While the formation of superatomic nanoclusters by the three-dimensional assembly of icosahedral units was predicted in 1987, the synthesis and structural determination of such clusters have proven to be incredibly challenging. Herein, we employ a mixedligand strategy to prepare phosphinous acid−phosphinito gold nanocluster Au 52 (HOPPh 2 ) 8 (OPPh 2 ) 4 (TBBT) 16 with a tetra-icosahedral kernel. Unlike expected, each icosahedral Au 13 unit shares one vertex gold atom with two adjacent units, resulting in a "puckered" ring shape with a nuclearity of 48 in the kernel. The phosphinous acid−phosphinito ligand set, which consists of two phosphinous acids and one phosphinito motif, has strong intramolecular hydrogen bonds; the π−π stacking interactions between the phosphorus-and sulfur-based ligands provide additional stabilization to the kernel. Highly stable Au 52 (HOPPh 2 ) 8 (OPPh 2 ) 4 (TBBT) 16 serves as an effective electrocatalyst in the oxygen reduction reaction. Density functional theory calculations suggest that the phosphinous acid− phosphinito ligands provide the most active sites in the electrochemical catalysis, with O* formation being the rate-determining step.
The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster‐based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au3 triangular units can be successfully introduced into the double‐stranded helical kernel of Au44(TBBT)28, where TBBT=4‐tert‐butylbenzenethiolate, resulting in the formation of two atomically precise defective Au44 nanoclusters. Along with the regular face‐centered‐cubic (fcc) nanocluster, the first series of mixed‐ligand cluster homologues is identified, with a unified formula of Au44(PPh3)n(TBBT)28−2n (n=0–2). The Au44(PPh3)(TBBT)26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the rate‐determining step in the whole catalytic process.
The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster-based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au 3 triangular units can be successfully introduced into the double-stranded helical kernel of Au 44 (TBBT) 28 , where TBBT = 4-tert-butylbenzenethiolate, resulting in the formation of two atomically precise defective Au 44 nanoclusters. Along with the regular face-centered-cubic (fcc) nanocluster, the first series of mixed-ligand cluster homologues is identified, with a unified formula of Au 44 (PPh 3 ) n (TBBT) 28À 2n (n = 0-2). The Au 44 (PPh 3 )-(TBBT) 26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO 2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the ratedetermining step in the whole catalytic process.
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