Partially Thiolated Au25 Cluster Anchored on Carbon Support via Noncovalent Ligand–Support Interactions: Active and Robust Catalyst for Aerobic Oxidation of Alcohols

Partially thiolated atomically precise Au cluster catalysts were developed by controlled calcination of presynthesized thiolate-protected Au clusters on a porous carbon support. X-ray absorption fine structure analysis, powder X-ray diffraction, and aberration-corrected high-angle annular dark field scanning transmission electron microscopy revealed that calcination of 1 wt % of Au25(SR)18 (RS = 2-phenylethanethiolate, 1-dodecanethiolate) on carbon at 450 °C for 8–12 h produced partially thiolated Au25 clusters Au25(SR)/C without sintering. The Au25(SR)/C catalyst exhibited comparable catalytic activity to that of the thiolate-free Au25 cluster Au25/C for benzyl alcohol oxidation, whereas Au25(SR)/C showed higher durability than Au25/C. These results suggested that the residual RS ligands were distributed at the interface between the clusters and the support and suppressed the diffusion of the clusters by multiple van der Waals interactions. Large kinetic isotope effects indicated that the hydride abstraction from the α-carbon of the alkoxide was the rate-determining step. The O2 pressure dependence on rate constants was comparable to that reported for negatively charged Au clusters stabilized by poly(N-vinyl-2-pyrrolidone). This comparison suggests that electron-rich Au atoms left behind by desorbed RS served as active sites, which was supported by density functional theory calculations on model clusters. The partially thiolated Au25 cluster catalysts oxidized various p-substituted benzyl alcohols and benzylic secondary alcohols, with turn-over numbers exceeding 1 × 104. This work demonstrates that partially ligated, atomically precise metal clusters anchored by noncovalent ligand–support interaction are promising model catalysts with both high activity and durability.