Ligand Effect‐Inspired Scalable Synthesis and Catalytic CO 2 Fixation of Cobalt Nanoclusters

Metal nanoclusters have attracted wide research interest in catalysis because they have abundant activation sites on the surface, and meanwhile, their atomically precise structures provide ideal models for mechanism studies. In spite of the current progress, the efficient and scalable synthesis of metal nanoclusters and their practical applications in industrial catalysis remain significant challenges. In this work, using the earth‐abundant cobalt nanocluster Co 6 S 8 L 6 ( L = phosphine ligand) as a platform, we systematically investigated its synthetic mechanism and catalytic properties. A positively charged intermediate during cluster formation was clarified based on kinetic studies, which inspired us to develop an efficient route to Co 6 S 8 L 6 nanoclusters by electronically modulating the phosphine ligands. An intriguing synergistic effect between the cobalt core and the surface ligand was further revealed in a Co 6 S 8 L 6 ‐catalyzed CO 2 chemical fixation reaction. Based on the in‐depth understanding of the synthetic and catalytic mechanisms of the cobalt nanoclusters, decagram‐scale synthesis of Co 6 S 8 L 6 and its efficient catalysis for CO 2 chemical fixation have been achieved.