Simultaneous electrochemical determination of nitrophenol isomers based on macroporous carbon functionalized with amino-bridged covalent organic polycalix[4]arenes.

A glassy carbon electrode (GCE) modified by a hybrid, macroporous carbon (MPC) functionalized with triazine bridged covalent organic polycalix[4]arenes (CalCOP) (CalCOP-MPC), has been fabricated and utilized for simultaneous detection of nitrophenols (NP). The obtained CalCOP-MPC were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), which confirmed that MPC had functionalized with CalCOP successfully. Benefiting from the synergistic supramolecular effect of macrocyclic receptor of CalCOP and the excellent electrical properties of MPC, the anodic peaks of o-nitrophenol (o-NP), m-nitrophenol (m-NP), and p-nitrophenol (p-NP) in their mixture can be well separated by the prepared electrode. Differential pulse voltammetry (DPV) measurements at CalCOP-MPC/GCE revealed that the linear ranges of NP isomers were all 1-400 μM, and the detection limit limits were 0.383 μM, 0.122 μM, and 0.212 μM for o-NP, m-NP, and p-NP, respectively. Moreover, the prepared modified electrodes showed a relatively good selectivity and stability, implying the prospect for detecting NP in real environmental samples.