Wang Hao, Su Jie, Ni Shou-Qing, Chen Jing, Cheng Shi-Bo
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Shandong Provincial Key Laboratory of Water Pollution Control and Resource Reuse, Shandong Key Laboratory of Environmental Processes and Health, School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China.
J Phys Chem A. 2024 Jul 18;128(28):5473-5480. doi: 10.1021/acs.jpca.4c01215. Epub 2024 Jul 5.
Liquid-phase synthesis of atomically precise nanoclusters has experienced rapid development recently, where polar solvents are indispensable in such a process. However, the regulation effect of solvents on the structural and electronic properties of different metal clusters and cluster assembly materials is still not well understood. Herein, a comprehensive density functional theory calculation has been performed to explore the solvation effect on heteroatom-doped endohedral gold clusters that always have remarkable stabilities and tunable electronic structures. The solvation free energy of the M@Au clusters (M = Cr, Mo, W, Co, Rh, Ir, Cu, Ag, and Au) was found to be related to the charge distribution of the central doped-atom M and the outer Au cage. Moreover, the aqueous solvent was observed to be able to increase the adsorption capacity of M@Au to O following the activation of O through the charge transfer from M@Au to O, in which the transferred electrons occupy the π antibonding orbital of O. In addition, the water solvent can also improve the hydrogenation reaction of O to form OOH over M@Au, where the activation energy barrier for this process is very low with the participation of the solvent. Considering the importance of solvents in the liquid-phase synthesis of atomically precise clusters, these findings highlighted here could provide valuable theoretical guidance in potential applications of functional gold nanoclusters, especially in the liquid-phase cluster catalysis.
近年来，原子精确纳米团簇的液相合成发展迅速，其中极性溶剂在这一过程中不可或缺。然而，溶剂对不同金属团簇及团簇组装材料的结构和电子性质的调控作用仍未得到充分理解。在此，我们进行了全面的密度泛函理论计算，以探究溶剂化对杂原子掺杂的内包金团簇的影响，这类团簇通常具有显著的稳定性和可调控的电子结构。结果发现，M@Au团簇（M = Cr、Mo、W、Co、Rh、Ir、Cu、Ag和Au）的溶剂化自由能与中心掺杂原子M和外层Au笼的电荷分布有关。此外，观察到水性溶剂能够通过M@Au向O的电荷转移激活O后，提高M@Au对O的吸附能力，其中转移的电子占据O的π反键轨道。另外，水溶剂还能促进O在M@Au上氢化生成OOH的反应，在溶剂参与下该过程的活化能垒非常低。鉴于溶剂在原子精确团簇液相合成中的重要性，此处突出的这些发现可为功能性金纳米团簇的潜在应用，尤其是在液相团簇催化方面，提供有价值的理论指导。
