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Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

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Abstract

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.

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Acknowledgements

This project was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Contract No. DE-AC02-05-CH11231 within the in-situ TEM (KC22ZH) program. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. We acknowledge Gatan Inc. for the advanced K2 IS camera and Dr. Ming Pan and Dr. Cory Czarnik for their help with part of experimental set up in this work. W. J. Z. acknowledges the support from Tianjin University Graduate School International Academic Exchange Fund. M. R. H. was funded by KAUST project under H. M. Z. at UC Berkeley.

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Authors and Affiliations

  1. Institute of New-Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China

    Wenjing Zheng & Xiwen Du

  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Wenjing Zheng, Matthew R. Hauwiller, Wen-I Liang, Mark Asta, A. Paul Alivisatos & Haimei Zheng

  3. Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA

    Matthew R. Hauwiller & A. Paul Alivisatos

  4. Department of Materials Science and Engineering, “National Chiao Tung University”, Hsinchu, 30010, Taiwan, China

    Wen-I Liang & Ying-Hao Chu

  5. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Colin Ophus, Peter Ercius & Emory M. Chan

  6. Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, CA, 94720, USA

    Mark Asta & Haimei Zheng

  7. Kavli Energy NanoScience Institute, University of California-Berkeley and Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    A. Paul Alivisatos

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  1. Wenjing Zheng
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Zheng, W., Hauwiller, M.R., Liang, WI. et al. Real time imaging of two-dimensional iron oxide spherulite nanostructure formation. Nano Res. 12, 2889–2893 (2019). https://doi.org/10.1007/s12274-019-2531-4

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