Clusters with an exact number of atoms are of particular interest in catalysis. Their catalytic behaviors can be potentially altered with the addition or removal of a single atom. Now the effects of doping with a single foreign atom (Au, Pd, and Pt) into the core of an Ag cluster with 25 atoms on the catalytic properties are explored, where the foreign atom is protected by 24 Ag atoms (Au@Ag , Pd@Ag , and Pt@Ag ). The central doping of a single atom into the Ag cluster has a substantial influence on the catalytic performance in the carboxylation reaction of CO with terminal alkyne through C-C bond formation to produce propiolic acid. These studies reveal that the catalytic properties of the cluster catalysts can be dramatically changed with the subtle alteration by a single atom away from the active sites.

Precise control of the composition and structure of active sites in an atom‐by‐atom fashion remains insuperable for heterogeneous catalysts. Here, we introduce tailor‐made catalytic sites for the cycloaddition of CO2 to epoxides achieved by implementing Ag atoms at different levels of liberation in atomically precise Au nanoclusters. Our results reveal that a single open Ag site on the Au19Ag4 cluster improves the ring‐opening of epoxides and sequent CO2 insertion, while the partially exposed Ag site on the Au20Ag1 cluster exhibits a weak affinity for epoxides and poor efficiency for CO2 capture. Structural tunability imparted by the atom‐by‐atom tailoring and unusual atomic charges distributed on Au and Ag atoms of the three clusters seem to be crucial for promoting challenging bond cleavages and formations in the chemical utilization of CO2.

The discovery of atomically precise nanoclusters is generally unpredictable, and the rational synthesis of nanoclusters guided by the theoretical design is still in its infancy. Here we present a de novo design of Au 36 (SR) 24 nanoclusters, from theoretical prediction to experimental synthesis and characterization of their physicochemical properties. The crystal structure of an Au 36 (SR) 24 nanocluster perfectly matches the simulated structural pattern with Au 4 tetrahedral units along a two-dimensional growth. The Au 36 (SR) 24 nanocluster indeed differs from its structural isomer whose kernel is dissected in an Au 4 tetrahedral manner along a one-dimensional growth. The structural isomerism in the Au 36 (SR) 24 nanoclusters further induces distinct differences in ultrafast electron dynamics and chirality. This work will not only promote the atomically precise synthesis of nanoclusters enlightened by theoretical science, but also open up exciting opportunities for underpinning the widespread applications of structural isomers with atomic precision.

It is challenging to control the catalyst activation and deactivation by removal and addition of only one central atom, as it is almost impossible to precisely abstract an atom from aconventional catalyst and analyze its catalysis.Here we report that the loss of one central atom in Au 25 (resulting in Au 24 ) enhances the catalytic activity in the oxidation of methane compared to the original Au 25 .M ore importantly,t he activity can be readily switched through shuttling the central atom into Au 24 and out of Au 25 .This work will serve as astarting point for design rules on howt oc ontrol catalytic performance of ac atalyst by an atom alteration.

Metal nanoclusters with accurate compositions and determined crystalline structures hold remarkable attention in serving as a unique model catalyst for well-defined correlation between structure and catalytic activity. More importantly, these metal nanoclusters exhibit strong quantum confinement effects, which differs from their larger nanoparticles in a number of catalytic reactions. This review focuses on recent advances of atomically precise metal nanoclusters for C 1 compounds conversion (CO, CO 2 , CH 4 and HCOOH), including thermal-driven catalysis, photocatalysis and electrocatalysis. The reaction mechanisms are discussed at an atomic-or even electron-level. It is anticipated that the progress in this research area could be extendable to explore the catalytic applications of metal nanoclusters in C 1 chemistry.