Jakhmola Anshuman, Vecchione Raffaele, Onesto Valentina, Gentile Francesco, Celentano Maurizio, Netti Paolo Antonio
Istituto Italiano di Tecnologia, IIT@CRIB, Largo Barsanti e Matteucci 53, 80125 Napoli, Italy.
Centro di Ricerca Interdipartimentale sui Biomateriali CRIB, Università di Napoli Federico II, Piazzale Tecchio 80, 80125 Napoli, Italy.
Nanomaterials (Basel). 2021 Jan 18;11(1):236. doi: 10.3390/nano11010236.
Gold nanoparticles depending on their shape and mixtures of multiple shapes can exhibit peculiar optical properties, including the dichroic effect typical of the Lycurgus cup, which has puzzled scientists for a long time. Such optical properties have been recently exploited in several fields such as paint technology, sensors, dichroic polarizers, display (LCD) devices, laser applications, solar cells and photothermal therapy among others. In this article, we have demonstrated a simple room temperature one-pot synthesis of gold sol displaying a dichroic effect using a slow reduction protocol involving only trisodium citrate as a reducing agent. We found that the dichroic gold sol can be easily formed at room temperature by reducing gold salt by trisodium citrate below a certain critical concentration. The sol displayed an orangish-brown color in scattered/reflected light and violet/blue/indigo/purple/red/pink in transmitted light, depending on the experimental conditions. With minor changes such as the introduction of a third molecule or replacing a small amount of water in the reaction mixture with ethanol, the color of the gold sol under transmitted light changed and a variety of shades of red, pink, cobalt blue, violet, magenta and purple were obtained. The main advantage of the proposed method lies in its simplicity, which involves the identification of the right ratio of the reactants, and simple mixing of reactants at room temperature with no other requirements. TEM micrographs displayed the formation of two main types of particles viz. single crystal gold nanoplates and polycrystalline faceted polyhedron nanoparticles. The mechanism of growth of the nanoplates and faceted polyhedron particles have been described by an enhanced diffusion limited aggregation numerical scheme, where it was assumed that both trisodium citrate and the gold ions in solution undergo a stochastic Brownian motion, and that the evolution of the entire system is regulated by a principle of energy minimization. The predictions of the model matched with the experiments with a good accuracy, indicating that the initial hypothesis is correct.
金纳米颗粒根据其形状以及多种形状的混合情况,会展现出奇特的光学特性,其中包括久负盛名的吕科斯杯所具有的二向色性效应,这一效应长期以来一直困扰着科学家们。此类光学特性最近已在多个领域得到应用,如涂料技术、传感器、二向色性偏振器、显示(液晶显示器)设备、激光应用、太阳能电池以及光热疗法等。在本文中,我们展示了一种简单的室温一锅法合成金溶胶的方法,该金溶胶通过仅使用柠檬酸钠作为还原剂的缓慢还原方案呈现出二向色性效应。我们发现,在室温下,当柠檬酸钠在一定临界浓度以下还原金盐时,很容易形成二向色性金溶胶。根据实验条件,该溶胶在散射/反射光中呈现橙棕色,而在透射光中呈现紫/蓝/靛/紫/红/粉色。通过一些微小的改变,例如引入第三种分子或用乙醇替代反应混合物中的少量水,透射光下金溶胶的颜色会发生变化,从而获得各种深浅不一的红色、粉色、钴蓝色、紫色、品红色和紫红色。所提出方法的主要优点在于其简单性,这涉及确定反应物的正确比例,以及在室温下简单混合反应物,无需其他条件。透射电子显微镜图像显示形成了两种主要类型的颗粒,即单晶金纳米板和多晶刻面多面体纳米颗粒。纳米板和刻面多面体颗粒的生长机制已通过一种增强的扩散限制聚集数值方案进行了描述,该方案假设溶液中的柠檬酸钠和金离子都经历随机布朗运动,并且整个系统的演化受能量最小化原则调控。该模型的预测与实验结果高度吻合,表明初始假设是正确的。