Kinetically Controlled Self-Assembly of Binary Polymer-Grafted Nanocrystals into Ordered Superstructures via Solvent Vapor Annealing
Kinetically Controlled Self-Assembly of Binary Polymer-Grafted Nanocrystals into Ordered Superstructures via Solvent Vapor Annealing
复制标题
通过溶剂蒸气退火将二元聚合物接枝纳米晶体动力学控制自组装成有序超结构
DOI：
10.1021/acs.nanolett.1c00890
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发表时间：
2021
期刊：
影响因子：
10.8
通讯作者：
Ye, Xingchen
中科院分区：
文献类型：
--
作者：
Wang, Yi;Chen, Jun;Zhu, Chenhui;Zhu, Baixu;Jeong, Soojin;Yi, Yi;Liu, Yang;Fiadorwu, Joshua;He, Peng;Ye, Xingchen
基于聚合物接枝纳米晶体（PGNC）的聚合物-无机纳米复合材料由于其独特的物理、化学和机械性能而使技术相关应用成为可能。虽然不同的PGNC超结构已经实现了通过蒸发驱动的自组装，这种方法提出了多方面的挑战，在实验上探测和控制组装动力学。在这里，我们报告了一个动力学控制的组装从一个均匀的无序PGNC混合物，利用溶剂蒸气退火（SVA）的二元超结构。使用NaZn 13型超结构作为模型系统，我们证明了在SVA过程中改变溶剂蒸气压可以精确控制PGNC组装的速率和程度，从而获得几乎完整的二元PGNC结晶动力学途径。动力学逮捕的中间体的表征表明，大会遵循多步结晶途径，涉及pGNCs的spinodal-like preordering之前，NaZn 13成核。我们的工作开辟了新的途径，多组分PGNC超结构的合成表现出多功能性和新兴的性能，通过深入了解动力学途径。
Polymer-inorganic nanocomposites based on polymer-grafted nanocrystals (PGNCs) are enabling technologically relevant applications owing to their unique physical, chemical, and mechanical properties. While diverse PGNC superstructures have been realized through evaporation-driven self-assembly, this approach presents multifaceted challenges in experimentally probing and controlling assembly kinetics. Here, we report a kinetically controlled assembly of binary superstructures from a homogeneous disordered PGNC mixture utilizing solvent vapor annealing (SVA). Using a NaZn13-type superstructure as a model system, we demonstrate that varying the solvent vapor pressure during SVA allows for exquisite control of the rate and extent of PGNC assembly, providing access to nearly complete kinetic pathways of binary PGNC crystallization. Characterization of kinetically arrested intermediates reveals that assembly follows a multistep crystallization pathway involving spinodal-like preordering of PGNCs prior to NaZn13nucleation. Our work opens up new avenues for the synthesis of multicomponent PGNC superstructures exhibiting multifunctionalities and emergent properties through a thorough understanding of kinetic pathways.