Electrochemical sensor based on amine- and thiol-modified multi-walled carbon nanotubes for sensitive and selective determination of uranyl ions in real water samples

Abstract

Novel selective and sensitive electrochemical sensors based on the modification of a carbon paste electrode (CPE) with novel amine- and thiol-functionalized multi-walled carbon nanotubes (MWCNT) have been developed for the detection and monitoring of uranyl ions in different real water samples. Multiwalled carbon nanotubes were grafted with 2-aminothiazole (AT/MWCNT) and melamine thiourea (MT/MWCNT) via an amidation reaction in the presence of dicyclohexyl carbodiimide (DCC) as a coupling agent. This modification for multiwalled carbon nanotubes has never been reported before. The amine and thiol groups were considered to be promising functional groups due to their high affinity toward coordination with uranyl ions. The modified multi-walled carbon nanotubes were characterized using different analytical techniques including FTIR, SEM, XPS, and elemental analysis. Subsequently, 10 wt% MT/MWCNT was mixed with 60 wt% graphite powder in the presence of 30 wt% paraffin oil to obtain a modified carbon paste electrode (MT/MWCNT/CPE). The electrochemical behavior and applications of the prepared sensors were examined using cyclic voltammetry, differential pulse anodic stripping voltammetry, and electrochemical impedance spectroscopy. The MT/MWCNT/CPE sensor exhibited a good linearity for UO₂²⁺ in the concentration range of 5.0 × 10⁻³ to 1.0 × 10⁻¹⁰ mol L⁻¹ with low limits of detection (LOD = 2.1 × 10⁻¹¹ mol L⁻¹) and quantification (LOQ = 7 × 10⁻¹¹ mol L⁻¹). In addition, high precision (RSD = 2.7%), good reproducibility (RSD = 2.1%), and high stability (six weeks) were displayed. Finally, MT-MWCNT@CPE was successfully utilized to measure the uranyl ions in an actual water sample with excellent recoveries (97.8–99.3%). These results demonstrate that MT-MWCNT@CPE possesses appropriate accuracy and is appropriate for environmental applications.