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通过半种子法快速合成高单分散性的 Au(x)Ag(1-x)合金纳米粒子。

Rapid synthesis of highly monodisperse Au(x)Ag(1-x) alloy nanoparticles via a half-seeding approach.

机构信息

Department of Chemical and Biomolecular Engineering and KAUST-NUS GCR Program, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260.

出版信息

Langmuir. 2011 May 3;27(9):5633-43. doi: 10.1021/la2005216. Epub 2011 Apr 4.

Abstract

Gold-silver alloy Au(x)Ag(1-x) is an important class of functional materials promising new applications across a wide array of technological fields. In this paper, we report a fast and facile synthetic protocol for preparation of highly monodisperse Au(x)Ag(1-x) alloy nanoparticles in the size range of 3-6 nm. The precursors employed in this work are M(I)-alkanethiolates (M = Au and Ag), which can be easily prepared by mixing common chemicals such as HAuCl(4) or AgNO(3) with alkanethiols at room temperature. In this half-seeding approach, one of the M(I)-alkanethiolates is first heated and reduced in oleylamine solvent, and freshly formed metal clusters will then act as premature seeds on which both the first and second metals (from M(I)-alkanethiolates, M = Au and Ag) can grow accordingly without additional nucleation and thus achieve high monodispersity for product alloy nanoparticles. Unlike in other prevailing methods, both Au and Ag elements present in these solid precursors are in the same monovalent state and have identical supramolecular structures, which may lead to a more homogeneous reduction and complete interdiffusion at elevated reaction temperatures. When the M(I)-alkanethiolates are reduced to metallic forms, the detached alkanethiolate ligands will serve as capping agent to control the growth. More importantly, composition, particle size, and optical properties of Au(x)Ag(1-x) alloy nanoparticles can be conveniently tuned with this approach. The optical limiting properties of the prepared particles have also been investigated at 532 and 1064 nm using 7 ns laser pulses, which reveals that the as-prepared alloy nanoparticles exhibit outstanding broadband optical limiting properties with low thresholds.

摘要

金-银合金 Au(x)Ag(1-x) 是一类重要的功能材料,有望在广泛的技术领域中开辟新的应用。本文报道了一种快速简便的方法,用于制备尺寸在 3-6nm 范围内的高度单分散 Au(x)Ag(1-x) 合金纳米粒子。该工作中使用的前驱体是 M(I)-烷硫醇盐(M = Au 和 Ag),可以通过将 HAuCl(4)或 AgNO(3)等常见化学品与烷硫醇在室温下混合来轻易制备。在这种半种子法中,首先将一种 M(I)-烷硫醇盐加热还原在油胺溶剂中,新形成的金属团簇将作为早期种子,随后两种金属(来自 M(I)-烷硫醇盐,M = Au 和 Ag)可以在其上相应地生长,而无需额外的成核,从而实现产物合金纳米粒子的高度单分散性。与其他流行的方法不同,这些固态前驱体中存在的 Au 和 Ag 元素均处于单价态且具有相同的超分子结构,这可能导致在较高反应温度下还原更均匀且完全互扩散。当 M(I)-烷硫醇盐还原为金属形式时,脱离的烷硫醇配体将充当封端剂以控制生长。更重要的是,通过这种方法可以方便地调节 Au(x)Ag(1-x) 合金纳米粒子的组成、粒径和光学性质。还使用 7ns 激光脉冲在 532nm 和 1064nm 处研究了所制备的粒子的光限幅性质,结果表明,所制备的合金纳米粒子具有低阈值的宽带光限幅性能。

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