{331}-Faceted trisoctahedral gold nanocrystals: synthesis, superior electrocatalytic performance and highly efficient SERS activity

Abstract

We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm⁻²), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm⁻²) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a₁ modes of 4-ATP molecules can reach the order of 10⁹ when the 4-ATP concentration is 3 × 10⁻⁶ M. Moreover, Raman signals (a_g modes) of 4,4′-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities.