University of Bremen, Institute of Applied and Physical Chemistry, Leobener Str. NW2, 28359, Bremen, Germany.
Nanoscale. 2012 Mar 7;4(5):1658-64. doi: 10.1039/c2nr11082b. Epub 2012 Feb 2.
We present a facile method for the preparation of bimetallic AuAg nanoparticles (NPs) with controlled size and composition rendering them ideally suitable for optical and catalytic applications. In analogy to methods for the generation of monometallic Au and Ag NPs, AuAg NPs were prepared inside polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block-copolymer micelles formed in toluene, by loading the P4VP cores of the micelles first with AgNO(3) and then with HAuCl(4). In contrast to the reverse sequence of loading, homogenously bimetallic AuAg particle arrays were achieved after reduction carried out in solution with hydrazine monohydrate as the reducing agent. TEM reveals that stable and spherical NPs can be prepared well separated from one another and with a narrow size distribution with diameters of ∼3 nm. The bimetallic NP composition was confirmed by energy-dispersive X-ray spectroscopy (EDX) of single NPs. The atomic ratio of Ag and Au contained in single particles is in good agreement with the relative concentrations of both metals used in the synthesis which was confirmed by atomic absorption spectroscopy. The atomic ratio Au : Ag was systematically varied between 3 : 1 and 1 : 3. For all ratios UV-vis spectra showed a single plasmon band. Its wavelength varied from 430 for Au : Ag = 1 : 3 to 515 nm for Au : Ag = 3 : 1, showing a linear dependence on the relative amount of gold within the range of plasmon wavelengths from monometallic gold (538 nm) to silver (415 nm).
我们提出了一种制备具有可控尺寸和组成的双金属 AuAg 纳米粒子(NPs)的简便方法,使它们非常适合光学和催化应用。类似于制备单金属 Au 和 Ag NPs 的方法,我们在甲苯中制备了 AuAg NPs,通过首先将 AgNO3 加载到 PS-b-P4VP 嵌段共聚物胶束的 P4VP 核中,然后加载 HAuCl4。与加载的相反顺序相反,在用肼一水合物作为还原剂在溶液中进行还原后,实现了均匀的双金属 AuAg 粒子阵列。TEM 揭示可以制备稳定的、球形的 NPs,它们彼此之间很好地分离,具有较窄的粒径分布,直径约为 3nm。通过对单个 NPs 进行能量色散 X 射线光谱(EDX)分析,证实了双金属 NP 的组成。单个颗粒中 Ag 和 Au 的原子比与合成中使用的两种金属的相对浓度非常吻合,这通过原子吸收光谱得到了证实。Au:Ag 原子比被系统地从 3:1 变化到 1:3。对于所有比例,UV-vis 光谱都显示出单个等离子体带。其波长从 Au:Ag = 1:3 时的 430nm 变化到 Au:Ag = 3:1 时的 515nm,在从单金属金(538nm)到银(415nm)的等离子体波长范围内表现出线性依赖于金的相对含量。