Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK.
Faraday Discuss. 2013;162:113-24. doi: 10.1039/c2fd20136d.
Helium droplets are large helium clusters that are capable of picking up individual atoms and molecules and show promise as nano-reactors for the synthesis of unique nanoparticles. In particular, the sequential addition of materials of different types offers opportunities for the fabrication of novel core-shell nanoparticles that cannot be synthesised by other methods. To exploit this potential, here we have carried out a mass spectrometry investigation on metal clusters in order to establish how to control the doping conditions for the fabrication of nanoparticles in superfluid helium droplets, and in particular to develop a recipe to control core and shell ratios in the case of core-shell nanoparticles. Several types of metal nanoparticles, including pure Ag, Au and Ni nanoparticles, and Ag/Au and Ni/Au core-shell systems, have been synthesised and then removed from the helium droplets by deposition on substrates for ex situ investigations using high-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The TEM imaging has been used to estimate the sizes of nanoparticles, which show a bimodel distribution under the conditions employed. We also present the first evidence that crystalline metal nanoparticles are formed by self-assembly of metal atoms in helium droplets. The XPS investigation of Ni/Au core-shell nanoparticles shows an absence of any Au 4f core-level shift that would occur on alloying of Au and Ni, which provides the first direct evidence for the successful formation of core-shell nanoparticles using superfluid helium droplets.
氦液滴是能够捕获单个原子和分子的大型氦团簇,有望成为合成独特纳米颗粒的纳米反应器。特别是,不同类型材料的顺序添加为制造其他方法无法合成的新型核壳纳米颗粒提供了机会。为了利用这一潜力,我们在这里对金属团簇进行了质谱研究,以确定如何控制在超流氦液滴中制造纳米颗粒的掺杂条件,特别是开发一种控制核壳纳米颗粒核壳比的方法。已经合成了几种类型的金属纳米颗粒,包括纯 Ag、Au 和 Ni 纳米颗粒,以及 Ag/Au 和 Ni/Au 核壳系统,然后通过沉积在衬底上将它们从氦液滴中去除,用于使用高分辨率透射电子显微镜 (TEM) 和 X 射线光电子能谱 (XPS) 的原位研究。TEM 成像用于估计纳米颗粒的尺寸,在使用的条件下,这些纳米颗粒呈现双峰分布。我们还首次证明了金属纳米颗粒是通过氦液滴中金属原子的自组装形成的。Ni/Au 核壳纳米颗粒的 XPS 研究表明,不存在 Au 和 Ni 合金化时会发生的任何 Au 4f 芯能级位移,这为使用超流氦液滴成功形成核壳纳米颗粒提供了第一个直接证据。