Tunable reactivity of silver nanoclusters: a facile route to synthesize a range of bimetallic nanostructures

Quantized energy levels and unique optoelectronic properties of atomically precise noble metal nanoclusters (NCs) have made them important in materials science, catalysis, sensors, and biomedicine. Recent studies on the profound chemical interactions of such NCs within themselves and with ultrasmall plasmonic nanoparticles (NPs) indicate that depending on the size, shape, and composition of the second reactant, NCs can either take part in colloidal assembly without any chemical modifications or lead to products with atoms exchanged. Anisotropic NPs are a unique class of plasmonic nanomaterials as their sharp edges and protrusions show higher chemical reactivity compared to flat surfaces, often leading to site-specific growth of foreign metals and metal oxide shells. Here, using chemical interactions between gold nanotriangles (AuNTs) and Ag NCs of different compositions, we show for the first time that metal atom etching, alloying/atom exchange, and colloidal assembly can all happen at a particular length scale. Specifically, Ag₂₅(DMBT)₁₈ NCs (denoted as 1), upon reacting with AuNTs of ∼57 nm edge length, etch gold atoms from their sharp tips and edges. Simultaneously, the two nanosystems exchange metal atoms, resulting in Ag-doped AuNTs and Au_xAg_24−x(DMBT)₁₈ (x = 1, 2). However, another Ag NC with the same metallic core, but a different ligand shell, namely, Ag₂₅H₂₂(DPPE)₈ (denoted as 2), creates dendritic shells made of Ag, surrounding these AuNTs under the same reaction conditions. Furthermore, we show that in the case of a more reactive thiol-protected Ag NC, namely, Ag₄₄(pMBA)₃₀ (denoted as 3), gold etching is faster from the edges and tips, which drastically alters the identities of both the reactants. Interestingly, when the AuNTs are protected by pMBA, 3 systematically assembles on AuNTs through H-bonding, resulting in an AuNT core-Ag NC shell nanocomposite. Thus, while shedding light on various factors affecting the reactivity of Ag NCs towards AuNTs, the present study proposes a single strategy to obtain a number of bimetallic nanosystems of targeted morphology and functionality.