Tripartite Detection and Sensing of Toxic Heavy Metals Using a Copper-Based Porphyrin Metal–Organic Framework

The detection of heavy metals in water sources is a critical concern for environmental preservation and public health. However, current electrochemical heavy metal sensors suffer from high sensing limits, cross-sensitivity, and poor selectivity. In this work, we present the possibility of an electrochemical sensor based on a copper (Cu) metal–organic framework for the detection of lead, cadmium, and mercury by replacing Cu metal nodes. The working electrode consists of a ∼5 μm thin layer of copper- tetracarboxyphenylporphyrin (Cu-TCPP) sheets that are adsorbed on a glassy carbon electrode (GCE). Upon interaction with Pb2+, Cd2+, and Hg2+, these ions are adsorbed on and incorporated into the metal nodes of the MOF. The adsorbed metallic species can be oxidized to the ionic form (Pb → Pb2+) electrochemically, which results in an oxidation response and enables the quantitative detection of these metals. The oxidation peak currents follow a (mostly) bimodal linear regression with a sensing range of up to 30 μM dependent on the deposition time and an ultralow limit of detection (LoD) of up to 5 nM. The system displays robust and selective sensing in saturated solutions of counterions and interfering metal ions (low error margins of <10%). This work represents the first report of a Cu-TCPP-modified GCE anode as an effective electrode for the sensitive detection of multiple heavy metals and an in-depth study into the Cu replacement kinetics of the Cu-MOF.