Ligand removal of Au25 nanoclusters by thermal and electrochemical treatments for selective CO2 electroreduction to CO.

Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au25 nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO2 to CO. The Au25 nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤-0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au25 nanoclusters concomitantly. The thermally and electrochemically treated Au25 nanoclusters show enhanced activity and selectivity for the electrochemical CO2-to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.

Size Transformation of the Au22(SG)18 Nanocluster and Its Surface-Sensitive Kinetics.

For many applications of well-defined gold nanoclusters, it is desirable to understand their structural evolution behavior under working conditions with molecular precision. Here we report the first systematic investigation of the size transformation products of the Au22(SG)18 nanocluster under representative working conditions and highlight the surface effect on the transformation kinetics. Under thermal and aerobic conditions, the consecutive and pH-dependent transformation from Au22 to both well-defined clusters and small Au(I)SR species was identified by ESI-MS and UV-vis spectroscopy. By introducing a perturbation onto the Au22 surface, significant changes in the activation parameters were determined from the kinetic study of the Au22 transformation. This indicates the sensitivity of the nanocluster transformation pathway to the cluster surface. The systematic study of cluster transformation and the sensitivity of cluster transformation to the surface revealed herein has significant implications for future attempts to design gold nanoparticles with adaptation to the working environment and the regeneration of active nanoparticles.