In this paper, the mechanism of water-gas shift reaction (WGSR) on Au₃₂M₆ (M = Cu, Pt, Pd, Rh, Ir) core-shell nanoclusters was investigated by density functional theory (DFT). The result shows that the unique synergistic effect in the core-shell structure of Au₃₂M₆ has a significant effect on the activity of the catalyst. Compared with the Au₃₈ nanocluster, in the case of Au₃₂M₆, the charge transfer between the M₆ core and the Au₃₂ shell is larger after the formation of the core-shell nanocluster. The calculation of the binding energy indicates that the Au₃₂M₆ core-shell nanoclusters is more stable than Au₃₈ nanocluster. The parameters for the center of d-band show that d-orbital electrons of Au₃₂Pd₆ nanoclusters closer to the Fermi level than other nanoclusters, which indicates the Au₃₂Pd₆ nanocluster have better electron activity. In addition, we also found out the minimum energy pathways (MEP) of each nanocluster based on the adsorption investigation of various species on Au₃₂M₆ in the WGSR. The calculation results show that Au₃₂Pd₆ nanocluster exhibits excellent catalytic activity for WGSR, the reaction pathway was ER 1 → ER 4 → ER 5-b → ER 6.

本文利用密度泛函理论（DFT）研究了Au ₃₂ M ₆（M = Cu，Pt，Pd，Rh，Ir）核壳纳米团簇上水煤气变换反应（WGSR）的机理。结果表明，Au ₃₂ M ₆的核-壳结构具有独特的协同作用，对催化剂的活性有显着影响。与Au ₃₈纳米簇相比，在Au ₃₂ M ₆的情况下，在形成核-壳纳米簇之后，M ₆核与Au ₃₂壳之间的电荷转移更大。结合能的计算表明Au ₃₂ M ₆核-壳纳米团簇比Au ₃₈纳米团簇更稳定。d带中心的参数表明，Au ₃₂ Pd ₆纳米团簇的d轨道电子比其他纳米团簇更靠近费米能级，这表明Au ₃₂ Pd ₆纳米团簇具有更好的电子活性。此外，我们还基于WGSR中Au ₃₂ M ₆上各种物种的吸附研究，找出了每个纳米簇的最小能量路径（MEP）。计算结果表明，Au ₃₂ Pd ₆ 纳米簇对WGSR表现出优异的催化活性，反应途径为ER 1→ER 4→ER 5-b→ER 6。