Unraveling the Mechanism of the Brust-Schiffrin Formation of Au 25 (SR) 18 through Mass Spectrometry.

The Brust-Schiffrin (BS) method for gold nanoparticle (Au NP) synthesis is celebrated for its ability to produce highly monodisperse NPs from toluene-water solutions, in contrast to aqueous methods, such as the Turkevich method. Despite the method's success, the actual formation mechanisms remain largely unknown due to difficulty in studying the intermediates with species-differentiating techniques such as mass spectrometry (MS) or nuclear magnetic resonance (NMR). The issue lies in the use of solvents poorly compatible with these techniques and the difficulty in differentiating useful intermediate species from side products and impurities in such one-pot reactions. Herein, we use our recently formulated fully aqueous BS reaction to study the formation mechanisms. MS is chiefly employed to capture the intermediate species, and the Au 25 (SR) 18 nanocluster is used as a thermodynamically reliable end-point. We find that the BS method may comprise a unilateral complex-shedding stage in addition to the known thiol-etching stage.