Construction of a new Au27Cd1(SAdm)14(DPPF)Cl nanocluster by surface engineering and insight into its structure–property correlation

A large surface-to-volume ratio is one of the most intriguing characteristics of nanoclusters, which endows the nanoclusters with novel properties and applications. In this work, surface engineering with a functional DPPF ligand and Cd atom is employed on a Au38 nanocluster to obtain a Au–Cd alloy nanocluster, that is, Au27Cd1(SAdm)14(DPPF)Cl (Au27Cd1 in short, DPPF = 1,1′-bis(diphenylphosphino)ferrocene, HSAdm = 1-adamantanethiol). Various characterization techniques are used to characterize the precise formulation and atomic structure of the Au27Cd1 nanocluster. To demonstrate the influence of surface engineering on the properties of nanoclusters, the difference in optical, electrochemical and electrocatalytic activities in the oxygen reduction reaction (ORR) between Au38 and Au27Cd1, as well as the stability of Au27Cd1, is explored. The results indicate the importance of surface engineering, that is, the introduction of functional ligands and surface doping of Cd atoms contribute to the enhancement of catalytic activity. This work sheds light on the surface engineering of nanoclusters and provides a new perspective for the performance optimization of nanoclusters.