A ratiometric electrochemical sensor for simultaneous detection of multiple heavy metal ions in water and herbal medicines based on methylene blue-functionalized metal–organic framework

Schematic ratio electrochemical sensor detection of Cd2+, Pb2+, and Hg2+. [Display omitted] •A ratiometric electrochemical sensor using methylene blue as internal reference detects Cd2+, Pb2+, and Hg2+.•The lowest detection limits were 11.08 nM for Cd2+, 5.47 nM for Pb2+, and 6.42 nM for Hg2+, respectively. (S/N = 3).•Simultaneous determination of Cd2+, Pb2+, and Hg2+ in real water and herbal medicine samples (Astragali Radix and Ginseng Radix et Rhizoma) was realized. Heavy metal contamination in water and herbal medicine poses a global threat to human health. There is a pressing need for the development of a simple and rapid method for simultaneous quantification. In this study, a ratiometric electrochemical sensor was first constructed using a hybrid material composed of methylene blue functionalized metal–organic framework (MB-UiO66-NH2) and multi-walled carbon nanotubes (MWCNTs). Then, MB-UiO66-NH2/MWCNTs harnessed the large specific surface area of UiO66-NH2 and good conductivity of MWCNTs, resulting in a sensor with superior analytical performance for Cd2+, Pb2+, and Hg2+ detection. Meanwhile, the ratiometric probe uses MB as an internal reference, with the ratio signal (Imetalion/IMB) serving as output. This ratiometric electrochemical sensor was able to enhance the reproducibility and reliability and eliminate interference, particularly in complex environments. Importantly, based on this ratiometric electrochemical platform, the low detection limit were 11.08 nM for Cd2+, 5.47 nM for Pb2+, and 6.42 nM for Hg2+, which realized the simultaneous, sensitive, and reliable detection. In addition, it has been successfully applied in real water and representative herbal medicine sample analysis. Therefore, this work provides a new approach for the risk assessment of heavy metal accumulation, which is conducive to safeguarding people's lives and health.