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Synthesis of orthogonally assembled 3D cross-stacked metal oxide semiconducting nanowires

Nature Materials volume 19, pages 203–211 (2020)Cite this article

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Abstract

Assemblies of metal oxide nanowires in 3D stacks can enable the realization of nanodevices with tailored conductivity, porous structure and a high surface area. Current fabrication methods require complicated multistep procedures that involve the initial preparation of nanowires followed by manual assembly or transfer printing, and thus lack synthesis flexibility and controllability. Here we report a general synthetic orthogonal assembly approach to controllably construct 3D multilayer-crossed metal oxide nanowire arrays. Taking tungsten oxide semiconducting nanowires as an example, we show the spontaneous orthogonal packing of composite nanorods of poly(ethylene oxide)-block-polystyrene and silicotungstic acid; the following calcination gives rise to 3D cross-stacked nanowire arrays of Si-doped metastable ε-phase WO3. This nanowire stack framework was also tested as a gas detector for the selective sensing of acetone. By using other polyoxometallates, this fabrication method for woodpile-like 3D nanostructures can also be generalized to different doped metal oxide nanowires, which provides a way to manipulate their physical properties for various applications.

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Fig. 1: Co-assembly of PEO-b-PS and H4SiW12O40.
Fig. 2: Elemental and structural analysis of the MC-WO3-NWAs.
Fig. 3: Different 3D cross-stacked nanowire structures by using other POMs as inorganic precursors.
Fig. 4: Schematic illustration and theoretical simulation of the formation process of the MC-WO3-NWAs.
Fig. 5: DFT calculation and EXAFS analysis of MC-WO3-NWAs.
Fig. 6: Gas-sensing performances of the MC-WO3-NWAs.

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Data availability

The datasets generated and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant nos 51422202, 21673048 and 21875044), Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (17JC1400100) and Youth Top-notch Talent Support Program of China. The authors thank G. Zhou and Z. Shan for assistance in TEM characterization.

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  1. These authors contributed equally: Yuan Ren, Yidong Zou.

Authors and Affiliations

  1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers, and iChEM, Fudan University, Shanghai, China

    Yuan Ren, Yidong Zou, Xinran Zhou, Junhao Ma, Dongyuan Zhao & Yonghui Deng

  2. College of Environmental Science and Engineering, North China Electric Power University, Beijing, China

    Yang Liu & Yuejie Ai

  3. School of Chemical Science and Engineering, Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University, Shanghai, China

    Guangfeng Wei

  4. Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research in Singapore (A*STAR), Jurong Island, Singapore

    Shibo Xi

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Contributions

Y.R., Y.Z. and Y.D. conceived the project and designed the experiments. Y.R., Y.Z., X.Z., J.M., D.Z., G.W. and Y.D. were primarily responsible for the data collection and analysis. Y.L. and Y.A. analysed the structures with DFT calculations. S.X. and Y.Z. analysed the EXAFS data. Y.R., Y.Z. and Y.D. prepared the figures and wrote the main manuscript text. All the authors contributed to the discussions and manuscript preparation.

Corresponding author

Correspondence to Yonghui Deng.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–35, Notes 1–7 and Tables 1–6.

Supplementary Video 1

In situ TEM observation was conducted to study the real time structure transformation of the as-casted PEO-b-PS/H4SiW hybrid film into 3D crossed multilayer Si-doped WO3 nanowires by heating the hybrid film under TEM and in situ recording images of the sample.

Supplementary Video 2

The animation about the formation mechanism of 3D crossed multilayer Si-doped WO3 nanowires by the solvent evaporation induced co-assembly of PEO-b-PS copolymers and H4SiW, followed with structure transformation induced by thermal treatment.

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Ren, Y., Zou, Y., Liu, Y. et al. Synthesis of orthogonally assembled 3D cross-stacked metal oxide semiconducting nanowires. Nat. Mater. 19, 203–211 (2020). https://doi.org/10.1038/s41563-019-0542-x

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