MOE Key Laboratory for Analytical Science of Food Safety and Biology, Fujian Provincial Key Laboratory of Analysis and Detection for Food Safety, College of Chemistry, Fuzhou University, Fuzhou, Fujian350108, China.
Anal Chem. 2022 Dec 13;94(49):17142-17150. doi: 10.1021/acs.analchem.2c03494. Epub 2022 Nov 29.
Perovskite quantum dots (PQDs) as recently emerging electrochemiluminescence (ECL) luminophores have been paid much attention due to their good ECL activity, narrow ECL spectra, and easy preparation. However, the PQDs used for ECL sensing were mainly inherited from those PQDs prepared as strong fluorescence (FL) luminophores, which would limit the finding of highly ECL PQDs for sensing due to the very different mechanisms in generating excited-state luminophores between ECL and FL. In order to obtain highly electrochemiluminescent PQDs, for the first time we proposed to synthesize PQDs for ECL sensing rather than for FL-based analysis by optimizing the synthesis conditions. It was revealed that the volume of the precursor solution, the concentrations of CsBr and PbBr, the amount of capping reagents, and the synthesis reaction temperature all significantly affect the ECL activity of PQDs. On the basis of the optimization of the synthesis conditions, we obtained a new type of PQDs with high ECL activity. The new PQDs were characterized by several technologies, such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy dispersive X-ray spectrum, to be the hybrids of 3D PQDs (CsPbBr) and 0D PQDs (CsPbBr) with unique morphologies, i.e., CsPbBr@CsPbBr PQD nanoacanthospheres (PNAs), in which CsPbBr was as the core and CsPbBr served as the shell. The obtained CsPbBr@CsPbBr PNAs had much higher (>4 times) ECL activity than the prevailing 3D (CsPbBr) PQDs. Finally, the novel CsPbBr@CsPbBr PNAs have been applied for the ECL sensing of bisphenol A (BPA), showing a promising application of the highly electrochemiluminescent PQDs in analytical chemistry.
钙钛矿量子点(PQDs)作为新兴的电致化学发光(ECL)发光体,由于其良好的 ECL 活性、窄的 ECL 光谱和易于制备而受到广泛关注。然而,用于 ECL 传感的 PQDs 主要继承自那些作为强荧光(FL)发光体制备的 PQDs,由于 ECL 和 FL 之间产生激发态发光体的机制非常不同,这将限制高 ECL PQDs 用于传感的发现。为了获得高电致化学发光 PQDs,我们首次提出通过优化合成条件来合成用于 ECL 传感而不是基于 FL 分析的 PQDs。结果表明,前驱体溶液的体积、CsBr 和 PbBr 的浓度、封端试剂的量以及合成反应温度都对 PQDs 的 ECL 活性有显著影响。在优化合成条件的基础上,我们获得了一种新型的具有高 ECL 活性的 PQDs。新的 PQDs 通过几种技术进行了表征,如扫描电子显微镜、透射电子显微镜、X 射线衍射和能谱,它们是 3D PQDs(CsPbBr)和 0D PQDs(CsPbBr)的混合物,具有独特的形态,即 CsPbBr@CsPbBr PQD 纳米棘球(PNAs),其中 CsPbBr 作为核,CsPbBr 作为壳。所获得的 CsPbBr@CsPbBr PNA 的 ECL 活性比现有的 3D(CsPbBr)PQDs 高得多(>4 倍)。最后,将新型 CsPbBr@CsPbBr PNA 应用于双酚 A(BPA)的 ECL 传感,表明高电致化学发光 PQDs 在分析化学中有很好的应用前景。