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Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis

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Abstract

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.

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Figure 1: Plasmon-driven synthesis of Au nanostructures.
Figure 2: The influence of plasmonic hotspots on Au nanoprism growth.
Figure 3: The role of PVP in directing the anisotropic growth of Au nanoprisms.
Figure 4: Plasmon-driven synthesis of hexagonal or triangular Au nanoprisms.

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Acknowledgements

The work is supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-14-1-0304. We also thank the National Science Foundation for support under Grant CHE-1308644 and the CCI Center for Nanostructured Electronic Materials (CHE-1038015). F.O. and B.D. acknowledge the generous support from the University of Florida (UF) Howard Hughes Medical Institute (HHMI) Intramural Award and the UF University Scholars Program. B.Y. acknowledges support from UF’s Student Science Training Program. We thank M. Hill and B. Sumerlin for assistance with zeta potential measurements. Electron microscopy work was carried out in part at the Center for Functional Nanomaterials at Brookhaven National Laboratory (Upton, New York) through User Proposal BNL-CFN-31913 and BNL-CFN-33789, supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, under Contract DE-SC0012704. A portion of the research (AFM and NanoSIMS characterization) was performed at the Environmental Molecular Sciences Laboratory (EMSL) through User Proposal 40065, a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research located at the Pacific Northwest National Laboratory (PNNL) (Richland, Washington). PNNL is operated by Battelle for the US DOE under contract DE-AC06-76RLO1930.

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Y.Z., J.S.D. and W.D.W. conceived the system and designed the experiments. Y.Z., J.S.D., B.Y. and W.G. synthesized the materials. J.S.D., A.C.J.-P., D.S. and E.A.S. performed the EELS and TEM characterization. Y.-C.W. and Z.Z. performed the NanoSIMS characterization. Y.Z., J.Q. and E.W.Z. performed the SEM measurements. Y.-C.W. and D.H. performed the AFM measurement. Y.Z., J.S.D. and W.D.W. analysed and interpreted the data. Y.Z., J.S.D. and W.D.W. prepared the manuscript with contributions from all authors. W.D.W. supervised the project.

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Correspondence to Wei David Wei.

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Zhai, Y., DuChene, J., Wang, YC. et al. Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis. Nature Mater 15, 889–895 (2016). https://doi.org/10.1038/nmat4683

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