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Morphology tuning of inorganic nanomaterials grown by precipitation through control of electrolytic dissociation and supersaturation

Abstract

The precise control of the morphology of inorganic materials during their synthesis is important yet challenging. Here we report that the morphology of a wide range of inorganic materials, grown by rapid precipitation from a metal cation solution, can be tuned during their crystallization from one- to three-dimensional (1D to 3D) structures without the need for capping agents or templates. This control is achieved by adjusting the balance between the electrolytic dissociation (α) of the reactants and the supersaturation (S) of the solutions. Low-α, weak electrolytes promoted the growth of anisotropic (1D and 2D) samples, with 1D materials favoured in particular at low S. In contrast, isotropic 3D polyhedral structures could only be prepared in the presence of strong electrolyte reactants (α ≈ 1) with low S. Using this strategy, a wide range of materials were prepared, including metal oxides, hydroxides, carbonates, molybdates, oxalates, phosphates, fluorides and iodate with a variety of morphologies.

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Fig. 1: Morphological evolution of typical materials with 1D, 2D and 3D nanostructures.
Fig. 2: TEM and SEM images of various materials produced by the versatile precipitation.
Fig. 3: Summary of the synergy between α and S for materials with different morphologies.
Fig. 4: The mechanism of the formation of 1D, 2D and 3D morphologies.

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Data availability

All data supporting the findings of this study are included in the article and its Supplementary Information, and are also available from the authors upon reasonable request.

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Acknowledgements

This work is financially supported by the Australian Research Council (ARC) (LP120200432, DE170100928, DP180101453 and DP140104062), the National Natural Science Foundation of China (nos 21835004, 41430644 and 21671131), MOST (2017YFA0206700 and 2016YFA0202500) and the Program for Changjiang Scholars and Innovation Research Team in University (no. IRT-17R71). We thank the UOW Electron Microscopy Centre for use of the facilities (LE0882813 and LE0237478). We also thank T. Silver for a critical reading of the manuscript and Y. Xu for her partial support in the synthesis of these materials.

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W.-H.L., Y.-X.W., and S.-L.C. conceived and designed the study. W.-H.L. performed the synthetic experiments. W.-H.L., Y.-X.W., Y.W., S.-L.C., J.-Z.W., M.W. and J.C. analysed the data for all the compounds. Y.-X.W. performed the initial experiments and tested the battery performance of certain materials. W.-H.L., Y.-X.W., Y.W., S.-L.C., M.W., J.-Z.W., J.C., S.-X.D. and H.-K.L. co-wrote the paper.

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Correspondence to Minghong Wu, Jia-Zhao Wang, Shu-Lei Chou or Jun Chen.

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Materials and Methods, Supplementary Figs. 1–34, Tables 1–4 and references.

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Lai, WH., Wang, YX., Wang, Y. et al. Morphology tuning of inorganic nanomaterials grown by precipitation through control of electrolytic dissociation and supersaturation. Nat. Chem. 11, 695–701 (2019). https://doi.org/10.1038/s41557-019-0298-6

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