Core-shell structured magnetic covalent organic frameworks for magnetic solid-phase extraction of diphenylamine and its analogs

Abstract

Core-shell structured magnetic covalent organic frameworks (Fe₃O₄@COFs) were synthesized via a facile approach at room temperature using 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,5-dibromo-1,4-benzenedicarboxaldehyde (DBDA) as two building blocks for the first time. The Fe₃O₄@COFs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), nitrogen adsorption-desorption isotherms, and zeta potentiometric analysis. The Fe₃O₄@COFs had a high specific surface area (141.94 m²·g^-1) and uniform pore size distribution (average 4.53 nm). They also demonstrated good magnetic response (32.49 emu·g^-1) and good thermal and chemical stabilities. Furthermore, adsorption experiments were conducted to evaluate the adsorption capacities and adsorption times of Fe₃O₄@COFs to diphenylamine (DPA) and its analogs, including benzidine (BZ), 1-naphthylamine (1-NA), 4-phenylphenol (4-PP), and O-tolidine (O-TD). From the experimental results, the maximum adsorption capacities of DPA, 1-NA, 4-PP, BZ, and O-TD were calculated as 246.25, 95.20, 85.85, 107.20, and 123.55 mg·g^-1, respectively. A duration of 20 min was sufficient for adsorption. The Fe₃O₄@COFs were explored as adsorbents for magnetic solid-phase extraction (MSPE) of DPA and its analogs, and the MSPE parameters, including adsorbent dosage, extraction time, pH, ionic strength, desorption solvent, desorption time, and desorption frequency were optimized. Combined with HPLC using diode-array detection, a simple, fast, and sensitive method was proposed to detect DPA and its analogs, which exhibited good linearity (r >0.9946) in the range of 0.1-100 μg·mL^-1. Moreover, the low limits of detection (ranging from 0.02 to 0.08 μg·mL^-1, S/N = 3), low limits of quantitation (ranging from 0.05 to 0.30 μg·mL^-1, S/N = 10), good precision with low relative SDs (<5.86% for intra-day and <6.44% for inter-day) were obtained. Finally, Fe₃O₄@COFs were applied to the effective MSPE of DPA and its analogs in actual samples chosen from the natural environment, and good recoveries (ranging from 79.97 to 122.52%) were observed.

Keywords: Covalent organic frameworks; Diphenylamine, Analogs; HPLC-DAD; Magnetic solid-phase extraction.