Guadagnini Andrea, Agnoli Stefano, Badocco Denis, Pastore Paolo, Coral Diego, Fernàndez van Raap Marcela B, Forrer Daniel, Amendola Vincenzo
Department of Chemical Sciences, Università di Padova, via Marzolo 1, I-35131 Padova, Italy.
Physics Institute of La Plata (IFLP-CONICET), Physics Department Faculty of Exact Sciences, National University of La Plata, La Plata, Argentina; Departamento de Fisica, Universidad del Cauca, 193577 Popayán Colombia.
J Colloid Interface Sci. 2021 Mar;585:267-275. doi: 10.1016/j.jcis.2020.11.089. Epub 2020 Nov 25.
Appealing physical and chemical properties are foreseen in nanoparticles containing immiscible elements, despite their synthesis is challenging due to the unfavorable thermodynamics. Here we show that silver nanoparticles doped with Co can be achieved by a facile one-step route relying on laser ablation in liquid. Structural analysis suggests that the bimetallic nanoparticles consist of a matrix of face-centred cubic Ag rich of cobalt as point defects or dislocations, in a structure that is stable over time even in aqueous solution. This happens despite the complete immiscibility of the two metals at any temperature in the solid and liquid phase, as confirmed also by density functional theory calculations. The nonequilibrium Co-Ag nanoparticles benefit of silver features such as the plasmonic response and the easy surface chemistry with thiolated ligands, combined with the magnetic properties of cobalt. Importantly, plasmonics and magnetism are not quenched after mixing, contrary to what was observed in other bimetallic systems like the Au-Fe one. This opens the way to several technologically relevant applications and, as a proof of concept, we demonstrate magnetophoretic assembly of Co-Ag nanoparticles into arrays of plasmonic dots exploitable for surface-enhanced Raman spectroscopy.
尽管由于不利的热力学条件,含有不混溶元素的纳米颗粒的合成具有挑战性,但预计它们会具有吸引人的物理和化学性质。在这里,我们表明,通过基于液体中的激光烧蚀的简便一步法可以实现掺杂钴的银纳米颗粒。结构分析表明,双金属纳米颗粒由富含钴作为点缺陷或位错的面心立方银基质组成,即使在水溶液中,这种结构也能随时间保持稳定。尽管这两种金属在任何温度下在固相和液相中都完全不混溶,密度泛函理论计算也证实了这一点,但仍会发生这种情况。非平衡的钴 - 银纳米颗粒兼具银的特性,如等离子体响应和与硫醇化配体的简便表面化学性质,以及钴的磁性。重要的是,与在其他双金属系统(如金 - 铁系统)中观察到的情况相反,混合后等离子体和磁性并未淬灭。这为多种技术相关应用开辟了道路,作为概念验证,我们展示了将钴 - 银纳米颗粒磁泳组装成可用于表面增强拉曼光谱的等离子体点阵列。