Metal-organic framework-101 grafted with amino groups as solid-phase extraction adsorbent coupled with liquid chromatography for the determination of phenoxycarboxylic acids in environmental samples

Abstract

Metal-Organic Framework (MOF) MIL-101 and three amino-modified MIL-101s were synthesized and used as adsorbents for solid-phase extraction of trace-level polar phenoxycarboxylic acids (PCAs) from environmental water samples for quantification by liquid chromatography. The four MOFs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, N₂ adsorption-desorption isotherm, pore structure analysis and powder X-ray diffraction analysis. Parameters which play important roles in the process of solid phase extraction were optimized. MIL-101-ethylenediamine (ED) was chosen as the optimum adsorbent for the extraction of PCAs due to electron donation of alkyl groups in aliphatic amino groups and the smaller steric hindrance. The extraction efficiency using MIL-101-ED compacted column was compared with three commercial columns and the influence of humic acid (HA) on extraction was investigated. The merits of newly-built SPE-LC method based on MIL-101-ED are as follows: (a) low limits of detection (0.052-0.160 ng mL^-1), (b) wide linear ranges (0.5-1000 ng mL^-1), (c) good repeatabilities (1.33-3.35%) and reproducibilities (2.51-3.49%) and (d) excludability of HA. This method has been applied to the determination of PCAs in environmental water samples successfully.

Keywords: Amino-modified MIL-101; Environmental water samples; Liquid chromatography (LC); Phenoxycarboxylic acid herbicides (PCAs); Solid phase extracton (SPE).