离子型共价有机框架材料的制备及对非甾体类抗炎药的吸附性能

doi:10.16085/j.issn.1000-6613.2024-1742

摘要/Abstract

摘要：

近年来，离子型共价有机框架（iCOFs）材料被作为环境修复领域中的优选吸附剂。因此，本文利用2,5-二羟基对苯二甲醛（DHA）与带正电荷的三氨基胍盐酸盐（TAGH）通过席夫碱缩合制备了一种薄片状iCOFs（COF_DHA-TAGH），用于吸附去除非甾体抗炎药吲哚美辛（IDM）。COF_DHA-TAGH均匀分布的吸附位点、表面丰富的官能团（胍基、羟基和芳香基团）有助于其通过静电、氢键和π-π相互作用高效去除IDM。考察了pH和吸附时间对COF_DHA-TAGH吸附IDM过程的影响。结果表明，COF_DHA-TAGH对IDM的吸附符合伪二级动力学模型和Langmuir吸附模型，最大吸附量可达498mg/g。本工作为从药物废水中去除非甾体抗炎药提供了新的途径和有益参考。

关键词: 离子型共价有机框架, 非甾体类药物, 吲哚美辛, 吸附

Abstract:

In recent years, ionic covalent organic frameworks (iCOFs) have been used as preferred adsorbents in the field of environmental remediation. Herein, a sheet iCOFs (COF_DHA-TAGH) was prepared by Schiff base condensation of 2,5-dihydroxyp-phenyldiformaldehyde (DHA) and positively charged triaminoguanidine hydrochloride (TAGH) for adsorption of non-steroidal anti-inflammatory drug indomethacin (IDM). COF_DHA-TAGH's evenly distributed adsorption sites and abundant surface functional groups (guanidine, hydroxyl and aromatic groups) contributed to its efficient removal of IDM by electrostatic, hydrogen bonding and π-π interactions. The effects of pH and adsorption time on the adsorption of IDM by COF_DHA-TAGH were investigated. The results showed that the adsorption of IDM by COF_DHA-TAGH conformed to the pseudo-second-order kinetic model and Langmuir adsorption model, and the maximum adsorption capacity could reach 498mg/g. This work provided a new approach and useful references for removing non-steroidal anti-inflammatory drugs from pharmaceutical wastewater.

Key words: ionic covalent organic framework, non-steroidal anti-inflammatory drugs, indomethacin, adsorb

中图分类号:

王乐, 徐桥英, 匡仁云, 曾可妮, 傅文杰, 候林丽. 离子型共价有机框架材料的制备及对非甾体类抗炎药的吸附性能[J]. 化工进展, 2025, 44(11): 6737-6746.

WANG Le, XU Qiaoying, KUANG Renyun, ZENG Keni, FU Wenjie, HOU Linli. Preparation of ionic covalent organic framework materials and their adsorption properties for non-steroidal anti-inflammatory drugs[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6737-6746.

图/表 14

图1 COFDHA-TAGH的合成过程（1Å=0.1nm）

图2 COFDHA-TAGH的扫描电镜图

图3 COFDHA-TAGH的粉末衍射图

图6 COFDHA-TAGH的傅里叶红外光谱及氮气吸脱附曲线

图7 COFDHA-TAGH的孔径分布及固态核磁谱图

图8 COFDHA-TAGH的X射线光电子能谱和相对应元素的高分辨率光谱

图9 pH和吸附时间对COFDHA-TAGH吸附IDM的影响

图10 COFDHA-TAGH吸附IDM前后的X射线光电子能谱和高分辨率光谱对比

图11 COFDHA-TAGH对IDM的吸附动力学曲线

表1 COFDHA-TAGH对IDM吸附动力学参数

伪一级动力学模型				伪二级动力学模型
q_e/mg·g^-1	K₁/min^-1	R^２		q_e/mg·g^-1	K₂/g·mg^-1·min^-1	R^２
294	0.05805	0.94876		497.51	0.00074	0.99704

图12 COFDHA-TAGH对IDM吸附等温模型拟合曲线

表2 COFDHA-TAGH对IDM吸附等温模型拟合参数

Langmuir模型				Freundlich模型
q_max/mg·g^-1	K_L/L·mg^-1	R^２		K_F/mg·g^-1·(mg·L)^-1/ⁿ	n	R^２
473.93	0.22860	0.98666		103.85	2.34582	0.95784

图13 COFDHA-TAGH对不同药物的去除率和吸附-解析循环的吸附量

表3 不同类型COFs对NSAIDs的吸附性能

吸附剂	目标吸附药物	最大吸附量/mg·g^-1	比表面积/m²·g^-1	平衡时间/h	参考文献
COF-NO₂	布洛芬	94	679	2	[12]
OH-MCOF	双氯芬酸钠	203	89.80	0.5	[13]
MCC/COF/PANI	吲哚美辛	149.1	69.86	1	[22]
COF-3-NH₂	双氯芬酸钠	410	114	1	[28]
iCOFs	吲哚美欣	498	34.63	1	本次工作

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