Green, Water-Dispersible Photoluminescent On-Off-On Probe for Selective Detection of Fluoride Ions.

Abstract

Considering the high toxicity and widespread availability of fluoride ions in different environmental matrices, it is imperative to design a probe for its detection. In view of this, a selective fluorescent on-off-on probe based on carbon quantum dots (CQDs) and Eu3+ has been designed. We have synthesized water-soluble carboxylic acid-functionalized CQDs and monitored their interaction with Eu3+. Luminescence quenching in the CQD emission was observed (switch-off) on adding Eu3+ ions. We investigate the reason for this luminescence quenching using time-resolved emission and high-resolution transmission electron microscopy (HRTEM) studies and observed that both electron transfer from CQDs to Eu3+ and aggregation of CQDs are responsible for the luminescence quenching. ζ-Potential and X-ray photoelectron spectroscopy studies confirm Eu3+ binding with the COOH groups on CQD surface. Interestingly, luminescence regains after the addition of fluoride ions to the CQDs/Eu3+ system (switch-on). This has been assigned to the removal of Eu3+ from the CQD surface due to the formation of EuF3 and is confirmed by X-ray diffraction and HRTEM measurements. The sensitivity of the probe was tested by carrying out experiments with other competing ions and was found to be selective for fluoride ions. Experiments with variable concentrations of fluoride ions suggest that the working range of the probe is 1-25 ppm. The probe has been successfully tested for the detection of fluoride ions in a toothpaste sample and the results were compared to those of ion chromatography. To the best of our knowledge, this is the first report based on CQDs and Eu3+ for the detection of fluoride ions, wherein a clear mechanism of the detection has been demonstrated, which, in turn, will help to develop better detection methods. The suggested probe is green, economical, rapid, efficient, and, most importantly, selective and can be used for the detection of fluoride ions in real environmental samples.