配体-表面界面及其对纳米粒子性质的影响,Accounts of Chemical Research

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配体-表面界面及其对纳米粒子性质的影响
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2023-09-05 , DOI: 10.1021/acs.accounts.3c00416
Jwa-Min Nam ₁ , Jonathan S Owen ₂ , Dmitri V Talapin ₃

Affiliation

化学研究特刊“纳米颗粒的配体和表面化学”的客座编辑。几十年来，学术界和工业界的科学家和工程师一直在积极研究半导体、金属、磁体和其他功能材料的胶体纳米颗粒。胶体纳米粒子提供了对成核和生长以及表面反应性的特殊性的见解，而业界在纳米粒子中看到了将无机固体的典型功能与聚合物的结构灵活性和可加工性相结合的独特机会。这两项研究的核心是无机纳米粒子核心与共价或静电结合到核心表面的表面配体之间的界面（图 1）。这些表面配体是纳米材料的组成部分。它们指导纳米颗粒的形成，影响其化学反应性和电子结构，并介导与环境的相互作用。因此，核心-配体相互作用的研究以及配体多样化新方法的设计是与纳米科学密不可分的一个研究领域。图 1. 典型的胶体纳米颗粒由核心和表面配体组成。（根据 Zherebetskyy, D. 等人的修改进行改编。Science 2014 , 344 , 1380 。）本期特刊中包含的内容探讨了与纳米粒子“生命”不同阶段的纳米粒子配体的结构和功能相关的重要问题，从成核在诊断和光电设备中的应用。配体-表面键合的强度和配体的覆盖度对纳米颗粒的成核和生长具有重要影响。配体排列及其结合平衡和交换反应性的更详细表征可以告诉我们配体对纳米颗粒形成的影响。结合和交换的核心尺寸依赖性与纳米颗粒的成核和生长动力学及其与合成后纳米颗粒多分散性的联系尤其相关。核磁共振 (NMR) 光谱已被证明是原位研究表面-配体相互作用的宝贵工具，特别是考虑到其数量性质。最近，核磁共振波谱已被用来解决表面配体结合和覆盖的异质性。包括定量电子显微镜方法在内的新技术可以帮助确定配体的空间分布。表面的计算描述提供了另一种补充方法，可以在更精细的水平上理解配体壳结构。这些方法可以帮助我们了解配体引导纳米粒子形成并控制纳米粒子形状、暴露的面和最终产品的相的方式。有机和无机、分子和晶体化合物在许多方面是相互补充的。近年来，人们做出了巨大的努力，将这些世界的优点融合到混合物质中，将有机分子的多样性和模块化与无机固体的电子、热和机械特性结合起来。金属有机框架是此类杂化材料的一个很好的例子。具有有机表面配体的无机纳米粒子代表了桥接有机和无机、分子和固态成分的另一种多功能平台（图1）。在无机纳米颗粒表面添加有机功能会影响颗粒的分散性和组装性，并调节表面与其环境的相互作用。在生物学背景下，这些因素影响颗粒在组织内的分布方式并决定它们的治疗和诊断效用。表面配体还影响纳米颗粒与传感和治疗应用中特定分析物或细胞类型的相互作用。表面配体直接影响纳米颗粒主体的电子结构，并可以提高半导体量子点的光致发光效率。类似地，配体结合影响过渡金属纳米粒子表面催化反应的反应性和选择性。了解表面-配体相互作用的基本物理和化学原理可以为现实世界的应用带来更复杂的设备和催化剂。例如，纳米颗粒的突出应用之一是商业上成功的 QLED 电视，其中量子点用作颜色转换器。红外光电探测器和电致发光量子点器件的持续发展也取决于纳米粒子表面配体的优化。表面配体在所有电子和光电器件中发挥着关键作用，它们调节电子进出纳米颗粒核心的传输。此外，配体可用于通过二维和三维增材制造促进纳米晶体在器件中的集成。在许多方面，纳米粒子及其表面配体的研究是类似于有机聚合物的大分子科学的一个不断发展的分支。该学科的基础正在积极发展，商业应用的数量和重要性都在不断增长。这方面的工作还远未完成──固体分子界面的复杂性将带来许多难题和技术突破的机会。这篇文章尚未被其他出版物引用。图 1. 典型的胶体纳米颗粒由核心和表面配体组成。（改编自 Zherebetskyy, D. 等人的修改。科学 2014 年，344，1380。）

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The Ligand–Surface Interface and Its Influence on Nanoparticle Properties

