q.C. and G.S. performed the DFT calculations. X.C. contributed to the aberration-corrected high-angle annular dark-field scanning transmission electron microscopy. M.P., J.D., B.S., and Y.W. performed some of the experiments. The manuscript was primarily written by J.C., H.L., and D.M. J.C., H.C., X.C., Y.W., G.S., D.M., and H.L. contributed to discussions and manuscript review.
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Chen, J., Chen, H., Cai, X. et al. Dual-atom Rh-Co catalysts for synergistically boosting nitrile hydrogenation. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69778-2
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DOI: https://doi.org/10.1038/s41467-026-69778-2
