New atomically precise (M = Au/Ag) nanoclusters as excellent oxygen reduction reaction catalysts.

By introducing 1,1'-bis-(diphenylphosphino)ferrocene (dppf) as an activating ligand, two novel nanoclusters, (M = Au/Ag), have been controllably synthesized and structurally characterized. The atomically precise structures of the nanoclusters were determined by SCXC and further confirmed by ESI-TOF-MS, TGA, XPS, DPV, and FT-IR measurements. The nanoclusters supported on activated carbon (C) are exploited as efficient oxygen reduction reaction (ORR) catalysts in alkaline solutions. Density functional theory (DFT) calculations verify that the catalytic activities of the two cluster-based systems originate from the significant ensemble synergy effect between the M kernel and dppf ligand in . This work sheds lights on the preparation of cluster-based electrocatalysts and other catalysts that are activated and modified by peripheral ligands.