Abstract
Controlling the selectivity of chemical products on small Co nanoparticles is crucial in many catalytic applications. Reaction-driven structural changes offer an alternative methodology to regulate their properties. Herein, carbon-induced surface restructuring occurs on a 2Co/MnOₓ catalyst (cobalt nanoclusters with 2% mass loading on manganese oxide) during thermal CO2 hydrogenation, driven by the formation of bridging Co-C-O-Mn interfacial sites. This leads to a shift in selectivity from methane to CO, with a remarkable enhancement of the CO/CH4 product ratio from 0.89 to 13.4. Such a Co/MnOx system has unique interfacial properties, including strong carbonophilic and oxophilic characteristics. It chemisorbs reaction-derived CO and facilitates C-O bond breaking, promoting rapid CO dissociation and subsequent carbon coverage on Co nanoclusters. This restructuring of Co nanoclusters suppresses the hydrogenation of CO intermediates to methane. This effect is unique to 2Co/MnOₓ and absent at higher/lower Co loadings or other oxide supports. This insight shows how structural evolution during catalysis enables precise surface engineering, overcoming the structure-sensitivity limits of Co nanoclusters.
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Data generated and analyzed in this study are included in the manuscript, Supplementary Information. All data are available from the corresponding author upon request. Source data are provided with this paper.
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Acknowledgements
This work was financially supported by the National Key Research and Development Program of China (2024YFB4006600 to Y.L.), the National Natural Science Foundation of China (22502018 to H.K., 22472168 to Y.L., and U23A20132 to R.Z.), Sichuan Science and Technology Program, China (2025ZNSFSC0901 to H.K.), Natural Science Foundation of Liaoning Province (2024-MSBA-57 to Y.L.), Dalian Science and Technology Innovation Fund (2024JJ12RC034 to Y.L.), Dalian Institute of Chemical Physics (DICP I202421 to Y.L.), the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy (E411030705 to Y.L.) and the Postdoctoral Science Foundation of China (2024M762752 to L.L.). We also thank in-situ synchrotron XPS experiments supporting from BL02B beamline (31124.02.SSRF.BL02B01) at the Shanghai Synchrotron Radiation Facility (SSRF) in Shanghai, China.
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H.K. conceived and performed the experiments, analysed the data and wrote the paper. R.C. and R.Z. carried out the DFT calculations and wrote the related section. Y.Z., X.W., L.L., W.C., S.P., and G.C. analysed the data and provided helpful discussions. R.Z., S.P., and G.C. revised the paper. Y.L. conceived and directed the research, analysed the data, and wrote the paper. All authors contributed to the discussion and manuscript preparation.
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Kang, H., Cao, R., Zhang, Y. et al. Reaction-induced modification of Co nanoclusters driven by Co-Mn interfacial sites to control selectivity in CO2 hydrogenation. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70328-z
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DOI: https://doi.org/10.1038/s41467-026-70328-z
