Potentiodynamic Fabrication of Aromatic Diamine Linkers on Electrochemically Reduced Graphene Oxide Surface for Environmental Pollutant Nitrobenzene Monitoring

The structure of self-assembled monolayers (SAMs) greatly influences electrochemical interface behavior. This study systematically examines how positional isomers of aromatic diamines (ADMs) assemble on a glassy carbon (GC) electrode and how such ordering affects the attachment and performance of electrochemically reduced graphene oxide (ERGO). SAMs of ortho-, meta-, and para-phenylenediamine (o-PDA, m-PDA, and p-PDA) were fabricated on GC and characterized using atomic force microscopy (AFM) and Raman spectroscopy. Among them, GC/p-PDA exhibited the most compact and homogeneous interfacial structure. ERGO was subsequently immobilized through the free amine functionalities of the SAM, as confirmed by attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV). Strong covalent coupling and electrostatic interactions between the positively charged ERGO and terminal amines enabled stable attachment. Under optimized conditions, the modified GC/p-PDA/ERGO electrode demonstrated exceptional electrocatalytic activity toward nitrobenzene (NBz) reduction, achieving a high sensitivity of 1410 μA mM−1 cm−2 and a low detection limit of 0.040 μM. In addition, this sensor displayed outstanding anti-interference capability, stability, and recovery in a water sample. These results establish GC/p-PDA/ERGO sensor as a robust and efficient electrocatalytically active interface for nitroaromatic pollutants detection and sustainable environmental monitoring.