Pyranochromene/Nafion-Modified Glassy Carbon Electrode for Selective Electrochemical Determination of Cd(II): Synthesis, Interfacial Mechanism, and Water Analysis

Abstract

A pyranochromene-based ligand, 2-amino-4-(4-chlorophenyl)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile (ACLPh-PC-3-CN), was employed as a chelating modifier for the electrochemical determination of Cd(II) in water samples. ACLPh-PC-3-CN was co-immobilized with Nafion on a glassy carbon electrode to form a stable ACLPh-PC-3-CN/Nafion film that combines ligand-based coordination with cation-exchange-assisted preconcentration of Cd2+ at the electrode surface. The Cd(II) response at the modified electrode was characterized by cyclic voltammetry and differential pulse anodic stripping voltammetry, and the data support a predominantly 1:1 Cd(II)–ligand interaction at the interface under the selected conditions. At an optimized pH of 6.0, the sensor provided a linear calibration range from 16.21 to 56.72 μM, with a detection limit of 0.60 μM and a quantification limit of 2.0 μM, and showed good precision (repeatability 2.3% RSD, reproducibility 3.1% RSD) and short-term stability (94% of the initial response after 14 days). The ACLPh-PC-3-CN/Nafion-modified electrode tolerated common inorganic ions and surfactant species (≤5% signal change) and was successfully applied to the determination of Cd(II) in tap water and Red Sea water, affording recoveries between 98.7% and 101%. While the current detection limit is higher than typical guideline values for Cd in drinking water, the proposed sensor compares favorably with several reported electrochemical Cd(II) sensors in terms of simplicity, precision, and matrix tolerance, and represents a useful platform for coordination-based electrochemical sensing of cadmium in environmental water samples.