Atomically precise alloy nanoclusters: syntheses, structures, and properties.

Metal nanoclusters fill the gap between discrete atoms and plasmonic nanoparticles, providing unique opportunities for investigating the quantum effects and precise structure-property correlations at the atomic level. As a versatile strategy, alloying can largely improve the physicochemical performances compared to the corresponding homo-metal nanoclusters, and thus benefit the applications of such nanomaterials. In this review, we highlight the achievements of atomically precise alloy nanoclusters, and summarize the alloying principles and fundamentals, including the synthetic methods, site-preferences for different heteroatoms in the templates, and alloying-induced structure and property changes. First, based on various Au or Ag nanocluster templates, heteroatom doping modes are presented. The templates with electronic shell-closing configurations tend to maintain their structures during doping, while the others may undergo transformation and give rise to alloy nanoclusters with new structures. Second, alloy nanoclusters of specific magic sizes are reviewed. The arrangement of different atoms is related to the symmetry of the structures; that is, different atoms are symmetrically located in the nanoclusters of smaller sizes, and evolve into shell-by-shell structures at larger sizes. Then, we elaborate on the alloying effects in terms of optical, electrochemical, electroluminescent, magnetic and chiral properties, as well as the stability and reactivity via comparisons between the doped nanoclusters and their homo-metal counterparts. For example, central heteroatom-induced photoluminescence enhancement is emphasized. The applications of alloy nanoclusters in catalysis, chemical sensing, bio-labeling, and other fields are further discussed. Finally, we provide perspectives on existing issues and future efforts. Overall, this review provides a comprehensive synthetic toolbox and controllable doping modes so as to achieve more alloy nanoclusters with customized compositions, structures, and properties for applications. This review is based on publications available up to February 2020.