The capability of precisely constructing bimetallic clusters with atomic accuracy provides exciting opportunities for establishing their structure–property correlations. However, the chemistry (the charge state of precursors, the property of ligands, the amount of dopant, and so forth) dictating the fabrication of clusters with atomic-level control has been a long-standing challenge. Herein, based on the well-defined Au25(SR)18 cluster (SR = thiolates), we have systematically investigated the factors of steric hindrance and electronic effect of ligands, the charge state of Au25(SR)18, and the amount of dopant that may determine the structure of AuCd clusters. It is revealed that [Au19Cd3(SR)18]− can be obtained when a ligand of smaller steric hindrance is used, while Au24Cd(SR)18 is attained when a larger steric hindrance ligand is used. In addition, negatively charged [Au25(SR)18]− is apt to form [Au19Cd3(SR)18]− during Cd doping, while Au24Cd(SR)18 is produced when neutral Au25(SR)18 is used as a precursor. Intriguingly, the reversible transformation between [Au19Cd3(SR)18]− and Au24Cd(SR)18 is feasible by subtly manipulating ligands with different steric hindrances. Most importantly, by introducing the excess amount of dopant, a novel bimetallic cluster, Au4Cd4(SR)12 is successfully fabricated and its total structure is fully determined. The electronic structures and the chirality of Au4Cd4(SR)12 have been elucidated by density functional theory (DFT) calculations. Au4Cd4(SR)12 reported herein represents the smallest AuCd bimetallic cluster with chirality.
Metal nanoparticles occupy an important position in electrocatalysis. Unfortunately, by using conventional synthetic methodology, it is a great challenge to realize the monodisperse composition/structure of metal nanoparticles at the atomic level, and to establish correlations between the catalytic properties and the structure of individual catalyst particles. For the study of well‐defined nanocatalysts, great advances have been made for the successful synthesis of nanoparticles with atomic precision, notably ligand‐passivated metal nanoclusters. Such well‐defined metal nanoclusters have become a type of model catalyst and have shown great potential in catalysis research. In this review, the authors summarize the advances in the utilization of atomically precise metal nanoclusters for electrocatalysis. In particular, the factors (e.g., size, metal doping/alloying, ligand engineering, support materials as well as charge state of clusters) affecting selectivity and activity of catalysts are highlighted. The authors aim to provide insightful guidelines for the rational design of electrocatalysts with high performance and perspectives on potential challenges and opportunities in this emerging field.
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