Single-atom catalysts with uniform metal active sites show potential for selectivity control. However, their application to high-temperature propane dehydrogenation remains challenging. Here we develop a highly stable and efficient single-atom catalyst for propane dehydrogenation that is based on Ru single atoms on nitrogen-doped carbon (Ru1/NC). The turnover frequency of Ru1/NC is at least three times higher than that of nanoparticle counterparts, resulting in propylene selectivity of around 92% with a lower deactivation rate at 560 °C. Experimental and density functional theory studies reveal the important role of peripheral N species around the Ru1 centre. The inner-shell N stabilizes the atomically dispersed Ru to inhibit structure-sensitive propane cracking, while the outer-shell N promotes electron accumulation at the Ru1 centre, inducing a significant charge repulsion between Ru1 and propylene to facilitate its desorption. The combined functions of inner-shell and outer-shell N species at single-atom Ru sites contribute to the high efficiency of Ru1/NC.
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The original data about experiments and DFT calculations in the manuscript are available at https://github.com/FenfeiWei118/RuNC-Data. The data that support the findings of this study are included in the article (and its Supplementary Information) or are available from the corresponding author on reasonable request.
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This work was supported by the National Natural Science Foundation of China (grant nos. 22022814, J.L.; 21878283, J.L.; 22178337, X.W.; 22132006, A.W.; 22172159, A.W.; 22108037, Y.Z.; 21973013, S.L.), the Strategic Priority Research Program of the Chinese Academy of Sciences (CAS; grant no. XDB17020100, T.Z.), National Key R&D Program of China (grant no. 2016YFA0202-801, T.Z. and X.W.), the Youth Innovation Promotion Association CAS (grant no. Y2021057, J.L.), Dalian Science Foundation for Distinguished Young Scholars (grant no. 2021RJ10, J.L.), CAS Project for Young Scientists in Basic Research (grant no. YSBR-022, A.W.), the National Natural Science Foundation of Fujian Province, China (grant no. 2020J02025, S.L.) and the ‘Chuying Program’ for the Top Young Talents of Fujian Province (S.L.). Computations were performed at the Hefei Advanced Computing Centre and Supercomputing Centre of Fujian.
The authors declare no competing interests.
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Zhou, Y., Wei, F., Qi, H. et al. Peripheral-nitrogen effects on the Ru1 centre for highly efficient propane dehydrogenation. Nat Catal 5, 1145–1156 (2022). https://doi.org/10.1038/s41929-022-00885-1