Reduction of HAuCl<sub>4</sub> by Na<sub>2</sub>S revisited [electronic resource] : The case for Au nanoparticle aggregates and against Au<sub>2</sub>S/Au core/shell particles
- Washington, D.C. : United States. Dept. of Energy, 2007.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- pages 8,892-8,901 : digital, PDF file
- Additional Creators:
- Lawrence Berkeley National Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
- Restrictions on Access:
- Free-to-read Unrestricted online access
- The reaction of sodium sulfide with chloroauric acid has been surrounded by a controversy over the structure of the resulting product. The original report proposed a Au2S/Au core/shell structure based on strong near-IR resonance and limited transmission electron microscopy. Subsequent reports used the same model without further attempts to determine the structure of the products. With a significant body of experimental work compiled over a period of several years, we have shown that the major product of this reaction is aggregated spherical nanoparticles of gold with a minority component consisting of triangular and rod-like structures. This is in contradiction to the core/shell structures as originally proposed. Recently, there have been additional reports that again suggest a Au2S/Au core/shell structure or irregularly shaped Au nanoparticles as an explanation for the near-IR resonance. To help resolve this issue, we have carried out further experiments to determine how the reaction products may depend on experimental conditions such as concentration and aging of the reactants, particularly Na2S. It has been determined that sodium thiosulfate is the likely product from Na2S aging. In addition, persistent spectral hole burning experiments have been conducted on gold nanoparticle aggregate (GNA) samples at excitation intensities that are lower than that required to melt the nanostructures. We have observed a decrease in optical absorption on resonance with the excitation laser wavelength, with simultaneous increases in absorption to the blue and red of this wavelength region. However, in the presence of the stabilizer poly(vinyl pyrrolidone) (PVP), no increase in absorbance was observed but rather a blue shifting and decrease in intensity of the near-IR plasmon resonance. These results imply that the non-stabilized GNAs are able to break apart and reform into off resonant aggregate structures. In contrast, this behavior is suppressed in PVP stabilized GNAs because of the presence of polymer which quickly passivates the individual nanoparticles that comprise the GNAs after they are disrupted by laser irradiation. These results would be very difficult to explain if the nanostructures were core/shell. Furthermore, these new results again support the model of GNAs as the best possible explanation for the product of the HAuCl4 and Na2S reaction.
- Report Numbers:
- E 1.99:ucrl-jrnl--227541
- Published through SciTech Connect.
Journal of Physical Chemistry. C 111 25 ISSN 1932-7447 AM
A. M. Schwartzberg; C. D. Grant; Tony van Buuren; J. Z. Zhang.
- Funding Information:
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