Constructing Functional Mesostructured Materials from Colloidal Nanocrystal Building Blocks

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• 作者：Delia J. Milliron ; Raffaella Buonsanti ; Anna Llordes ; Brett A. Helms
• 刊名：Accounts of Chemical Research
• 出版年：2014
• 出版时间：January 21, 2014
• 年：2014
• 卷：47
• 期：1
• 页码：236-246
• 全文大小：611K
• ISSN：1520-4898

文摘

Through synthesizing colloidal nanocrystals (NCs) in the organic phase, chemists gain fine control over their composition, size, and shape. Strategies for arranging them into ordered superlattices have followed closely behind synthetic advances. Nonetheless, the same hydrophobic ligands that help their assembly also severely limit interactions between adjacent nanocrystals. As a result, examples of nanocrystal-based materials whose functionality derives from their mesoscale structure have lagged well behind advances in synthesis and assembly.
In this Account, we describe how recent insights into NC surface chemistry have fueled dramatic progress in functional mesostructures. In these constructs, intimate contact between NCs as well as with heterogeneous components is key in determining macroscopic behavior. The simplest mesoscale assemblies we consider are networks of NCs constructed by in situ replacement of their bulky, insulating surface ligands with small molecules. Transistors are a test bed for understanding conductivity, setting the stage for new functionality. For instance, we demonstrated that by electrochemically charging and discharging networks of plasmonic metal oxide NCs, the transmittance of near infrared light can be strongly and reversibly modulated.
When we assemble NCs with heterogeneous components, there is an even greater potential for generating complex functionality. Nanocomposites can exhibit favorable characteristics of their component materials, yet the interaction between components can also have a strong influence. Realizing such opportunities requires an intimate linking of embedded NCs to the surrounding matrix phase. We accomplish this link by coordinating inorganic anionic clusters directly to NC surfaces. By exploiting this connection, we found enhanced ionic conductivity in Ag₂S-in-GeS₂ nanocrystal-in-glass electrodes. In another example, we also found enhanced optical contrast when linking electrochromic niobium oxide to embedded tin-doped indium oxide (ITO) NCs. These dramatic effects emerge from reconstruction of the inorganic glass immediately adjacent to the NC interface.
When co-assembling NCs with block copolymers, direct coordination of the polymer to NC surfaces again opens new opportunities for functional mesoscale constructs. We strip NCs of their native ligands and design block copolymers containing a NC tethering domain that bonds strongly, yet dynamically, to the resulting open coordination sites. This strategy enables their co-assembly at high volume fractions of NCs and leads to well-ordered mesoporous NC networks. We find these architectures to be exceptionally stable under chemical transformations driven by cation insertion, removal, and exchange.
These developments offer a modular toolbox for arranging NCs deliberately with respect to heterogeneous elements and open space. We have control over metrics that define such architectures from the atomic scale (bonding and crystal structure) through the mesoscale (crystallite shapes and sizes and pore dimensions). By tuning these parameters and better understanding the interactions between components, we look forward to boundless opportunities to employ mesoscale structure, in tandem with composition, to develop functional materials.