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Synergizing metal–support interactions and spatial confinement boosts dynamics of atomic nickel for hydrogenations

Nature Nanotechnology volume 16, pages 1141–1149 (2021)Cite this article

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Abstract

Atomically dispersed metal catalysts maximize atom efficiency and display unique catalytic properties compared with regular metal nanoparticles. However, achieving high reactivity while preserving high stability at appreciable loadings remains challenging. Here we solve the challenge by synergizing metal–support interactions and spatial confinement, which enables the fabrication of highly loaded atomic nickel (3.1 wt%) along with dense atomic copper grippers (8.1 wt%) on a graphitic carbon nitride support. For the semi-hydrogenation of acetylene in excess ethylene, the fabricated catalyst shows extraordinary catalytic performance in terms of activity, selectivity and stability—far superior to supported atomic nickel alone in the absence of a synergizing effect. Comprehensive characterization and theoretical calculations reveal that the active nickel site confined in two stable hydroxylated copper grippers dynamically changes by breaking the interfacial nickel–support bonds on reactant adsorption and making these bonds on product desorption. Such a dynamic effect confers high catalytic performance, providing an avenue to rationally design efficient, stable and highly loaded, yet atomically dispersed, catalysts.

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Fig. 1: Catalytic performance of Ni–Cu pincer complex catalyst.
Fig. 2: Structural characterization.
Fig. 3: In situ DRIFTS investigation of C2H2 hydrogenation.
Fig. 4: Theoretical insights into stability and hydrogenation mechanism.

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Source data are provided with this paper. The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0208603 and 2017YFA0402800); the National Natural Science Foundation of China (22025205, 21673215, 91645202, 91845203, 11621063 and 91945302); the Frontier Science Key Project of the Chinese Academy of Sciences (CAS) (QYZDJ-SSW-SLH054); the Dalian National Laboratory for Clean Energy (DNL) Cooperation Fund (DNL201907 and DNL201920); Beijing Outstanding Young Scientist Program (BJJWZYJH01201914430039); Key Research Program of Frontier Sciences, CAS (QYZDB-SSW-JSC019); Bureau of Frontier of Sciences and Education, CAS (ZDBS-LY-SLH003); the Fundamental Research Funds for the Central Universities (WK2060030029 and WK3430000005); Users with Excellence Program of Hefei Science Center, CAS (2019HSC-UE016); and the Max Planck Partner Group. We also gratefully thank the BL14W1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF), and the BL10B and BL04B beamlines at the National Synchrotron Radiation Laboratory (NSRL), China, and the Supercomputing Center, University of Science and Technology of China.

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  1. These authors contributed equally: Jian Gu, Minzhen Jian, Li Huang.

Authors and Affiliations

  1. Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, China

    Jian Gu, Minzhen Jian, Yue Lin, Xinyu Liu, Leilei Wang, Xianxian Shi, Xiaohui Huang, Lina Cao, Si Chen, Wei-Xue Li & Junling Lu

  2. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, China

    Li Huang, Zhihu Sun, Yang Pan, Jiuzhong Yang, Wu Wen, Xusheng Zheng, Haibin Pan, Junfa Zhu & Shiqiang Wei

  3. School of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, China

    Aowen Li & Wu Zhou

  4. CAS Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, China

    Wu Zhou

  5. Experimental Center of Engineering and Materials Science, University of Science and Technology of China, Hefei, China

    Hui-Juan Wang

  6. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Wei-Xue Li & Junling Lu

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Contributions

J.L. designed the experiments and W.-X.L. designed the DFT calculations. J.G. performed the catalytic performance evaluation. S.W., L.H., Z.S., L.C. and S.C. performed the XAFS measurements. M.J. performed the DFT calculations. Y.P., J.Y. and W.W. performed the SVUV-PIMS measurements. Y.L. conducted the HAADF-STEM measurements. A.L. and W.Z. performed the atomic-resolution EELS measurements. H.-J.W., X.L. and L.W. performed the TEM measurements. X.S. and X.H. performed the TGA measurements. X.Z., H.P. and J.Z. performed the XPS measurements. J.L. and W.-X.L. co-wrote the manuscript, and all the authors contributed to the overall scientific interpretation and edited the manuscript. We gratefully thank P. C. Stair for his insightful suggestions and manuscript polishing.

Corresponding authors

Correspondence to Shiqiang Wei, Wei-Xue Li or Junling Lu.

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Peer review information Nature Nanotechnology thanks Dehui Deng and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–46 and Tables 1–12.

Supplementary Data 1

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Supplementary Video 1

Hydrogenation of C2H2 on Ni1Cu2.

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Gu, J., Jian, M., Huang, L. et al. Synergizing metal–support interactions and spatial confinement boosts dynamics of atomic nickel for hydrogenations. Nat. Nanotechnol. 16, 1141–1149 (2021). https://doi.org/10.1038/s41565-021-00951-y

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