Disproportional surface segregation in ligand-free gold-silver alloy solid solution nanoparticles, and its...

Catalytic activity and toxicity of mixed-metal nanoparticles have been shown to correlate and are known to be dependent on surface composition. The surface chemistry of the fully inorganic, ligand-free silver-gold alloy nanoparticle molar fraction series, is highly interesting for applications in heterogeneous catalysis, which is determined by active surface sites which are also relevant for understanding their dissolution behavior in biomedically-relevant ion-release scenarios. However, such information has never been systematically obtained for colloidal nanoparticles without organic surface ligands and has to date, not been analyzed in a surface-normalized manner to exclude density effects. For this, we used detailed electrochemical measurements based on cyclic voltammetry to systematically analyze the redox chemistry of particle-surface-normalized gold-silver alloy nanoparticles with varying gold molar fractions. The study addressed a broad range of gold molar fractions (Ag₉₀Au₁₀, Ag₈₀Au₂₀, Ag₇₀Au₃₀, Ag₅₀Au₅₀, Ag₄₀Au₆₀, and Ag₂₀Au₈₀) as well as monometallic Ag and Au nanoparticle controls. Oxygen reduction reaction (ORR) measurements in O₂ saturated 0.1 M KOH revealed a linear reduction of the overpotential with increasing gold content on the surface, probably attributed to the higher ORR activity of gold over silver, verified by monometallic Ag and Au controls. These findings were complemented by detailed XPS studies revealing an accumulation of the minor constituent of the alloy on the surface, e.g., silver surface enrichment in gold-rich particles. Furthermore, highly oxidized Ag surface site enrichment was detected after the ORR reaction, most pronounced in gold-rich alloys. Further, detailed CV studies at acidic pH, analyzing the position, onset potential, and peak integrals of silver oxidation and silver reduction peaks revealed particularly low reactivity and high chemical stability of the equimolar Au₅₀Ag₅₀ composition, a phenomenon attributed to the outstanding thermodynamic, entropically driven, stabilization arising at this composition.