Guadagnini Andrea, Agnoli Stefano, Badocco Denis, Pastore Paolo, Pilot Roberto, Ravelle-Chapuis Régis, van Raap Marcela B Fernández, Amendola Vincenzo
Department of Chemical Sciences, Università di Padova, via Marzolo 1, I-35131, Padova, Italy.
Consorzio INSTM, UdR Padova, Italy.
Chemphyschem. 2021 Apr 7;22(7):657-664. doi: 10.1002/cphc.202100021. Epub 2021 Mar 19.
Nonequilibrium nanoalloys are metastable solids obtained at the nanoscale under nonequilibrium conditions that allow the study of kinetically frozen atoms and the discovery of new physical and chemical properties. However, the stabilization of metastable phases in the nanometric size regime is challenging and the synthetic route should be easy and sustainable, for the nonequilibrium nanoalloys to be practically available. Here we report on the one-step laser ablation synthesis in solution (LASiS) of nonequilibrium Au-Co alloy nanoparticles (NPs) and their characterization on ensembles and at the single nanoparticle level. The NPs are obtained as a polycrystalline solid solution stable in air and water, although surface cobalt atoms undergo oxidation to Co(II). Since gold is a renowned plasmonic material and metallic cobalt is ferromagnetic at room temperature, these properties are both found in the NPs. Besides, surface conjugation with thiolated molecules is possible and it was exploited to obtain colloidally stable solutions in water. Taking advantage of these features, an array of magnetic-plasmonic dots was obtained and used for surface-enhanced Raman scattering experiments. Overall, this study confirms that LASiS is an effective method for the formation of kinetically stable nonequilibrium nanoalloys and shows that Au-Co alloy NPs are appealing magnetically responsive plasmonic building blocks for several nanotechnological applications.
非平衡纳米合金是在非平衡条件下于纳米尺度获得的亚稳固体,这使得对动力学冻结原子的研究以及新物理和化学性质的发现成为可能。然而,在纳米尺寸范围内稳定亚稳相具有挑战性,并且合成路线应该简单且可持续,以便非平衡纳米合金能够实际应用。在此,我们报道了非平衡金 - 钴合金纳米颗粒(NPs)的溶液一步激光烧蚀合成(LASiS)及其在整体和单个纳米颗粒水平上的表征。这些纳米颗粒以多晶固溶体形式获得,在空气和水中稳定,尽管表面钴原子会氧化为Co(II)。由于金是著名的等离子体材料,而金属钴在室温下是铁磁性的,这些性质在纳米颗粒中均有体现。此外,与硫醇化分子进行表面共轭是可行的,并利用这一点获得了在水中胶体稳定的溶液。利用这些特性,制备了一系列磁性 - 等离子体点并用于表面增强拉曼散射实验。总体而言,这项研究证实LASiS是形成动力学稳定的非平衡纳米合金的有效方法,并表明金 - 钴合金纳米颗粒是用于多种纳米技术应用的有吸引力的磁响应等离子体构建块。