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A total-synthesis framework for the construction of high-order colloidal hybrid nanoparticles

Nature Chemistry volume 4, pages 37–44 (2012)Cite this article

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Abstract

Colloidal hybrid nanoparticles contain multiple nanoscale domains fused together by solid-state interfaces. They represent an emerging class of multifunctional lab-on-a-particle architectures that underpin future advances in solar energy conversion, fuel-cell catalysis, medical imaging and therapy, and electronics. The complexity of these ‘artificial molecules’ is limited ultimately by the lack of a mechanism-driven design framework. Here, we show that known chemical reactions can be applied in a predictable and stepwise manner to build complex hybrid nanoparticle architectures that include M–Pt–Fe3O4 (M = Au, Ag, Ni, Pd) heterotrimers, MxS–Au–Pt–Fe3O4 (M = Pb, Cu) heterotetramers and higher-order oligomers based on the heterotrimeric Au–Pt–Fe3O4 building block. This synthetic framework conceptually mimics the total-synthesis approach used by chemists to construct complex organic molecules. The reaction toolkit applies solid-state nanoparticle analogues of chemoselective reactions, regiospecificity, coupling reactions and molecular substituent effects to the construction of exceptionally complex hybrid nanoparticle oligomers.

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Figure 1: Stepwise construction of M–Pt–Fe3O4 heterotrimers (M = Ag, Au, Ni, Pd).
Figure 2: Characterization data for M–Pt–Fe3O4 heterotrimers (M = Au, Ag, Ni, Pd).
Figure 3: Chemoselective nucleation in the Ag–Pt–Fe3O4 heterotrimer system.
Figure 4: Stepwise construction of MxSy–Au–Pt–Fe3O4 heterotetramers (M = Cu, Pb).
Figure 5: Higher-order hetero-oligomers based on the Au–Pt–Fe3O4 heterotrimer building block.

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Acknowledgements

This work was supported primarily by the US National Science Foundation (NSF) (CHE-0845258), but with additional partial support to M.R.B. by the Penn State Materials Research Science and Engineering Center (DMR-0820404). Electron microscopy was performed at the Electron Microscopy Facility at the Huck Institutes of the Life Sciences and at the Materials Characterization Facility of the Penn State Materials Research Institute. The authors thank J. Kulik for assistance with collecting the STEM data. The authors also thank V. Bojan for acquisition and interpretation of XPS data and H. Gong for ICP-AES measurements.

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  1. Department of Chemistry and Materials Research Institute, The Pennsylvania State University, University Park, 16802, Pennsylvania, USA

    Matthew R. Buck, James F. Bondi & Raymond E. Schaak

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  1. Matthew R. Buck
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Contributions

M.R.B. carried out all of the synthetic work and characterization by XRD, TEM and UV-vis. J.F.B. carried out and analysed the HRTEM, STEM, SAED and EDS element-mapping work. R.E.S. conceived and directed the project. M.R.B. and R.E.S. prepared the manuscript.

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Correspondence to Raymond E. Schaak.

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Buck, M., Bondi, J. & Schaak, R. A total-synthesis framework for the construction of high-order colloidal hybrid nanoparticles. Nature Chem 4, 37–44 (2012). https://doi.org/10.1038/nchem.1195

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