College of Chemistry, Nanchang University, Nanchang 330031, China; Nanchang Institute for Food and Drug Control, Nanchang 330038, China.
College of Chemistry, Nanchang University, Nanchang 330031, China.
J Hazard Mater. 2021 Jul 5;413:125302. doi: 10.1016/j.jhazmat.2021.125302. Epub 2021 Feb 5.
Due to the low efficiency of traditional sewage treatment methods, the effective removal of zwitterionic fluoroquinolone (FQs) antibiotics is of vital significant for environment protection. In this work, a SOH-anchored covalent organic framework (TpPa-SOH) was deliberately designed by linking phenolic trialdehyde with triamine through Schiff reaction, then low-content Tb ions were loaded onto covalent organic framework according to wet-chemistry immersion dispersion method which benefitting for efficient FQs antibiotics uptaking. Tb@TpPa-SOH functionalized with regularly distributed sulfonic acid groups and terbium ions which could provide difunctional binding sites. Tb sites could capture carboxylic acid group of FQs molecules according to the complexes coordination effect and sulfonic acid sites play a significant role in the adsorption of FQs molecules through electrostatic interaction with amine group. Tb@TpPa-SOH with dual complementary function sites exhibited ultra-fast adsorption kinetics (< 2 min, average over 99% removing rate) and high adsorption capacities of 989, 956, and 998 mg g for Norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENR), respectively. Furthermore, Tb@TpPa-SOH showed excellent selectivity for the adsorption of FQs in tanglesome system. This work not only explored synergistic adsorption in ion-functionalized 2D covalent organic framework with dual binding sites, but also delineated a promising strategy for the elimination of organic pollutants in environmental remediation.
由于传统污水处理方法效率低下，有效去除两性离子氟喹诺酮（FQs）抗生素对环境保护至关重要。在这项工作中，通过席夫反应将酚醛三醛与三胺连接，精心设计了一种 SOH 锚定的共价有机骨架（TpPa-SOH），然后根据湿化学浸渍分散法将低含量的 Tb 离子负载到共价有机骨架上，有利于高效 FQs 抗生素的吸收。Tb@TpPa-SOH 功能化的磺酸基团和铽离子均匀分布，提供双功能结合位点。Tb 位可根据配合物的配位效应捕获 FQs 分子的羧酸基团，磺酸位通过与胺基的静电相互作用对 FQs 分子的吸附起重要作用。具有双重互补功能位点的 Tb@TpPa-SOH 表现出超快的吸附动力学（<2 min，平均去除率超过 99%）和对诺氟沙星（NOR）、环丙沙星（CIP）、恩诺沙星（ENR）的高吸附容量，分别为 989、956 和 998 mg/g。此外，Tb@TpPa-SOH 在复杂体系中对 FQs 的吸附表现出优异的选择性。这项工作不仅探索了具有双结合位点的离子功能化二维共价有机骨架中的协同吸附，还为环境修复中有机污染物的消除描绘了一种很有前途的策略。
