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Self-assembly of self-limiting monodisperse supraparticles from polydisperse nanoparticles

An Addendum to this article was published on 04 July 2012

This article has been updated

Abstract

Nanoparticles are known to self-assemble into larger structures through growth processes that typically occur continuously and depend on the uniformity of the individual nanoparticles. Here, we show that inorganic nanoparticles with non-uniform size distributions can spontaneously assemble into uniformly sized supraparticles with core–shell morphologies. This self-limiting growth process is governed by a balance between electrostatic repulsion and van der Waals attraction, which is aided by the broad polydispersity of the nanoparticles. The generic nature of the interactions creates flexibility in the composition, size and shape of the constituent nanoparticles, and leads to a large family of self-assembled structures, including hierarchically organized colloidal crystals.

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Figure 1: Electron microscopy and size distribution for supraparticles.
Figure 2: Intermediate stages of formation of supraparticle at 40 °C and detailed structural characterization of supraparticles.
Figure 3: Computer simulation results.
Figure 4: Analogous supraparticle assemblies from different materials.

Change history

  • 26 August 2011

    In the version of this Article originally published online, the full list of corresponding authors should have been Zhiyong Tang, Sharon C. Glotzer and Nicholas A. Kotov. This has been corrected in all versions of the Article.

  • 25 May 2012

    This Article has an addendum associated with it, for details see pdf.

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Acknowledgements

The authors thank the 100 Talents Program of the Chinese Academy of Sciences (Z.Y.T.), the National Natural Science Foundation for Distinguished Youth Scholars of China (21025310, Z.Y.T.) the National Research Fund for Fundamental Key Project no. 2009CB930401 (Z.Y.T.), National Natural Science Foundation of China (nos 91027011 and 20973047, Z.Y.T.). This material is based on work supported in part by the US Army Research Office (grant award no. W911NF-10-1-0518, S.C.G. and N.A.K.). S.C.G. and T.D.N. also acknowledge support from the James S. McDonnell Foundation 21st Century Science Research Award/Studying Complex Systems (award no. 220020139). This material is based on work supported by the Department of Defense, Office of the Director, Defense Research and Engineering (DOD/DDRE) (award no. N00244-09-1-0062, S.C.G.). Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the DOD/DDRE. Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE (contract no. DE-AC02-06CH11357). This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US DOE, Office of Science, Basic Energy Sciences (award no. DE-SC0000957, N.A.K.). The authors acknowledge support from the National Science Foundation (grant nos ECS-0601345, EFRI-BSBA 0938019, CBET 0933384 and CBET 0932823, N.A.K.). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The work is also partially supported by NIH 1R21CA121841-01A2 (NAK). S.C.G. is grateful to the University of Michigan Center for Advanced Computing for cluster support. The authors thank the University of Michigan's EMAL for its assistance with electron microscopy, and for NSF grant no. DMR-9871177 for funding for the JEOL 2010F analytical electron microscope used in this work. T.D.N. acknowledges support from the Vietnam Education Foundation. B.L. thanks the Argonne National Laboratory for use of the APS. Work at the Center for Nanoscale Materials was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE (contract no. DE-AC02-06CH-11357). P.P. acknowledges the support of a Willard Frank Libby postdoctoral fellowship from Argonne National Laboratory.

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Y.S.X., Z.Y.T., and N.A.K. conceived and designed the experiments. Y.S.X. performed the experiments. T.D.N., A.S. and S.C.G. designed and performed the computer simulations. B.L. and P.P. carried out SAXS measurements and corresponding data analysis. M.Y. contributed to the nanoparticle synthesis. Y.S.X., T.D.N., B.L., Z.Y.T., S.C.G. and N.A.K. analysed the data. Y.S.X., T.D.N., B.L., Z.Y.T., S.C.G. and N.A.K. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Zhiyong Tang, Sharon C. Glotzer or Nicholas A. Kotov.

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Xia, Y., Nguyen, T., Yang, M. et al. Self-assembly of self-limiting monodisperse supraparticles from polydisperse nanoparticles. Nature Nanotech 6, 580–587 (2011). https://doi.org/10.1038/nnano.2011.121

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