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

• Published in: Angewandte Chemie International Edition 2023-08, Vol.62 (33), p.e202306696-n/a
• Main Authors: Zhuang, Shengli, Chen, Dong, Ng, Wai‐Pan, Liu, Li‐Juan, Sun, Meng‐Ying, Liu, Dongyi, Nawaz, Tehseen, Xia, Qi, Wu, Xia, Huang, Yong‐Liang, Lee, Seungkyu, Yang, Jun, He, Jian
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalysts; Chemical reduction; Cluster Assembly; Clusters; Defects; Density functional theory; Free energy; Gold Nanoclusters; Homologues; Homology; Ligands; Nanoclusters; Phosphine; Phosphine Ligands; Phosphines; Structural Defects
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202306696

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 first series of dual‐ligand‐protected nanocluster homologues is demonstrated, with a unified formula of Au44(PPh3)n(TBBT)28−2n (n=0–2) and similar cuboctahedral interpenetrating structures. The structural defects at the bottom of the Au44(PPh3)(TBBT)26 nanocluster facilitate electrochemical CO2 reduction to CO by lowering the free energy for the *COOH formation.