Petit Guillaume, Malherbe Cedric, Bianchi Pauline, Monbaliu Jean-Christophe M
Center for Integrated Technology and Organic Synthesis (CiTOS), MolSys Research Unit, University of Liège B-4000 Liège (Sart Tilman) Belgium
Mass Spectrometry Laboratory, MolSys Research Unit, University of Liège B-4000 Liège (Sart Tilman) Belgium.
Chem Sci. 2024 Jul 30;15(33):13148-59. doi: 10.1039/d4sc01135j.
An innovative approach to chalcogenide precursor synthesis and their subsequent use for the production of CdX (X = S, Se, Te) quantum dots (QDs) in water under scalable and intensified continuous flow conditions is introduced. Herein, tris(2-carboxyethyl)phosphine (TCEP) is identified as a novel, efficient and water-soluble vehicle for chalcogenide transfer to form CdX QDs under aqueous conditions. A comprehensive exploration of critical process parameters, including pH, chalcogen excess, and residence time, utilizing a Design of Experiments (DoE) approach is reported. Reaction kinetics are investigated in real-time using a combination of Raman spectroscopy and in-line P NMR spectroscopy. The conversion of TCEP into TCEP[double bond, length as m-dash]X (X = S, Se, Te) species is seamlessly adapted to continuous flow conditions. TCEP[double bond, length as m-dash]X precursors are subsequently employed in the synthesis of CdX QDs. Scalability trials are successfully demonstrated, with experiments conducted at flow rates of up to 80 mL min using a commercially available mesofluidic flow reactor with favorable metrics. Furthermore, biocompatible and aqueous CdSe/ZnS core-shell QDs are for the first time prepared in flow within a fully concatenated process. These results emphasize the potential for widespread biological or industrial applications of this novel protocol.
介绍了一种创新方法,用于硫族化物前驱体的合成及其随后在可扩展和强化的连续流动条件下于水中制备CdX(X = S、Se、Te)量子点(QDs)。在此,三(2-羧乙基)膦(TCEP)被确定为一种新型、高效且水溶性的载体,用于在水性条件下将硫族化物转移以形成CdX量子点。报道了利用实验设计(DoE)方法对关键工艺参数(包括pH值、硫族元素过量和停留时间)进行的全面探索。使用拉曼光谱和在线磷核磁共振光谱相结合的方法实时研究反应动力学。TCEP向TCEP[双键,长度为m破折号]X(X = S、Se、Te)物种的转化可无缝适应连续流动条件。随后将TCEP[双键,长度为m破折号]X前驱体用于CdX量子点的合成。成功进行了可扩展性试验,使用具有良好指标的市售微流体流动反应器,以高达80 mL/min的流速进行了实验。此外,首次在完全串联的流程中于流动状态下制备了生物相容性的水性CdSe/ZnS核壳量子点。这些结果强调了这种新方案在广泛的生物或工业应用中的潜力。