Role of bromide in hydrogen peroxide oxidation of CTAB-stabilized gold nanorods in aqueous solutions.

In recent years hydrogen peroxide has often been used as the oxidizing agent to tune the resonance wavelength of gold nanorods (AuNRs) through anisotropic shortening in the presence of cetyltrimethylammonium bromide (CTAB). However, a complete picture of the reaction mechanism remains elusive. In this work, we present a systematic study on the mechanism of the AuNR oxidation by revealing the important role of bromide. Hydrogen peroxide slowly oxidizes bromide into elemental bromine. The latter two form tribromide, which exhibits a characteristic 272 nm absorption peak. The peak intensity, representing the concentration of tribromide, is found to have a linear correlation with the oxidation rate of AuNRs. Tribromide approaches AuNRs through conjugating strongly with CTA cationic micelles, which leads to the oxidation occurring on the surface of AuNRs. In contrast, the CTA micelles protect AuNRs from the direct oxidation by hydrogen peroxide. Our findings are believed to provide new insights into the reaction mechanism occurring in the relevant CTAB-AuNR systems, which can be important for understanding the principles governing the reaction dynamics.