The role of ligands in atomically precise nanocluster-catalyzed CO2 electrochemical reduction

Ligand effects are of major interest in catalytic reactions owing to their potential critical role in determining the reaction activity and selectivity. Herein, we report ligand effects in the CO2 electrochemical reduction reaction at the atomic level with three unique Au-25 nanoclusters comprising the same kernel but different protecting ligands (-XR, where X = S or Se, and R represents the carbon tail). It is observed that a change in the carbon tail shows no obvious impact on the catalytic selectivity and activity, but the anchoring atom (X = S or Se) strongly affects the electrocatalytic selectivity. Specifically, the S site acts as the active site and sustains CO selectivity, while the Se site shows a higher tendency of hydrogen evolution. Density functional theory (DFT) calculations reveal that the energy penalty associated with the *COOH formation is lower on the S site by 0.26 eV compared to that on the Se site. Additionally, the formation energy of the product (*CO) is lower on the sulfur-based Au nanocluster by 0.43 eV. We attribute these energetic differences to the higher electron density on the sulfur sites of the Au nanocluster, resulting in a modified bonding character of the reaction intermediates that reduce the energetic penalty for the *COOH and *CO formation. Overall, this work demonstrates that S/Se atoms at the metal-ligand interface can play an important role in determining the overall electrocatalytic performance of Au nanoclusters.

Automated summary

This study investigates the effects of different protecting ligands on Au nanoclusters in the CO2 electrochemical reduction reaction, revealing that the sulfur site acts as the active site supporting CO selectivity, while the selenium site shows a higher tendency for hydrogen evolution. Energy calculations demonstrate that the sulfur-based Au nanocluster exhibits lower energy penalties for key reaction steps, leading to improved catalytic performance.