Body-Centered-Cubic-Kernelled Ag₁₅Cu₆ Nanocluster with Alkynyl Protection: Synthesis, Total Structure, and CO₂...

While atomically monodisperse nanostructured materials are highly desirable to unravel the size- and structure-catalysis relationships, their controlled synthesis and the atomic-level structure determination pose challenges. Particularly, copper-containing atomically precise alloy nanoclusters are potential catalyst candidates for the electrochemical CO₂ reduction reaction (eCO₂RR) due to high abundance and tunable catalytic activity of copper. Herein, we report the synthesis and total structure of an alkynyl-protected 21-atom AgCu alloy nanocluster [Ag₁₅Cu₆(C≡CR)₁₈(DPPE)₂]^-, denoted as Ag (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene; DPPE: 1,2-bis(diphenylphosphino)ethane). The single-crystal X-ray diffraction reveals that Ag consists of an Ag₁₁Cu₄ metal core exhibiting a body-centered cubic (bcc) structure, which is capped by 2 Cu atoms, 2 Ag₂DPPE motifs, and 18 alkynyl ligands. Interestingly, the Ag cluster exhibits excellent catalytic activity for eCO₂RR with a CO faradaic efficiency (FE_CO) of 91.3% at -0.81 V (vs the reversible hydrogen electrode, RHE), which is much higher than that (FE_CO: 48.5% at -0.89 V vs RHE) of Ag with bcc structure. Furthermore, Ag shows superior stability with no significant decay in the current density and FE_CO during a long-term operation of 145 h. Density functional theory calculations reveal that the de-ligated Ag cluster can expose more space at the pair of AgCu dual metals as the efficient active sites for CO formation.