School of Materials Science and Engineering, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, China.
J Am Chem Soc. 2017 Sep 20;139(37):12956-12967. doi: 10.1021/jacs.7b04545. Epub 2017 Sep 11.
The ability to tailor the size and shape of nanoparticles (NPs) enables the investigation into the correlation between these parameters and optical, optoelectronic, electrical, magnetic, and catalytic properties. Despite several effective approaches available to synthesize NPs with a hollow interior, it remains challenging to have a general strategy for creating a wide diversity of high-quality hollow NPs with different dimensions and compositions on demand. Herein, we report on a general and robust strategy to in situ crafting of monodisperse hairy hollow noble metal NPs by capitalizing on rationally designed amphiphilic star-like triblock copolymers as nanoreactors. The intermediate blocks of star-like triblock copolymers can associate with metal precursors via strong interaction (i.e., direct coordination or electrostatic interaction), followed by reduction to yield hollow noble metal NPs. Notably, the outer blocks of star-like triblock copolymers function as ligands that intimately and permanently passivate the surface of hollow noble metal NPs (i.e., forming hairy permanently ligated hollow NPs with superior solubility in nonpolar solvents). More importantly, the diameter of the hollow interior and the thickness of the shell of NPs can be readily controlled. As such, the dimension-dependent optical properties of hollow NPs are scrutinized by combining experimental studies and theoretical modeling. The dye encapsulation/release studies indicated that hollow NPs may be utilized as attractive guest molecule nanocarriers. As the diversity of precursors are amenable to this star-like triblock copolymer nanoreactor strategy, it can conceptually be extended to produce a rich variety of hairy hollow NPs with different dimensions and functionalities for applications in catalysis, water purification, optical devices, lightweight fillers, and energy conversion and storage.
定制纳米粒子（NPs）的大小和形状的能力使人们能够研究这些参数与光学、光电、电学、磁学和催化性能之间的相关性。尽管有几种有效的方法可用于合成具有中空内部的 NPs，但仍然难以开发一种通用策略，以便根据需要按需创建具有不同尺寸和组成的各种高质量的空心 NPs。在此，我们报告了一种通用且稳健的策略，通过合理设计的两亲性星形嵌段共聚物作为纳米反应器，原位制备单分散的毛发状空心贵金属 NPs。星形嵌段共聚物的中间嵌段可以通过强相互作用（例如直接配位或静电相互作用）与金属前体结合，然后还原得到空心贵金属 NPs。值得注意的是，星形嵌段共聚物的外部嵌段作为配体，可紧密且永久地钝化空心贵金属 NPs 的表面（即形成具有优异非极性溶剂溶解度的毛发状永久配位的空心 NPs）。更重要的是，空心 NPs 的内径和壳层厚度可以很容易地控制。因此，通过结合实验研究和理论建模，研究了空心 NPs 的尺寸依赖性光学性质。染料包封/释放研究表明，空心 NPs 可用作有吸引力的客体分子纳米载体。由于这种星形嵌段共聚物纳米反应器策略适用于多种前体，因此可以将其概念扩展到用于催化、水净化、光学器件、轻质填料以及能量转换和存储等领域的不同尺寸和功能的各种毛发状空心 NPs 的制备。
