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Peripheral-nitrogen effects on the Ru1 centre for highly efficient propane dehydrogenation

Nature Catalysis volume 5, pages 1145–1156 (2022)Cite this article

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A Publisher Correction to this article was published on 12 January 2023

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Abstract

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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Fig. 1: The synthesis and structural characterization of Ru1/NC.
Fig. 2: Coordination and electronic states of Ru in Ru1/NC.
Fig. 3: Catalytic performance for the PDH reaction.
Fig. 4: Stabilization of the Ru1 centre by coordination of N species for Ru1/NC.
Fig. 5: Theoretical investigation on the effects of peripheral nitrogen and the reaction pathway.

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Data availability

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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Acknowledgements

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.

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  1. These authors contributed equally: Yanliang Zhou, Fenfei Wei, Haifeng Qi.

Authors and Affiliations

  1. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, P. R. China

    Yanliang Zhou, Haifeng Qi, Yicong Chai, Liru Cao, Jian Lin, Xiaoyan Liu, Yanan Xing, Aiqin Wang, Xiaodong Wang & Tao Zhang

  2. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, P. R. China

    Fenfei Wei, Qiang Wan & Sen Lin

  3. University of Chinese Academy of Sciences, Beijing, P. R. China

    Yicong Chai, Liru Cao & Yanan Xing

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Contributions

Y.Z. performed the characterizations, catalytic tests and wrote the first draft of the paper. F.W. contributed to the DFT calculations and paper writing. H.Q. performed the synthesis and characterizations of catalyst. Y.C. and L.C. were responsible for catalytic tests. Q.W. helped with the DFT calculations and data analysis. X.L. and Y.X. contributed to XAS testing and data analysis. J.L., S.L., A.W. and X.W. conceived the idea, directed the project and contributed to writing the manuscript. T.Z. proposed the idea behind the research and supervised the project. All the authors discussed the results and commented on the manuscript.

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Correspondence to Jian Lin, Sen Lin, Aiqin Wang or Xiaodong Wang.

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Nature Catalysis thanks Yafei Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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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

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