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We demonstrate here that the gold nanoparticles (AuNPs) obtained in micellarsolutions are susceptible to the precursor complex nature and specificcounterion effects controlling the reaction kinetics, particles size and shape.The tested approach consisted in reducing the HAuCl4 complex with ascorbic acidor citric acid in dodecyltrimethylammonium (DTA) solutions, at 318 K, in thepresence of bromide (Br), methanesulfonate (Ms), trifluoroacetate (TFA) ortrifluoromethanesulfonate (Tf) ions. Bromide ions replaced the chloride ions inthe precursor gold complex, and no nanoparticle formation could be observed inDTA-Br media, in the absence of seeds. In contrast, scanning electronmicroscopy images and atomic force microscopy measurements showed thatquasi-spherical AuNPs were formed in DTA-Ms and DTA-TFA solutions, while flatdisk-like or triangular AuNPs were obtained in DTA-Tf solutions, with no needof adding seeds in all such cases. The results indicated that the reduction ofthe precursor gold complex takes place at the micellar interface and that thespecific counterion effects should be taken into account for controllingnanoparticles formation in micellar media.

A Critical Evaluation of the Role of the Precursor Complex and Counterions in Synthesis of Gold Nanoparticles in Micellar Media