Phosphine‐Triggered Structural Defects in Au44 Homologues Boost Electrocatalytic CO2 Reduction

Abstract 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) 28−2 n ( 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 rate‐determining step in the whole catalytic process.