Department of Chemistry, Indian Institute of Technology, Palakkad-678623, Kerala, India.
Department of Chemistry, National Institute of Technology Meghalaya, Shillong, 793003, Meghalaya, India.
J Mater Chem B. 2024 Apr 24;12(16):3908-3916. doi: 10.1039/d3tb02474a.
The fabrication of shape-selective coinage metal nanoclusters (MNCs) has promising applications due to their exceptional physical and chemical molecule-like properties. However, the stability of the specific geometry of the nanoclusters, such as their cubic shapes, is unclear and has been unraveled by assessing the nanoclusters' interactions with different environments. In this work, we investigate the morphological stability of cubic structured, coinage metal nanoclusters of varying sizes ranging from 14 to 1099 atoms. The impact of solvent environments like water and the presence of ionic liquids (IL) on the stabilization of the MNCs were assessed using molecular dynamics (MD) simulations. In general, smaller MNCs composed of less than 256 atoms encountered structural distortion easily compared to the larger ones, which preserved their cubic morphology with minimal surface aberrations in water. However, in the presence of 4M 1-butyl-1,1,1-trimethyl ammonium methane sulfonate [N1114][C1SO3] IL solution, the overall cubic shape of the MNCs was successfully preserved. Strikingly, it is observed that in contrast to the noble MNCs like Au and Ag, the cubic morphology for Cu MNCs with sizes less than 256 atoms exhibited significant stability even in the absence of IL.
由于具有独特的物理和化学分子性质，制备具有选择性形状的金属纳米团簇（MNCs）具有广阔的应用前景。然而，纳米团簇特定几何形状的稳定性（如立方形状）尚不清楚，需要通过评估纳米团簇与不同环境的相互作用来揭示。在这项工作中，我们研究了从 14 到 1099 个原子不等的不同尺寸的立方结构金属纳米团簇的形态稳定性。通过分子动力学（MD）模拟评估了溶剂环境（如水）和离子液体（IL）的存在对 MNCs 稳定化的影响。一般来说，与较大的纳米团簇相比，由少于 256 个原子组成的较小的纳米团簇更容易发生结构变形，在水中最小化表面畸变的情况下保持其立方形态。然而，在 4M 1-丁基-1,1,1-三甲基铵甲烷磺酸盐 [N1114][C1SO3] IL 溶液中，MNCs 的整体立方形状成功得到保持。值得注意的是，与 Au 和 Ag 等贵金属纳米团簇相比，在没有 IL 的情况下，尺寸小于 256 个原子的 Cu 纳米团簇的立方形态表现出显著的稳定性。
