Elucidating the Role of Dissolved Organic Matter and Sunlight in Mediating the Formation of Ag-Au Bimetallic Alloy Nanoparticles in the Aquatic Environment.

Elucidating the interactions between metal ions and dissolved organic matter and deciphering mechanisms for their mineralization in the aquatic environment are central to understanding the speciation, transport, and toxicity of nanoparticles (NPs). Herein, we examine the interactions between Ag+ and Au3+ ions in mixed solutions (χAg = 0.2, 0.5, and 0.8) in the presence of humic acids (HAs) under simulated sunlight; these conditions result in the formation of bimetallic Ag-Au NPs. A key distinction is that the obtained alloy NPs are compositionally and morphologically rather different from NPs obtained from thermally activated dark processes. Photoillumination triggers a distinctive plasmon-mediated process for HA-assisted reductive mineralization of ions to bimetallic alloy NPs which is not observed in its dark thermal reduction counterpart. The initial nucleation of bimetallic NPs is dominated by differences in the cohesive energies of Ag and Au crystal lattices, whereas the growth mechanisms are governed by the strongly preferred incorporation of Ag ions, which stems from their greater photoreactivity. The bimetallic NPs crystallize in shapes governed by the countervailing influence of minimizing free energy through the adoption of Wulff constructions and the energetic penalties associated with twin faults. As such, assessments of the stability and the potential toxic effects of bimetallic NPs arising from their possible existence in aquatic environments will depend sensitively on the origins of their formation.