Alkynyl and halogen co-protected (AuAg)44 nano-clusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

作者：Tang, Yun; Sun, Fang; Ma, Xiaoshuang; Qin, Lubing; Ma, Guanyu; Tang, Qing; Tang, Zhenghua^*

来源：Dalton Transactions, 2022, 51(20): 7845-7850.

DOI：10.1039/d2dt00634k

• RAY CRYSTAL-STRUCTURE
• METAL NANOCLUSTERS
• LIGANDS
• ATOMS
• GOLD

We report the synthesis, structure, and electrochemical hydrogen evolution reaction (HER) performance of two alkynyl and halogen coprotected AuAg alloy nanoclusters, namely Au24Ag70((BuPh)-Bu-t-C C)(24)Cl-2(NC 1 for short) and Au22Ag22 ((BuC)-Bu-t C)(16)Br3.28Cl2.72 (NC 2 for short). Single crystal X-ray structural analysis revealed that the two nanoclusters possess a rather similar core@shell@shell keplerate metal core configuration to M-12@M-20@M-12 with the main difference in the outermost shell (Au-12 vs. Au10Ag2). Interestingly, such a subtle difference in the two-metal-atoms results in different optical absorbance features and drastically different HER performances. Both NCs have excellent long-term stability for the HER, but NC 1 possesses superior activity to NC 2, and density functional theory calculations disclosed that the binding energy of hydrogen to form the key *H intermediate for NC 1 is much lower and hence it adopts a more energetically feasible HER pathway.

• 单位
  重庆大学