Ligand effect on the catalytic activity of porphyrin-protected gold clusters in the electrochemical hydrogen evolution reaction

reversible hydrogen electrode (RHE) was 460% higher than that of phenylethanethiol-protected AuCs. X-ray photoemission spectroscopy indicated that the approach of porphyrin to the Au surface induced charge migration from the porphyrin to the Au core, leading to a shift in the 5d state of AuCs that resulted in enhanced HER activities. This ligand effect is pronounced in the cluster region due to the large surface-to-volume ratio. These results pave the way for enhancing catalytic activity of metal clusters using ligand design.