Electron Push-Pull Effect of Benzotrithiophene-Based Covalent Organic Frameworks on the Photocatalytic Degradation of Pharmaceuticals and Personal Care Products

苯并三噻吩基共价有机框架的电子推拉效应对药物和个人护理产品光催化降解的影响

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Abstract

A covalent organic framework (COF) has emerged as a promising photocatalyst for the removal of pharmaceutical and personal care product (PPCP) contaminants; however, high-performance COF photocatalysts are still scarce. In this study, three COF photocatalysts were successfully synthesized by the condensation of benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) with 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (TAPT), 1,3,5-Tris(4-aminophenyl)benzene (TAPB), and 4,4',4''-nitrilotris(benzenamine) (TAPA), namely, BTT-TAPA, BTT-TAPB, and BTT-TAPT, respectively. The surface areas of BTT-TAPA, BTT-TAPB, and BTT-TAPT were found to be 800.46, 1203.60, and 1413.58 cm(2)∙g(-1), respectively, providing abundant active sites for photocatalytic reactions. Under visible-light irradiation, BTT-TAPT exhibited the highest removal rate of tetracycline (TC), reaching 82.7% after 240 min. The superior photocatalytic performance of BTT-TAPT was attributed to its large specific surface area and the strong electron-acceptor properties of the triazine group. Electron paramagnetic resonance capture experiments and liquid chromatograph mass spectrometer analysis confirmed that superoxide radicals played a pivotal role in the degradation of TC and ciprofloxacin. Moreover, BTT-TAPT exhibited high stability and reproducibility during the photocatalytic degradation process. This study confirms that BTT-based COFs are a class of promising photocatalysts for the degradation of PPCPs in water, and their performance can be further optimized by tuning the structure and composition of the frameworks.

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