Yuan Xun, Chng Leng Leng, Yang Jinhua, Ying Jackie Y
NanoBio Lab, Agency for Science, Technology and Research, 31 Biopolis Way, The Nanos, Singapore, 138669, Singapore.
Adv Mater. 2020 Mar;32(9):e1906063. doi: 10.1002/adma.201906063. Epub 2020 Jan 27.
Effective yet versatile synthetic strategies for size-tunable metal nanoclusters (NCs) are scarce. This has hampered the development of this unique class of nanomaterials. Here, a general protocol is reported for the synthesis of high-quality metal NCs protected by a variety of organic ligands (e.g., selenolate, thiolate, and phosphine) based on a miscible-solvent-assisted phase transfer between water and organic solution. This method is demonstrated to be facile, rapid (≤3 h), scalable (gram-scale), and versatile. The size of the selenolated and thiolated Au NCs can be tuned from Au to Au by simply varying the miscible solvent in proportions and types. The advantages of this method, such as quick phase separation and no need for purification treatment, enable real-time monitoring of metal NC growth within the NaBH reduction system. The results show that the size of Au NCs gradually increases with increasing valence electron count by a stepwise 2x e hopping mechanism (x = 0-5), i.e., 0 e → 2 e → 4 e → 8 e → 18 e → 22 e → 32 e .
用于尺寸可调的金属纳米团簇（NCs）的有效且通用的合成策略稀缺。这阻碍了这类独特纳米材料的发展。在此，报道了一种通用方法，用于基于水和有机溶液之间的混溶溶剂辅助相转移来合成由多种有机配体（如硒醇盐、硫醇盐和膦）保护的高质量金属纳米团簇。该方法被证明是简便、快速（≤3小时）、可扩展（克级规模）且通用的。通过简单改变混溶溶剂的比例和类型，硒醇化和硫醇化金纳米团簇的尺寸可从Au调至Au。该方法的优点，如快速相分离和无需纯化处理，能够实时监测NaBH还原系统中金属纳米团簇的生长。结果表明，金纳米团簇的尺寸通过逐步2x e跳跃机制（x = 0 - 5），即0 e → 2 e → 4 e → 8 e → 18 e → 22 e → 32 e，随着价电子数的增加而逐渐增大。
