Structure of the Au23−xAgx(S‐Adm)15 Nanocluster and Its Application for Photocatalytic Degradation of Organic Pollutants

Ligands play an important role in determining the atomic arrangement within the metal nanoclusters. Here, we report a new nanocluster Au_23?xAg_x(S‐Adm)₁₅] protected by bulky adamantanethiol ligands which was obtained through a one‐pot synthesis. The total structure of Au_23?xAg_x(S‐Adm)₁₅] comprises an Au_13?xAg_x icosahedral core, three Au₃(SR)₄ units, and one AgS₃ staple motif in contrast to the 15‐atom bipyramidal core previously seen in Au_23?xAg_x(SR)₁₆]. UV/Vis spectroscopy indicates that the HOMO–LUMO gap of Au_23?xAg_x(S‐Adm)₁₅] is 1.5 eV. DFT calculations reveal that Au₁₉Ag₄(S‐Adm)₁₅] is the most stable structure among all structural possibilities. Benefitting from Ag doping, Au_23?xAg_x(S‐Adm)₁₅] exhibits drastically improved photocatalytic activity for the degradation of rhodamine B (RhB) and phenol under visible‐light irradiation compared to Au₂₃ nanoclusters.