Rapid Synthesis of Highly Monodisperse Au_xAg_1−x Alloy Nanoparticles via a Half-Seeding Approach

Gold−silver alloy Au_xAg_1−x is an important class of functional materials promising new applications across a wide array of technological fields. In this paper, we report a fast and facile synthetic protocol for preparation of highly monodisperse Au_xAg_1−x alloy nanoparticles in the size range of 3−6 nm. The precursors employed in this work are M(I)−alkanethiolates (M = Au and Ag), which can be easily prepared by mixing common chemicals such as HAuCl₄ or AgNO₃ with alkanethiols at room temperature. In this half-seeding approach, one of the M(I)−alkanethiolates is first heated and reduced in oleylamine solvent, and freshly formed metal clusters will then act as premature seeds on which both the first and second metals (from M(I)−alkanethiolates, M = Au and Ag) can grow accordingly without additional nucleation and thus achieve high monodispersity for product alloy nanoparticles. Unlike in other prevailing methods, both Au and Ag elements present in these solid precursors are in the same monovalent state and have identical supramolecular structures, which may lead to a more homogeneous reduction and complete interdiffusion at elevated reaction temperatures. When the M(I)−alkanethiolates are reduced to metallic forms, the detached alkanethiolate ligands will serve as capping agent to control the growth. More importantly, composition, particle size, and optical properties of Au_xAg_1−x alloy nanoparticles can be conveniently tuned with this approach. The optical limiting properties of the prepared particles have also been investigated at 532 and 1064 nm using 7 ns laser pulses, which reveals that the as-prepared alloy nanoparticles exhibit outstanding broadband optical limiting properties with low thresholds.