Department of Biomedical Engineering, Washington University in St. Louis, Saint Louis, Missouri 63130, USA.
Chemistry. 2009 Dec 7;15(47):13181-7. doi: 10.1002/chem.200901440.
Herein we describe a protocol that generates Au icosahedra in high yields by simply mixing aqueous solutions of HAuCl(4) and N-vinyl pyrrolidone. Our mechanistic study reveals that water plays an important role in this synthesis: as a nucleophile, it attacks the gold-vinyl complex, leading to the production of an alcohol-based Au(I) intermediate. This intermediate then undergoes a redox reaction in which Au(I) is reduced to Au(0), leading to the formation of Au atoms and then Au icosahedra of about 18 nm in size at a yield of 94 %, together with a carboxylic acid in the final product. This new protocol has also been employed to prepare multiply twinned nanoparticles of Ag (15-20 nm in size), spherical aggregates (25-30 nm in size) of Pd nanoparticles, and very small nanoparticles of Pt (2 nm in size). Since no organic solvent, surfactant, or polymer stabilizer is needed for all these syntheses, this protocol may provide a simple, versatile, and environmentally benign route to noble-metal nanoparticles having various compositions and morphologies.
在此,我们描述了一种通过简单混合 HAuCl(4) 和 N-乙烯基吡咯烷酮的水溶液即可高产率生成 Au 二十面体的方案。我们的机理研究表明,水在该合成中起着重要作用:作为亲核试剂,它攻击金-乙烯基配合物,导致产生基于醇的 Au(I)中间体。然后,该中间体经历一个氧化还原反应,其中 Au(I)被还原为 Au(0),导致 Au 原子的形成,然后在 94%的产率下形成约 18nm 大小的 Au 二十面体,最终产物中还有羧酸。该新方案还被用于制备 Ag 的多孪晶纳米粒子(尺寸为 15-20nm)、Pd 纳米粒子的球形聚集体(尺寸为 25-30nm)以及 Pt 的非常小的纳米粒子(尺寸为 2nm)。由于所有这些合成都不需要有机溶剂、表面活性剂或聚合物稳定剂,因此该方案可能为具有各种组成和形态的贵金属纳米粒子提供了一种简单、通用且环境友好的途径。