Revealing the composition-dependent structural evolution fundamentals of bimetallic nanoparticles through an inter-particle alloying reaction

Alloy nanoparticles represent one of the most important metal materials, finding increasing applications in diverse fields of catalysis, biomedicine, and nano-optics. However, the structural evolution of bimetallic nanoparticles in their full composition spectrum has been rarely explored at the molecular and atomic levels, imparting inherent difficulties to establish a reliable structure–property relationship in practical applications. Here, through an inter-particle reaction between [Au(44)(SR)(26)](2−) and [Ag(44)(SR)(30)](4−) nanoparticles or nanoclusters (NCs), which possess the same number of metal atoms, but different atomic packing structures, we reveal the composition-dependent structural evolution of alloy NCs in the alloying process at the molecular and atomic levels. In particular, an inter-cluster reaction can produce three sets of Au(x)Ag(44−x) NCs in a wide composition range, and the structure of Au(x)Ag(44−x) NCs evolves from Ag-rich [Au(x)Ag(44−x)(SR)(30)](4−) (x = 1–12), to evenly mixed [Au(x)Ag(44−x)(SR)(27)](3−) (x = 19–24), and finally to Au-rich [Au(x)Ag(44−x)(SR)(26)](2−) (x = 40–43) NCs, with the increase of the Au/Ag atomic ratio in the NC composition. In addition, leveraging on real-time electrospray ionization mass spectrometry (ESI-MS), we reveal the different inter-cluster reaction mechanisms for the alloying process in the sub-3-nm regime, including partial decomposition–reconstruction and metal exchange reactions. The molecular-level inter-cluster reaction demonstrated in this study provides a fine chemistry to customize the composition and structure of bimetallic NCs in their full alloy composition spectrum, which will greatly increase the acceptance of bimetallic NCs in both basic and applied research.