单烷基膦酸作为配体在纳米晶体合成中的应用

Evert Dhaene, P. Smet, Klaartje De Buysser, J. De Roo
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引用次数: 5

摘要

表面活性剂在胶体纳米晶体的合成中起着至关重要的作用。然而,目前只使用少数分子,油酸是最典型的例子。在这里,我们表明单烷基次膦酸是一种有趣的表面活性剂,其反应性介于羧酸和膦酸之间。我们首先介绍了正己基、2-乙基己基、正十四烷基、正十八烷基和油基次膦酸的合成。在高温纳米晶体合成(240-300°C)过程中,这些化合物是合适的表面活性剂。与膦酸相反,它们不形成聚酸酐凝胶。因此,用十八烷基次膦酸合成的CdSe量子点可以方便地纯化,并且在UV-Vis中没有背景散射。CdSe纳米晶体具有非常低的多分散性和高达18%的光致发光量子产率,而没有额外的壳层。此外,我们可以使用次膦酸配体合成CdSe和CdS纳米棒,并发现了显著的纯度(即没有四足杂质)。我们得出的结论是,对TOP-S和TOP-Se前体的反应性依次降低:羧酸镉>次膦酸镉>膦酸镉。通过引入第三类和中间类表面活性剂,我们增强了表面活性剂辅助合成的通用性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Mono-alkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis
Surfactants play a crucial role in the synthesis of colloidal nanocrystals. Nevertheless, only a handful molecules are currently used, oleic acid being the most typical example. Here, we show that mono-alkyl phosphinic acids are an interesting surfactant class with a reactivity that is intermediate between carboxylic acids and phosphonic acids. We first present the synthesis of n-hexyl, 2-ethylhexyl, n-tetradecyl, n-octadecyl, and oleyl phosphinic acid. These compounds are suitable surfactants during high-temperature nanocrystal synthesis (240-300°C). In contrast to phosphonic acids, they do not form poly anhydride gels. Consequently, CdSe quantum dots synthesized with octadecylphosphinic acid are conveniently purified, and are free from background scattering in UV-Vis. The CdSe nanocrystals have a very low polydispersity and a photoluminescence quantum yield up to 18%, without additional shell. Furthermore, we could synthesize CdSe and CdS nanorods using phosphinic acid ligands and found a remarkable purity (i.e. without tetrapod impurities). We conclude that the reactivity towards TOP-S and TOP-Se precursors decreases in the series: cadmium carboxylate > cadmium phosphinate > cadmium phosphonate. By introducing a third and intermediate class of surfactants, we enhance the versatility of surfactant-assisted syntheses.
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