Atomic‐level insights into the synergistic effect between ligands on electrochemical CO 2 reduction: based on Au 7 Ag 8 series nanoclusters

Abstract Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques. Herein, using precisely structured metal nanoclusters as models, we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters. This change leads to the selective dissociation of ligands during the catalytic process, thereby enabling control over catalytic selectivity with an abrupt increase in formate production from ~ 0% to 23%. This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.