Alkynyl‐protected Ag20Rh2 nanocluster with atomic precision: Structure analysis and tri‐functionality catalytic application

We report the overall structure and trifunctionality catalytic application of an atomically precise alloy nanocluster of Ag20Rh2(C≡C‐tBu)16(CF3CO2)6(H2O)2 (abbreviated as Ag20Rh2 hereafter). Ag20Rh2 has a twisted rod‐like structure, where a Ag4@Rh2 kernel is connected by two twisted Ag8 cubes on two sides. Ag20Rh2 is a superatomic cluster with four free valence electrons, and it has characteristic absorbance feature. Interestingly, Ag20Rh2 exhibited superior catalytic performance than the larger AgRh nanoparticle counterparts in electrochemical hydrogen evolution reaction (HER), reduction of 4‐nitrophenol, and the methyl orange degradation reaction. Such intriguing catalytic properties are attributed to the more exposed active sites from the ultrasmall nanoclusters than relatively large nanoparticles. This study not only enriches the family member of alkynyl‐protected AgRh nanoclusters with atomic precision, but also highlights the great advantages of employing nanoclusters as efficient catalysts for multiple functionalities.