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

• Published in: Angewandte Chemie Vol. 131; no. 33; pp. 11457 - 11461
• Main Authors: Liu, Chao, Ren, Xiuqing, Lin, Feng, Fu, Xuemei, Lin, Xinzhang, Li, Tao, Sun, Keju, Huang, Jiahui
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 12.08.2019
• Subjects: Catalytic activity; Chemistry; Environmental degradation; Icosahedral phase; Irradiation; Legierungen; Ligands; Light irradiation; Molecular orbitals; Nanocluster; Nanoclusters; Phenols; Photocatalysis; Photodegradation; Photokatalyse; Pollutants; Rhodamine; Spectroscopy; Thiole
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201904612

Ligands play an important role in determining the atomic arrangement within the metal nanoclusters. Here, we report a new nanocluster [Au23−xAgx(S‐Adm)15] protected by bulky adamantanethiol ligands which was obtained through a one‐pot synthesis. The total structure of [Au23−xAgx(S‐Adm)15] comprises an Au13−xAgx icosahedral core, three Au3(SR)4 units, and one AgS3 staple motif in contrast to the 15‐atom bipyramidal core previously seen in [Au23−xAgx(SR)16]. UV/Vis spectroscopy indicates that the HOMO–LUMO gap of [Au23−xAgx(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, [Au23−xAgx(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. Geschützt durch sperrige Liganden: Im Unterschied zum 15‐atomigen bipyramidalen Kern in [Au23−xAgx(SR)16] umfasst die Struktur von [Au23−xAgx(S‐Adm)15] einen ikosaedrischen Au13−xAgx‐Kern, drei Au3(SR)4‐Einheiten und ein klammerartiges AgS3‐Motiv. Dank der Ag‐Dotierung zeigt [Au23−xAgx(S‐Adm)15] eine deutlich bessere photokatalytische Aktivität für den Abbau von Rhodamin B und Phenol unter Bestrahlung mit sichtbarem Licht als Au23‐Nanocluster.