Solvent-Induced Morphological Changes of Polyhedral Silver Nanoparticles in Epoxy Resin

The use of just one material as reducing and capping agent during the synthesis of noble metal nanoparticles is of great interest for potential applications. This paper reports a simple method to prepare polyhedral silver nanoparticles at 80 °C using an epoxy resin (Araldite 506) as both reducing and capping agent. The formation of metal nanoparticles was investigated by Fourier-transform infrared spectroscopy, atomic force microscopy, transmission electronic microscopy, high-resolution transmission electronic microscopy and UV-vis spectroscopy. The proposed mechanism for the reduction of silver ions involves radicals as precursors of ketones and other products originated by thermo-oxidation of the resin. The nucleation of small spherical and polyhedral seeds (～7 nm) of polycrystalline silver and twin planes lead to big polyhedral silver nanoparticles of average size, 68 nm. On the other hand, the polyhedral silver nanoparticles dispersed in toluene changed to prolate-like particles, and their dispersion in dimethyl-sulphoxide and formamide originated elongated polyhedrons and concave nanostructures, respectively. These structural changes lead to unusual solvent-induced optical properties. For instance, the polyhedral nanoparticles dispersed in toluene red-shifted their surface plasmon resonance from 425 to 540 nm, in dimethyl-sulphoxide the spectrum exhibited a peak at 418 nm and a shoulder at 520 nm, and for the silver nanoparticles in formamide a broad band with maximum peak at 420 nm was observed. It is showed that the solvent/resin system works itself as structure-directing agent of silver nanoparticles. These results open the doors to achieve silver nanostructures highly sensitive to the dielectric environment, an ideal condition for applications in colorimetric sensors of molecules of biological or chemical interest.