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Encapsulating highly catalytically active metal nanoclusters inside porous organic cages

Abstract

The creation of metal nanoclusters with dimensions ranging from subnanometre to ~2 nm for heterogeneous catalysis has received substantial attention. However, synthesizing these structures while retaining surface activity and avoiding aggregation is challenging. Here, we report a reverse double-solvents approach that enables encapsulation of highly catalytically active Pd nanoclusters inside the newly formed discrete organic molecular cage, RCC3. By encapsulating within the open cavities of soluble RCC3 cages, the obtained Pd nanocluster cores are produced with precisely controlled size (~0.72 nm) and show high solubility, excellent dispersibility and accessibility in solution, presenting significantly enhanced catalytic activities towards various liquid-phase catalytic reactions. Moreover, owing to the effective confinement of cage cavities, the as-prepared Pd nanoclusters possess excellent stability and durability. The strategy of encapsulation of metal nanoclusters within soluble porous organic cages is promising for developing stable and active catalysts.

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Fig. 1: Synthesis and characterization of the RCC3-cage-encapsulated Pd nanoclusters.
Fig. 2: Morphological characterization of RCC3-cage-encapsulated Pd nanoclusters.
Fig. 3: Application of RCC3-cage-encapsulated Pd nanoclusters for catalytic reactions.

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Acknowledgements

The authors thank the Ministry of Economy, Trade and Industry, National Institute of Advanced Industrial Science and Technology and Kobe University for financial support. X.Y. is grateful to China Scholarship Council and the Ministry of Education, Culture, Sports, Science and Technology, Japan for a PhD scholarship.

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All authors contributed extensively to this work. X.Y. conducted the experiments and performed the characterizations. J.-K.S. helped to prepare the organic cages and analysed the experimental results. M.K. recorded the transmission electron microscopy data. H.P. helped to perform the characterizations. Q.X. designed the work. X.Y. and Q.X. wrote the manuscript with input from the other authors.

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Correspondence to Qiang Xu.

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Supplementary Methods, Supplementary Figures 1–40, Supplementary Table 1 and Supplementary References

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Yang, X., Sun, JK., Kitta, M. et al. Encapsulating highly catalytically active metal nanoclusters inside porous organic cages. Nat Catal 1, 214–220 (2018). https://doi.org/10.1038/s41929-018-0030-8

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