Rapid Synthesis of highly luminescent Carbon Quantum Dots using Low-Pressurized Microwave Solvothermal Heating

Kenta Hagiwara, S. Horikoshi
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Abstract

Since the first serendipity of carbon quantum dots (CQDs)1, it is expected to be used for imaging materials for reusable living bodies (e.g. Hela cells). However, the reported CQDs synthetic methods have yet to be at the practical levels; the quantum yields is low, and synthetic condition is over 5 hrs under more than 30 atms. In this research, we ameliorated the problems of CQDs synthesis and luminescence (quantum yields) by the novel synthesis protocol using microwave chemistry. Specifically, we synthesized high quantum yields CQDs (61%) by utilizing a microwave chemical synthesis, synthesizing at low pressure condition (lower than 5 atom) and short reaction time (3 hrs). The achievement of this high quantum yields made it clear that the contribution of polyethylene glycol (PEG) shell to CQDs is large. It was confirmed from the DLS and TEM image that the particle size of the synthesized particles was 8 to 13 nm (Fig. 1). On the other hand, the relationship between the polymerization degree of added PEG and the quantum yields to the addition amount is summarized in Table 1. The quantum yields of CQDs without addition of PEG was 16.7 %, while it was improved at 61.1 % when 0.6 g of PEG6000 (Molecular weight: 6000) was added.We succeeded in remarkably improving the quantum yields by using PEG, which is usually used as a protective agent, as a shell. By using this method, we succeeded in improving the quantum yields of the existing report by approximately 3 times. From the surface modified structure of PEG, the mechanism of improvement of quantum yields will be considered.[1] X. Xu et al., J. Am. Chem. Soc., 2004, 126, 12736–12737. 
利用低压微波溶剂热加热快速合成高发光碳量子点
由于碳量子点(CQDs)的首次发现,它有望用于可重复使用的活体(例如海拉细胞)的成像材料。然而,已报道的CQDs合成方法尚未达到实际水平;量子产率低,在30多台机器下的合成条件在5 HRS以上。在本研究中,我们通过微波化学的新合成方案改善了CQDs的合成和发光(量子产率)问题。具体而言,我们利用微波化学合成,在低压条件下(低于5个原子)和短反应时间(3小时)合成了高量子产率(61%)的CQDs。高量子产率的成就清楚地表明聚乙二醇(PEG)壳层对CQDs的贡献是巨大的。DLS和TEM图像证实,合成的颗粒粒径为8 ~ 13 nm(图1)。另一方面,添加的PEG的聚合度与量子产率与添加量的关系如表1所示。未添加PEG的CQDs的量子产率为16.7%,而添加0.6 g PEG6000(分子量为6000)的CQDs的量子产率为61.1%。我们成功地将通常用作保护剂的聚乙二醇作为壳层,显著提高了量子产率。通过使用这种方法,我们成功地将现有报告的量子产率提高了约3倍。从聚乙二醇的表面修饰结构出发,考虑提高量子产率的机理。[1]徐旭等。化学。Soc。浙江农业学报,2004,26(1):12736-12737。
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