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.
Unveiling the mystery of the contribution of nonsurface or noninterface sites in a catalyst to its catalytic performance remains a great challenge because of the difficulty in capturing precisely structural information (surface plus inner) encoded in the catalyst. This work attempts to elucidate the critical role of the internal vacancy in an atomically precise 24-atom gold cluster in regulating the catalytic performance on the hydrogenation reaction of CO 2 . The experiment results show that the Au 24 cluster with internal vacancy can mitigate sintering and exhibit high catalytic activity under relatively harsh reaction conditions, in contrast to the structurally similar Au 25 cluster without internal vacancy. Our computational study suggests that the internal vacancy in Au 24 provides the cluster with much more structural flexibility, which may be crucial to resisting the aggregation of the cluster and further postponing the deactivation. The hydrogenation and coupling stages of the reaction intermediates are proposed to explain the potential reaction pathway of CO 2 with H 2 on the Au 24 catalyst with internal vacancy.
The work shows the evolution from monomeric Au24Au20 into dimeric Au43Ag38 nanoclusters and provides exciting opportunities for atomic manufacturing on metal nanoclusters to construct structures and functionality.
There are obstacles with using conventional nanoparticle catalysts for developing atomic-by-atom tailoring of active sites in the heterogeneous catalysis field. However, atomically precise metal clusters with precise formulas and crystallographically determined structures, which may build a bridge between single atoms and nanoparticles, may become possible to unravel the respective contributions of every atom in a cluster to its overall catalytic performances and build the structure−property relationship at an atomic-precision level. In this Review, we will first describe recent advances of CO 2 electronic reduction catalyzed by Au-based clusters including pure gold and its alloys. We will then put a particular emphasis on chemical fixation of CO 2 into organic molecules, such as alkyne, epoxide, and amine, over gold cluster catalysts. Additionally, we will concisely introduce the discovery of catalytic selectivity of the Au-based clusters in CO 2 hydrogenation toward C 1 and C 2 products. Finally, we will provide our perspectives on some issues for catalytic conversion of CO 2 over atomically precise metal clusters in future catalysis research.
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