Highly Sensitive and Selective Method for Detecting Ultratrace Levels of Aqueous Uranyl Ions by Strongly Photoluminescent-Responsive Amine-Modified Cadmium Sulfide Quantum Dots.

Abstract

Detection of ultratrace levels of aqueous uranyl ions without using sophisticated analytical instrumentation and a tedious sample preparation method is a challenge for environmental monitoring and mitigation. Here we present a novel yet simple analytical method for highly sensitive and specific detection of uranyl ions via photoluminescence quenching of CdS quantum dots. We have demonstrated a new approach for synthesizing highly water-soluble and strong photoluminescence-emitting CdS quantum dots (i.e., CdS-MAA and CdS-MAA-TU) of sizes less than 3 nm. The structural, morphological, and optical properties of both the batches of CdS quantum dots were thoroughly characterized by XRD, high-resolution transmission electron microscopy (HRTEM), zeta potential, UV-visible absorption, and photoluminescence spectroscopy. Compared to the batch of CdS quantum dots prepared by capping with only mercaptoacetic acid (CdS-MAA), the batch prepared by capping with mercaptoacetic acid and thiourea in tandem (CdS-MAA-TU) exhibited higher quantum yield= 16.64 ± 1.02%, and more importantly, CdS-MAA-TU exhibited significantly a higher order of photoluminescence quenching responses when treated with ultratrace concentrations of uranyl ions. Under the optimized conditions, the sensitivity of detecting uranyl ion by CdS-MAA-TU was several folds better (0.316 L/ μg) than that of CdS-MAA (0.0053 (L/μg/), as determined from their respective Stern-Volmer plots. Qualitatively, CdS-MAA-TU probe can be used for visual detection of uranyl ions of concentration greater than 5 μg/L. However, the instrumental method of analysis based on photoluminescence spectroscopy confirmed the feasibility for quantitative analysis of ultratrace concentrations of uranyl ions as implied from a very low limit of detection (LoD = 0.07 μg/L) and limit of quantification (LoQ = and 0.231 μg/L). Systematic studies revealed very high selectivity for uranyl ion detection, though minor interference from Cu(2+), Pb(2+), Hg(2+), CO3(2-), and SO4(2-) was found. The recovery analysis performed by spiking uranyl ions (0.5 μg/L to 10.0 μg/L) in groundwater and river water samples, confirmed the robustness of the as-developed CdS-MAA-TU QDs for detecting ultratrace levels of uranyl ions in real water sample matrix. The very simple and effective strategy reported here should facilitate developing reliable sensors for detecting uranyl ion contamination in drinking water.