Alkynyl‐protected Ag₂₀Rh₂ Nanocluster with Atomic Precision: Structure Analysis and Tri‐functionality Catalytic Application

Abstract We report the overall structure and trifunctionality catalytic application of an atomically precise alloy nanocluster of Ag 20 Rh 2 (C≡C‐ t Bu) 16 (CF 3 CO 2 ) 6 (H 2 O) 2 (abbreviated as Ag 20 Rh 2 hereafter). Ag 20 Rh 2 has a twisted rod‐like structure, where a Ag 4 @Rh 2 kernel is connected by two twisted Ag 8 cubes on two sides. Ag 20 Rh 2 is a superatomic cluster with four free valence electrons, and it has characteristic absorbance feature. Interestingly, Ag 20 Rh 2 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.