Abstract
Two-dimensional (2D) materials offer unique platforms for exploring electronic structures and catalytic applications. Nanoclusters, referred to as ‘superatoms’, can be directly connected to construct 2D nanostructure networks. Here eight kinds of 2D clusterphenes are prepared by assembling polyoxoniobate (PONb) clusters with transition or rare-earth metal ions through a facile wet-chemical synthesis at room temperature. Monolayer and few-layer PONb-clusterphenes with hexagonal structures are constructed by the direct bonding of C3v symmetric {Nb24O72} clusters. The PONb-clusterphenes show enhanced photocatalytic activity for benzyl alcohol oxidation, with a conversion rate ten times greater than that of the PONb cluster units. Theoretical investigations suggest this is because of a reduction in the reaction energy barrier due to the in-plane electron delocalization of the PONb-clusterphenes. The constructed 2D PONb-clusterphenes with hexagonal arrangement and unique electronic properties provide an atomically precise model with which to study the electronic structures of cluster-based assemblies in heterogeneous catalysis.
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Acknowledgements
This work was supported by the National Key R&D Program of China (2017YFA0700101), NSFC (22035004, 22241502), the XPLORER PRIZE and the China Postdoctoral Science Foundation (2022M721798).
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X.W. proposed and guided the project. Z.L. carried out the experiments and wrote the manuscript. Q.L. helped with the data analysis. Z.Z. and H.H. performed the calculations and analysed the results. X.W. and Q.L. helped with article revisions. All authors discussed the results and commented on the manuscript.
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Nature Synthesis thanks Carsten Streb, Shou-Tian Zheng 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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Supplementary Methods, Figs. 1–29 and Tables 1–5.
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Source Data Fig. 1
Data of height profile.
Source Data Fig. 2
Data of height profile, small-angle XRD, EXAFS and WT representation.
Source Data Fig. 4
Data of photocatalytic oxidation performance.
Source Data Fig. 5
Data of PDOS and conductivities.
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Li, Z., Zhang, Z., Hu, H. et al. Synthesis of two-dimensional polyoxoniobate-based clusterphenes with in-plane electron delocalization. Nat. Synth 2, 989–997 (2023). https://doi.org/10.1038/s44160-023-00305-7
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DOI: https://doi.org/10.1038/s44160-023-00305-7
