Double-Emission Ratiometric Fluorescent Sensors Composed of Rare-Earth-Doped ZnS Quantum Dots for Hg2+ Detection

Quantum dots (QDs) are a class of zero-dimensional nanocrystal materials, whose lengths are limited to 2-10 nm. Their unique advantages such as wide excitation spectra, narrow emission spectra, and high quantum yield make their application possible in fluorescence sensing, wherein QDs such as CdSe, CdTe, and CdS are used. Indeed, QDs have a wide range of applications in fluorescence sensing, and there have been many reports of applications based on QDs as ion probes. The emission spectra of QDs can be adjusted by changing the size of the QDs or doping them with other ions/elements. However, the high toxicity of Cd and the poor anti-interference ability of single-emission fluorescent probes greatly limit the applications of QDs in many fields. In this paper, ZnS QDs are doped with the rare-earth element Ce to form a low-toxicity double-emission ratiometric fluorescent sensor, ZnS:Ce, for Hg²⁺ detection. The results of transmission electron microscopy (TEM), X-ray diffractometry, X-ray photoelectron spectroscopy, and optical spectroscopy show that ZnS:Ce QDs were successfully synthesized. Under the optimal conditions, the concentration of Hg²⁺ was in the range of 10-100 μM, which had a linear relationship with the fluorescence intensity of the ZnS:Ce QDs: the linear correlation coefficient was 0.998, and the detection limit was 0.82 μM L^-1. In addition, the fluorescent sensor had good selectivity for Hg²⁺, and it was successfully applied to the detection of Hg²⁺ in laboratory water samples.