Sperry Breena M, Kukhta Nadzeya A, Huang Yunping, Luscombe Christine K
Department of Materials Science and Engineering, University of Washington, Seattle, Washington 98195, United States.
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Chem Mater. 2023 Jan 12;35(2):570-583. doi: 10.1021/acs.chemmater.2c03006. eCollection 2023 Jan 24.
Aliphatic amine and carboxylic acid ligands are widely used as organic solvents during the bottom-up synthesis of inorganic nanoparticles (NPs). Although the ligands' ability to alter final NP properties has been widely studied, side reactivity of these ligands is emerging as an important mechanism to consider. In this work, we study the thermal decomposition of common ligands with varying functional groups (amines and carboxylic acids) and bond saturations (from saturated to polyunsaturated). Here, we investigate how these ligand properties influence decomposition in the absence and presence of precursors used in NP synthesis. We show that during the synthesis of inorganic chalcogenide NPs (CuZnSnS, Cu S, and SnS ) with metal acetylacetonate precursors and elemental sulfur, the ligand pyrolyzes, producing alkylated graphitic species. Additionally, there was less to no ligand decomposition observed during the sulfur-free synthesis of ZnO and CuO with metal acetylacetonate precursors. These results will help guide ligand selection for NP syntheses and improve reaction purity, an important factor in many applications.
在无机纳米颗粒（NP）的自下而上合成过程中，脂肪族胺和羧酸配体被广泛用作有机溶剂。尽管配体改变最终NP性质的能力已得到广泛研究，但这些配体的副反应正成为一个需要考虑的重要机制。在这项工作中，我们研究了具有不同官能团（胺和羧酸）和键饱和度（从饱和到多不饱和）的常见配体的热分解。在这里，我们研究了这些配体性质如何在不存在和存在NP合成中使用的前驱体的情况下影响分解。我们表明，在用金属乙酰丙酮前驱体和元素硫合成无机硫属化物NP（CuZnSnS、Cu₂S和SnS₂）的过程中，配体发生热解，生成烷基化石墨物种。此外，在用金属乙酰丙酮前驱体进行无硫合成ZnO和CuO的过程中，观察到配体分解较少或没有分解。这些结果将有助于指导NP合成的配体选择，并提高反应纯度，这在许多应用中是一个重要因素。
