Effect of Metal Nanoparticle Aggregate Structure on the Thermodynamics of Oxidative Dissolution

Here, we compare the electrochemical oxidation potential of 15 nm diameter citrate-stabilized Au NPs aggregated by acid (low pH) to those aggregated by tetrakis(hydroxymethyl) phosphonium chloride (THPC). For acid-induced aggregation, the solution changes to a blue-violet color, the localized surface plasmon resonance (LSPR) band of Au NPs at 520 nm decreases along with an increase in absorbance at higher wavelengths (600-800 nm), and the peak oxidation potential (E_p) in anodic stripping voltammetry (ASV) obtained in bromide has a positive shift by as large as 200 mV. For THPC-induced aggregation (Au/THPC mole ratio = 62.5), the solution changes to a blue color as the LSPR band at 520 nm decreases and a new distinct peak at 700 nm appears, but the E_p does not exhibit a positive shift. Scanning transmission electron microscopy (STEM) images reveal that acid-induced aggregates are three-dimensional with strongly fused Au NP-Au NP contacts, while THPC-induced aggregates are linear or two-dimensional with ∼1 nm separation between Au NPs. The surface area-to-volume ratio (SA/V) decreases for acid-aggregated Au NPs due to strong Au NP-Au NP contacts, which leads to lower surface free energy and a higher E_p. The SA/V does not change for THPC-aggregated Au NPs since space remains between them and their SA is fully accessible. These findings show that metal NP oxidative stability, as determined by ASV, is highly sensitive to the details of the aggregate structure.