Photochemical synthesis of group 10 metal nanoclusters for electrocatalysis

Four group 10 metal nanoclusters, Ni₁₀(4-MePhS)₂₀, Ni₁₁(PhS)₂₂, Pd₉(PhS)₁₈ and Pd₁₀(PhS)₂₀ were synthesized from disulfides based on a photochemical reduction-oxidation cascade process, which proceeds via a different mechanism to that of the conventional two-step reduction process. The as-obtained nanoclusters possess oxidative resistance and structural robustness under different conditions. Their atomically precise structures are determined to be nickel or palladium rings in which the metal atoms are bridged by Ar-S groups. Their catalytic performance in oxygen reduction reaction was compared, and the ring size-dependent catalytic activity of the group 10 metal nanoclusters was revealed. This work provides an efficient route to atomically precise and structurally stable group 10 metal nanoclusters, and sheds light on their further applications in electrocatalysis.