Stabilization of Ag-Au Bimetallic Nanocrystals in Aquatic Environments Mediated by Dissolved Organic Matter: A Mechanistic Perspective.
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Gold and silver nanoparticles can be stabilized endogenously within aquatic environments from dissolved ionic species as a result of mineralization induced by dissolved organic matter. However, the ability of fulvic and humic acids to stabilize bimetallic nanoparticles is entirely unexplored. Elucidating the formation of such particles is imperative given their potential ecological toxicity. Herein, we demonstrate the nucleation, growth, and stabilization of bimetallic Ag-Au nanocrystals from the interactions of Ag+ and Au3+ with Suwannee River fulvic and humic acids. The mechanisms underpinning the stabilization of Ag-Au alloy NPs at different pH (6.0-9.0) values are studied by UV-vis spectrophotometry, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED). Complexation of free Ag+ and Au3+ ions with the Lewis basic groups (carbonyls, carboxyls, and thiols) of FA and HA, followed by electron-transfer from redox-active moieties present in dissolved organic matter initiates the nucleation of the NPs. Alloy formation and interdiffusion of Au and Ag atoms are further facilitated by a galvanic replacement reaction between AuCl4- and Ag. Charge-transfer from Au to Ag stabilizes the formed bimetallic NPs. A more pronounced agglomeration of the Ag-Au NPs is observed when HA is used compared to FA as the reducing agent. The bimetallic NPs are stable for greater than four months, which suggests the possible persistence and dispersion of these materials in aquatic environments. The mechanistic ideas have broad generalizability to reductive mineralization processes mediated by dissolved organic matter.