Atomically precise gold-based nanoclusters have attracted increasing attention in catalysis owing to their well-defined atomic structures, discretely tunable electronic energy levels, and highly designable surface chemical environments. Serving as an important bridge between molecular complexes and metal nanoparticles, gold nanoclusters not only exhibit outstanding catalytic activity and selectivity, but also provide ideal model systems for elucidating structure-property-reactivity relationships at the atomic level. In recent years, advances in synthetic and characterization techniques have led to remarkable progress in the application of gold nanoclusters in both photocatalytic and thermal catalytic reactions, encompassing selective oxidation and reduction, C−C and C−heteroatom coupling, multicomponent transformations, and asymmetric catalysis. This review systematically summarizes recent developments in gold nanocluster catalysis across different reaction classes, with particular emphasis on the roles of heterometal doping, ligand engineering, and metal-metal cooperative effects in modulating catalytic behavior. Furthermore, fundamental design principles for achieving reaction pathway and selectivity control at the atomic scale are distilled, aiming to provide guidance for the rational development of efficient and sustainable catalytic systems.

Herein, the overall structure of a nanocluster coprotected by phosphine and mercaptan ligands [Au₇Ag₈(SPh)₆((p-OMePh)₃P)₈]NO₃ (Au₇Ag₈) was reported. For comparison, a previously reported nanocluster with the same structure, but a different metal composition, [Au₁₃Cu₂(TBBT)₆((p-ClPh)₃P)₈]SbF₆ (Au₁₃Cu₂), was synthesized. In addition, their optical and electrocatalytic CO₂ reduction properties were comprehensively compared. The results reveal that the photoluminescence quantum yield (PLQY) of the Ag-doped Au₇Ag₈ nanocluster is 1.62%, which is seven times greater than that of the Cu-doped Au₁₃Cu₂ nanocluster (PLQY = 0.23%). Furthermore, the Au₁₃Cu₂ nanocluster demonstrates significantly enhanced catalytic selectivity for CO, with a CO Faradaic efficiency ranging from 79.7% to 90.4%, compared with that of the Au₇Ag₈ nanocluster (CO Faradaic efficiency: 67.2%–77.7%) within a potential range of 0.5 to −1.1 V. From structural analyses, the superior CO selectivity of Au₁₃Cu₂ is attributed to the copper dopant.