Hydrothermal Synthesis of Functionalized Carbon Nanodots and Their Clusters as Ionic Probe for High Sensitivity and Selectivity for Sulfate Anions with Excellent Detection Level.

Nitrogen-doped carbon nanodots (CNDs) were synthesized and utilized as sensing probes to detect different anions and metallic ions within aqueous solutions. The pristine CNDs were developed through a one-pot hydrothermal synthesis. o-Phenylenediamine was used as the precursor. A similar hydrothermal synthesis technique in the presence of polyethylene glycol (PEG) was adopted to form the PEG-coated CND clusters (CND-100k). Through photoluminescence (PL) quenching, both CND and PEG-coated CND suspensions display ultra-high sensitivity and selectivity towards HSO4- anions (Stern-Volmer quenching constant (KSV) value: 0.021 ppm-1 for CND and 0.062 ppm-1 for CND-100k) with an ultra-low detection limit (LOD value: 0.57 ppm for the CND and 0.19 ppm for CND-100k) in the liquid phase. The quenching mechanism of N-doped CNDs towards HSO4- ions involves forming the bidentate as well as the monodentate hydrogen bonding with the sulfate anionic moieties. The detection mechanism of metallic ions analyzed through the Stern-Volmer formulation reveals that the CND suspension is well suited for the detection of Fe3+ (KSV value: 0.043 ppm-1) and Fe2+ (KSV value: 0.0191 ppm-1) ions, whereas Hg2+ (KSV value: 0.078 ppm-1) sensing can be precisely performed by the PEG-coated CND clusters. Accordingly, the CND suspensions developed in this work can be employed as high-performance PL probes for detecting various anions and metallic ions in the liquid phase.