Graphitic Carbon Nitride Based 3D Printed Mixed Matrix Membrane Thin Film as a Novel Adsorbent for Estrogenic Hormone Extraction from Aqueous Samples

Abstract

3D printed mixed matrix membrane (MMM) thin film, as a novel adsorbent, was introduced for the extraction of two steroid hormones from wastewater and tap water samples before their determination by high-performance liquid chromatography. The designed adsorbent was fabricated as thin film utilizing digital light processing (DLP) 3D printing. The thin film was made of acrylate photo resin, graphitic carbon nitride (g-C3N4), and polyvinylpyrrolidone and its application was investigated for thin film microextraction of 17β-estradiol (E2) and estrone (E1). The morphology of the 3D printed film surface and its chemical changes were studied using field emission scanning electron microscopy and attenuated total reflectance-Fourier transform infrared spectroscopy, respectively. The surface wettability of the proposed MMM films was measured by water contact angle analysis and its porosity was studied by N2 adsorption/desorption analysis. To attain optimal microextraction performance, optimization of both thin film composition and microextraction procedure was conducted, followed by a thorough evaluation of figures of merit under the optimized conditions. The limits of detection and quantitation were determined to be 1.5 and 5 µg L−1 for both E2 and E1. The linear dynamic range for both compounds was from 5 to 150 µg L−1. The method’s repeatability was investigated on a single film for 6 extractions, as well as on 3 different films and the relative standard deviation values were 4.43 and 4.91 for E2 and 5.36 and 6.03 for E1, respectively.