Cationic metal-organic framework based mixed-matrix membrane for extraction of phenoxy carboxylic acid (PCA) herbicides from water samples followed by UHPLC-MS/MS determination

Abstract

A novel kind of cationic metal-organic framework(MOF) based mixed-matrix membrane(MMM) namely cationic MOF-MMM was firstly designed and used for simultaneous dispersive membrane extraction(DME) of six phenoxy carboxylic acid(PCA) herbicides from water samples followed by determination using ultrahigh-performance liquid chromatography tandem mass spectrometry. The cationic MOF-MMM was synthesized by soaking the zirconium-based MOFs in a polyvinylidene fluoride(PVDF) solution and further functionalization with quaternary amine groups, viz., UiO-66-NMe₃⁺ MMM. The well-prepared UiO-66-NMe₃⁺ MMM was characterized by FT-IR, SEM, XRD, XPS, NMR and etc. Several main variables influencing the MMM based DME efficiency were investigated and optimized in detail, such as dosage ratio of MOF/PVDF, solution pH, extraction time, coexistent anions and ionic strength. Electrostatic interactions dominated adsorption mechanism between anionic PCAs and cationic UiO-66-NMe₃⁺ MMM, along with ππ conjugation and cation-π bonding, leading to better adsorption performance. Low limits of detection in the range of 0.03-0.59 ng/L and satisfactory recoveries within 80.06-117.40 % for all the PCAs are a reliable witness to demonstrate supreme sensitivity and the applicability of the developed method. By relying on the obtained results, the present work implied cationic MOF-MMM based DME can be a versatile and worthy utility for extraction of pollutants from different water samples with high throughput.

Keywords: Dispersion membrane extraction (DME); Ionic metal-organic frameworks (MOFs); Mixed-matrix membrane (MMM); Phenoxy carboxylic acid (PCA) herbicides; Water sample.