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A precursor-valence-gating strategy for controllable synthesis of metal nanocrystal catalysts with varied periodicities

Nature Synthesis (2026)Cite this article

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Abstract

Transition-metal nanocrystal (TMN) catalysts are essential for energy conversion and storage, but their facile and controllable synthesis remains challenging. Here we report a general precursor-valence-gating strategy to prepare various monocrystalline and polycrystalline TMNs (MC/PC-TMNs, M = Co, Ni or Cu). Unlike complex regulation of traditional experimental parameters, we discover that the solid-state precursor’s oxidation state—an intrinsic parameter—governs the nucleation rate and ultimately dictates atomic crystallization periodicity. Consequently, the controllable preparation of MC/PC-TMNs was readily achieved through designing the valence diversity of the corresponding precursors. Furthermore, taking MC/PC-Co catalysts as examples, we investigate the correlation between atomic arrangements and catalytic dynamics and reveal that the PC-Co catalyst with the lower-coordination environment, compared with MC-Co, substantially promotes the conversion of reaction intermediates in the hydrazine oxidation reaction. As a result, PC-Co exhibits an ultralow Tafel slope of 14 mV dec−1, and an assembled hydrazine oxidation reaction-based battery demonstrates excellent stability for 1,200 h at 10 mA cm−2. This work paves the way for controllable synthesis of MC/PC-TMNs and fundamentally advances the understanding of precursor-guided crystal growth kinetics.

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Fig. 1: Synthesis and structural characterizations of MC/PC-TMNs.
Fig. 2: Electrocatalytic performance for HzOR in 1 M KOH and 0.1 M N2H4 electrolytes.
Fig. 3: Catalytic mechanism for HzOR.
Fig. 4: Electrochemical performance and economic analyses of H-ZABs.

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All data that support the findings of this study are available in the article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant no. 92572103, G.Z.), Guangdong Basic and Applied Basic Research Foundation (2023B1515120099, G.Z.), Guangdong Innovative and Entrepreneurial Research Team Program (2021ZT09L197, G.Z.), and Shenzhen Science and Technology Program (KQTD20210811090112002, G.Z.). This work made use of the TEM facilities at the Institute of Materials Research, Tsinghua Shenzhen International Graduate School (Tsinghua SIGS).

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  1. These authors contributed equally: Zhiyang Zheng, Feng-Yi Zheng.

Authors and Affiliations

  1. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, People’s Republic of China

    Zhiyang Zheng, Feng-Yi Zheng, Yifei Zhu, Bosi Huang, Tongtong Li, Boran Wang, Xiongwei Zhong, Zhexuan Liu, Guanjun Ji, Qingjin Fu & Guangmin Zhou

  2. Green Chemical New Materials Engineering Research Center of Guangxi Colleges and Universities, Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, People’s Republic of China

    Boran Wang

  3. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, People’s Republic of China

    Xiongwei Zhong

Authors
  1. Zhiyang Zheng
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Contributions

G.Z. and Z.Z. conceived the project. Z.Z., T.L., B.W. and G.J. synthesized the materials. Z.Z. and F.-Y.Z. carried out the materials characterization and analysed the data. Z.Z. conducted the TEAs. Y.Z. and B.H. conducted theoretical simulations. X.Z., Z.L. and Q.F. provided experimental insights. All authors participated in paper preparation.

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Correspondence to Guangmin Zhou.

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Nature Synthesis thanks Hanfeng Liang, Duy Thanh Tran and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Zheng, Z., Zheng, FY., Zhu, Y. et al. A precursor-valence-gating strategy for controllable synthesis of metal nanocrystal catalysts with varied periodicities. Nat. Synth (2026). https://doi.org/10.1038/s44160-026-01022-7

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