| Affiliation: | 1. KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia;2. KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia These authors contributed equally to this work.;3. Advanced Membranes and Porous Materials Center (AMPMC), KAUST Catalysis Center (KCC), Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia;4. Department of Chemistry & Chemical Engineering, Syed Babar Ali School of Science & Engineering, Lahore University of Management Sciences (LUMS), DHA, 54792 Lahore, Pakistan |
| Abstract: | Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58H20PET36(PPh3)4]2+ ( Cu58 ; PET: phenylethanethiolate; PPh3: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface-defective analog [Cu57H20PET36(PPh3)4]+ ( Cu57 ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57 . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58 , Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts. |
