Interfacial Assembly of Tunable Anisotropic Nanoparticle Architectures
Interfacial Assembly of Tunable Anisotropic Nanoparticle Architectures
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DOI：
10.1021/acsnano.8b08733
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发表时间：
2019-04-01
期刊：
影响因子：
17.1
通讯作者：
Arya, Gaurav
中科院分区：
文献类型：
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作者：
Tang, Tsung-Yeh;Zhou, Yilong;Arya, Gaurav
我们提出了一种将球形纳米颗粒（NP）组装成聚合物基质中的各向异性结构的策略。该方法利用形成双层的两种相互不混溶的聚合物之间的界面张力以及两个聚合物层与颗粒上聚合物接枝物的相容性差异，将纳米颗粒捕获在平行于界面的二维平面内。通过纳米粒子接枝密度精确调整捕获平面位置的能力，以及将多个相互作用的粒子捕获在不同平面内的能力，可以用于将纳米粒子组装成界面附近的非常规排列。我们对聚合物双层中的聚合物接枝纳米粒子进行了分子动力学模拟，以证明所提出的方法在距界面可调距离处捕获纳米粒子并将其组装成各种不寻常的纳米结构的可行性。我们说明了纳米粒子团簇的组装，例如相对于界面具有可调倾斜的二聚体和具有可调弯曲角度的三聚体，以及各向异性宏观相，包括蛇形和分支结构、脊状六边形单层和方形有序双层。我们还开发了一个理论模型来预测捕获在界面处或界面附近的纳米粒子的首选位置和自由能，这有助于指导聚合物接枝纳米粒子的设计，以实现目标纳米粒子结构。总体而言，这项工作表明，纳米粒子的界面组装可能是制造下一代聚合物纳米复合材料的一种有前景的方法，在等离激元、电子学、光学和催化等领域具有潜在的应用，在这些领域中，需要精确排列聚合物嵌入的纳米粒子来实现功能。
We propose a strategy for assembling spherical nanoparticles (NPs) into anisotropic architectures in a polymer matrix. The approach takes advantage of the interfacial tension between two mutually immiscible polymers forming a bilayer and differences in the compatibility of the two polymer layers with polymer grafts on particles to trap NPs within two-dimensional planes parallel to the interface. The ability to precisely tune the location of the entrapment planes via the NP grafting density, and to trap multiple interacting particles within distinct planes, can then be used to assemble NPs into unconventional arrangements near the interface. We carry out molecular dynamics simulations of polymer-grafted NPs in a polymer bilayer to demonstrate the viability of the proposed approach in both trapping NPs at tunable distances from the interface and assembling them into a variety of unusual nanostructures. We illustrate the assembly of NP clusters, such as dimers with tunable tilt relative to the interface and trimers with tunable bending angle, as well as anisotropic macroscopic phases, including serpentine and branched structures, ridged hexagonal monolayers, and square-ordered bilayers. We also develop a theoretical model to predict the preferred positions and free energies of NPs trapped at or near the interface that could help guide the design of polymer-grafted NPs for achieving target NP architectures. Overall, this work suggests that interfacial assembly of NPs could be a promising approach for fabricating next-generation polymer nanocomposites with potential applications in plasmonics, electronics, optics, and catalysis where precise arrangement of polymer embedded NPs is required for function.