Guest Editorial for the Accounts of Chemical Research special issue “Ligand and Surface Chemistry of Nanoparticles”. Colloidal nanoparticles of semiconductors, metals, magnets, and other functional materials have been actively researched for several decades by both academic and industrial scientists and engineers. Colloidal nanoparticles offer insights into the peculiarities of nucleation and growth and the reactivity of surfaces, while the industry sees in nanoparticles a unique opportunity to combine functionalities typical for inorganic solids with structural flexibility and processability of polymers. Central to both of these pursuits is the interface between the inorganic nanoparticle core and the surface ligands that are covalently or electrostatically bound to the core surface (Figure 1). These surface ligands are integral components of nanomaterials. They direct nanoparticle formation, influence their chemical reactivity and electronic structure, and mediate interactions with the environment. The study of core–ligand interaction and the design of new ways to diversify the ligands is therefore an area of study that is inextricably linked to nanoscience. Figure 1. A typical colloidal nanoparticle consists of a core and surface ligands. (Adapted with modifications from Zherebetskyy, D., et al. Science 2014, 344, 1380.) Accounts contained within this special issue explore the important questions related to the structure and function of nanoparticle ligands at different stages of nanoparticle “life”, from nucleation to the applications in diagnostics and optoelectronic devices. The strength of the ligand–surface bonding and the coverage of ligands have an important influence on the nanoparticle nucleation and growth. A more detailed characterization of the arrangements of ligands and their binding equilibria and exchange reactivity can teach us about the influence of ligands on the formation of nanoparticles. The core size dependence of the binding and exchange is especially relevant to the nucleation and growth kinetics of nanoparticles and their connection to the nanoparticle polydispersity after synthesis. Nuclear magnetic resonance (NMR) spectroscopy has proven to be a valuable tool to study surface–ligand interactions in situ, especially given its quantitative nature. Recently, NMR spectroscopy has been used to address the heterogeneity of surface ligand binding and coverage. New techniques including quantitative electron microscopy methods can help determine the spatial distribution of ligands. Computational descriptions of surfaces provide another complementary approach to understanding the ligand shell structure on a much finer level. Such approaches can help us understand the ways that ligands direct the formation of nanoparticles and control the nanoparticle shapes, the facets exposed, and the phase of the final product. Organic and inorganic, molecular and crystalline compounds are, in many aspects, complementary to each other. In recent years, there have been significant efforts to merge the benefits of these worlds into hybrid matter that combines the diversity and modularity of organic molecules with the electronic, thermal, and mechanical properties of inorganic solids. Metal–organic frameworks are a good example of such hybrid materials. Inorganic nanoparticles with organic surface ligands represent another versatile platform for bridging organic and inorganic, molecular and solid-state constituents (Figure 1). Appending organic functionality to inorganic nanoparticle surfaces influences the dispersibility and assembly of particles and modulates the interaction of surfaces with their environment. In a biological context, these factors influence how particles distribute within tissue and dictate their therapeutic and diagnostic utility. Surface ligands also influence the interaction of nanoparticles with specific analytes or cell types in sensing and therapeutic applications. Surface ligands directly influence the electronic structure of their nanoparticle hosts and can increase the photoluminescence efficiency of semiconductor quantum dots. Similarly, ligand binding influences the reactivity and the selectivity of catalytic reactions at the surfaces of transition-metal nanoparticles. Understanding the underlying physics and chemistry of the surface–ligand interactions can lead to more sophisticated devices and catalysts for real-world applications. For example, one of the prominent applications of nanoparticles is commercially successful QLED TVs where quantum dots are used as color converters. Ongoing development of infrared photodetectors and electroluminescent quantum dot devices also depends on the optimization of the nanoparticle surface ligands. Surface ligands play key roles in all electronic and optoelectronic devices where they modulate the transport of electrons into and out of nanoparticle cores. Moreover, ligands can be used to facilitate integration of nanocrystals in devices by additive manufacturing in two and three dimensions. In many ways, the study of nanoparticles and their surface ligands is a growing branch of macromolecular science akin to organic polymers. The foundations of this discipline are actively developing, and commercial applications are growing in number and importance. The work in this regard is far from complete─the complexity of the solid-molecule interfaces will bring many puzzles and opportunities for technological breakthroughs. This article has not yet been cited by other publications. Figure 1. A typical colloidal nanoparticle consists of a core and surface ligands. (Adapted with modifications from Zherebetskyy, D., et al. Science 2014, 344, 1380.)

更新日期：2023-09-06

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