Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 16628 - Prague 6, Czech Republic.
Department of Chemical Engineering, Faculty of Geotechnical Sciences and Environmental Management, Cyprus University of Technology, 3036 Limassol, Cyprus.
Nanoscale Horiz. 2022 Aug 22;7(9):941-1015. doi: 10.1039/d2nh00111j.
A variety of colloidal chemical approaches has been developed in the last few decades for the controlled synthesis of nanostructured materials in either water or organic solvents. Besides the precursors, the solvents, reducing agents, and the choice of surfactants are crucial for tuning the composition, morphology and other properties of the resulting nanoparticles. The ligands employed include thiols, amines, carboxylic acids, phosphines and phosphine oxides. Generally, adding a single ligand to the reaction mixture is not always adequate to yield the desired features. In this review, we discuss in detail the role of the oleic acid/oleylamine ligand pair in the chemical synthesis of nanoparticles. The combined use of these ligands belonging to two different categories of molecules aims to control the size and shape of nanoparticles and prevent their aggregation, not only during their synthesis but also after their dispersion in a carrier solvent. We show how the different binding strengths of these two molecules and their distinct binding modes on specific facets affect the reaction kinetics toward the production of nanostructures with tailored characteristics. Additional functions, such as the reducing function, are also noted, especially for oleylamine. Sometimes, the carboxylic acid will react with the alkylamine to form an acid-base complex, which may serve as a binary capping agent and reductant; however, its reducing capacity may range from lower to much lower than that of oleylamine. The types of nanoparticles synthesized in the simultaneous presence of oleic acid and oleylamine and discussed herein include metal oxides, metal chalcogenides, metals, bimetallic structures, perovskites, upconversion particles and rare earth-based materials. Diverse morphologies, ranging from spherical nanoparticles to anisotropic, core-shell and hetero-structured configurations are presented. Finally, the relation between tuning the resulting surface and volume nanoparticle properties and the relevant applications is highlighted.
在过去的几十年中,已经开发出了各种胶体化学方法,用于在水或有机溶剂中控制合成纳米结构材料。除了前体之外,溶剂、还原剂和表面活性剂的选择对于调整所得纳米粒子的组成、形态和其他性质至关重要。所使用的配体包括硫醇、胺、羧酸、膦和氧化膦。通常,向反应混合物中添加单一配体并不总是足以产生所需的特性。在这篇综述中,我们详细讨论了油酸/油胺配体对在纳米粒子的化学合成中的作用。这两种配体属于两种不同类别的分子,它们的联合使用旨在控制纳米粒子的尺寸和形状,并防止它们聚集,不仅在合成过程中,而且在将它们分散在载体溶剂中之后也是如此。我们展示了这两种分子的不同结合强度及其在特定晶面上的不同结合模式如何影响产生具有定制特性的纳米结构的反应动力学。还注意到了其他功能,例如还原功能,特别是对于油胺。有时,羧酸会与烷基胺反应形成酸碱络合物,该络合物可以用作二元封端剂和还原剂;然而,其还原能力可能从低于油胺到远低于油胺。本文讨论了在油酸和油胺同时存在下合成的纳米粒子的类型,包括金属氧化物、金属硫属化物、金属、双金属结构、钙钛矿、上转换粒子和基于稀土的材料。呈现了从球形纳米粒子到各向异性、核壳和异质结构的各种形态。最后,强调了调整所得表面和体积纳米粒子性质与相关应用之间的关系。