Synergism between Specific Halide Anions and pH Effects during Nanosecond Laser Fragmentation of Ligand-Free Gold Nanoparticles

Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately. Pulsed laser fragmentation in liquids (LFL) is a convenient route for the synthesis of ligand-free AuNCs. The influence of physical parameters, such as melting and evaporation, on the LFL process is well understood both theoretically and experimentally. However, the impact of the chemical composition of the medium during LFL, which critically affects the particle formation process, has been less well examined. Therefore, in this work, we elucidate the extent to which the ionic strength, the pH value, and the nature of the halide anion that is present, that is, F-, Cl-, Br-, or I-, influence the particle size distribution of the LFL product and the mean yield of small particles (<3 nm) of the product. We showed that the yield of small particles can be enhanced by the synergism between pH and specific ion effects, which probably is attributable to the adsorption of specific anions. In addition, our findings indicated that anion-based stabilization depends critically on the type of anion. A direct Hofmeister effect was observed for anions in the neutral pH regime, whereas an indirect Hofmeister series was reported in alkaline solution, which probably was due to the more hydrophilic surfaces of the AuNCs that were formed.