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Phosphine-Triggered Structural Defects in Au44 Homologues Boost Electrocatalytic CO2 Reduction |
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| Authors: | Dr Shengli Zhuang Dr Dong Chen Wai-Pan Ng Li-Juan Liu Meng-Ying Sun Dongyi Liu Tehseen Nawaz Qi Xia Xia Wu Dr Yong-Liang Huang Prof Dr Seungkyu Lee Prof Dr Jun Yang Prof Dr Jun Yang Prof Dr Jian He |
| Institution: | 1. Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China
State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China These authors contributed equally to this work.;2. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190 P. R. China These authors contributed equally to this work.;3. Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China Hong Kong Quantum AI Lab Limited, Hong Kong, P. R. China These authors contributed equally to this work.;4. Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China;5. Department of Medicinal Chemistry, Shantou University Medical College, Shantou, Guangdong, 515041 P. R. China;6. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190 P. R. China |
| 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 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. |
| Keywords: | Cluster Assembly Gold Nanoclusters Homologues Phosphine Ligands Structural Defects |