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Photo-induced synthesis of heteronuclear dual-atom catalysts

Nature Synthesis volume 3, pages 497–506 (2024)Cite this article

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Abstract

Dual-atom catalysts (DACs) have garnered significant interest due to their high atom utilization and synergistic catalysis. However, there is no universal synthetic method to precisely synthesize DACs. Here we propose a ‘navigation and positioning’ strategy for precise and scalable synthesis of a series of heteronuclear M1M2 DACs on polymeric carbon nitride (PCN). The primary nucleation sites, M1-PCN, were created by calcining urea and M1 metal salts. Upon light irradiation, the accumulated photoelectrons at the M1 site can navigate and position the second metal ion, M2, close to the M1 site, enabling the precise synthesis of heteronuclear DACs. Density functional theory calculations demonstrate that the hybridization of the Zn s orbital (M1) and Ru d orbital (M2) benefits the formation of stable ZnRu DAC on PCN. The ZnRu DACs were then investigated for photocatalytic hydrogen evolution. It was shown that the Ru site reduced H+ to H* and the Zn site acted as the H* desorption site, thus synergistically boosting activity.

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Fig. 1: The strategy for precise synthesis of heteronuclear DACs.
Fig. 2: Structure characterization of ZnRu-PCN.
Fig. 3: Structure characterization of M1M2-PCN.
Fig. 4: EELS characterization for M1M2-PCN.
Fig. 5: XANES patterns of ZnRu-PCN.
Fig. 6: Theoretical calculations of adsorption energies and electron density distribution.
Fig. 7: Photocatalytic H2 evolution performance.

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Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2022YFA1502902 to T.-B.L., 2022YFA1502902 to J.Z.), National Natural Science Foundation of China (21931007 to T.-B.L., 92161103 and 22071180 to Z.-M.Z.) and the Natural Science Foundation of Tianjin City of China (18JCJQJC47700 to Z.-M.Z.). We gratefully acknowledge BL14W1 beamline of Shanghai Synchrotron Radiation Facility, Shanghai, China, for providing the beam time, and the Electron Microscopy Center of the University of Chinese Academy Science for conducting the EELS measurements.

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Author notes

  1. These authors contributed equally: Qiu-Ping Zhao, Wen-Xiong Shi, Jiangwei Zhang.

Authors and Affiliations

  1. Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China

    Qiu-Ping Zhao, Wen-Xiong Shi, Zhi-Yuan Tian, Zhi-Ming Zhang, Peng Zhang, Ye Wang & Tong-Bu Lu

  2. Science Center of Energy Material and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, China

    Jiangwei Zhang

  3. School of Chemical Engineering, the University of Adelaide, Adelaide, South Australia, Australia

    Shi-Zhang Qiao

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  1. Qiu-Ping Zhao
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Contributions

Z.-M.Z. and T.-B.L. conceived and designed this project. Q.-P.Z., Z.-Y.T., P.Z. and Y.W. performed the experiments. W.-X.S. carried out the density functional theory calculation. J.Z. carried out and analysed the X-ray absorption fine structure spectroscopy. Q.-P.Z., Z.-M.Z. and T.-B.L. analysed the data. Q.-P.Z., W.-X.S., Z.-M.Z., S.-Z.Q. and T.-B.L. wrote and revised the article.

Corresponding authors

Correspondence to Zhi-Ming Zhang or Tong-Bu Lu.

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Nature Synthesis thanks Mihaela Florea, Yujing Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Zhao, QP., Shi, WX., Zhang, J. et al. Photo-induced synthesis of heteronuclear dual-atom catalysts. Nat. Synth 3, 497–506 (2024). https://doi.org/10.1038/s44160-024-00486-9

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