Faceting of Nanocrystals during Chemical Transformation: FromSolid Silver Spheres to Hollow Gold Octahedra
Sustained progress in nanocrystal synthesis has enabled recent use of these materials as inorganic, macromolecular precursors that can be chemically transformed into new nanostructures. The literature now contains several cases with chemical transformations being accompanied by varying degrees of modification of properties, including crystal structure and particle shape. As a recent example, we demonstrated that as-synthesized metallic nanocrystals yield, upon oxidation, nanostructures with modified morphologies such as hollow particles. This morphological change derives from directional material flows due to differing diffusivities for the reacting atomic species, in a nanoscale version of the well-known Kirkendall Effect. This general methodology has since been extended by other groups to produce nanostructures with various compositions and shapes. We demonstrate that performing a replacement reaction on single crystalline Ag nanospheres of {approx}10 nm in diameter in an organic solvent produces hollow Au nanocrystals with an octahedral shape. Different from those Au shells made by starting with Ag particles about one order of magnitude larger, which largely reproduce that of the sacrificial Ag counterparts, the hollow nanocrystals obtained in this work show significant changes in the external morphology from the spherical Ag precursors. This evolution of a faceted external morphology during chemical transformation is made possible by the enhanced role of surface effects in our smaller nanocrystals. The competition between the Au atom deposition and Ag atom dissolution on various nanocrystal surfaces is believed to determine the final octahedral shape of the hollow Au nanocrystals. Simultaneous achievement of surface-mediated shape control and a hollow morphology in a one-pot, single-step synthetic procedure in this study promises an avenue to finer tuning of particle morphology, and thus physical properties such as surface plasmon resonance.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Director. Office of Science. Office of AdvancedScientific Computing Research. Office of Basic EnergySciences
- DOE Contract Number:
- DE-AC02-05CH11231
- OSTI ID:
- 901045
- Report Number(s):
- LBNL-60696; R&D Project: 508401; BnR: KC0203010; TRN: US200711%%772
- Journal Information:
- Journal of American Chemical Society, Vol. 128, Issue 39; Related Information: Journal Publication Date: 2006
- Country of Publication:
- United States
- Language:
- English
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