铁负载纤维素<strong>/</strong>单宁吸附剂的制备及其对氟硅诺酮类抗生素的吸附性能

doi:10.11901/1005.3093.2023.229

材料研究学报

2024, Vol. 38

Issue (2): 92-104 DOI: 10.11901/1005.3093.2023.229

研究论文

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铁负载纤维素/单宁吸附剂的制备及其对氟硅诺酮类抗生素的吸附性能

翁鑫¹, 李琦琪¹, 杨桂芳², 吕源财¹, 刘以凡¹, 刘明华¹^,²(

)

^1.福州大学环境与安全工程学院福州 350116
^2.莆田学院环境与生物工程学院莆田 351100

Preparation of Adsorbent Fe-loaded Cellulose/Tannin and Its Adsorption Characteristics for Fluoroquinolones Antibiotics

WENG Xin¹, LI Qiqi¹, YANG Guifang², LV Yuancai¹, LIU Yifan¹, LIU Minghua¹^,²(

)

^1.College of Environment and Safety Engineering, Fuzhou University, Fuzhou 350116, China
^2.College of Environmental and Biological Engineering, Putian University, Putian 351100, China

引用本文:

翁鑫, 李琦琪, 杨桂芳, 吕源财, 刘以凡, 刘明华. 铁负载纤维素/单宁吸附剂的制备及其对氟硅诺酮类抗生素的吸附性能[J]. 材料研究学报, 2024, 38(2): 92-104.
Xin WENG, Qiqi LI, Guifang YANG, Yuancai LV, Yifan LIU, Minghua LIU. Preparation of Adsorbent Fe-loaded Cellulose/Tannin and Its Adsorption Characteristics for Fluoroquinolones Antibiotics[J]. Chinese Journal of Materials Research, 2024, 38(2): 92-104.

全文: PDF(10463 KB) HTML

摘要:

采用纤维素/杨梅单宁复合气凝胶(CBT)为载体，用浸渍和原位还原法制备铁负载纤维素/单宁吸附剂(Fe-CBT)，使用扫描电镜、傅里叶红外光谱和X射线能谱等手段对其表征，研究了三种典型氟喹诺酮类(FQs)抗生素诺氟沙星(NOR)、盐酸洛美沙星(LOM)和盐酸左氧氟沙星(LVX)的静态吸附性能。结果表明：共存阳离子Na⁺、K⁺、Mg²⁺和Ca²⁺都对吸附过程有明显的干扰。吸附过程是自发进行的放热反应，主要为单分子层吸附，而化学吸附是主要的限速步骤。准二级和Langmuir模型能很好地拟合这种吸附行为。这种吸附剂在298 K对NOR、LOM和LVX的最大理论吸附量分别达到99.07、74.17和40.14 mg/g。NaOH和NaCl对Fe-CBT都表现出较优的洗脱效果，用NaOH和NaCl溶液4次再生后Fe-CBT对NOR的吸附能力仍高于70%。Fe-CBT对FQs的去除，主要是静电引力、表面络合、氢键和π-π堆积间的协同作用造成的。

关键词 ：有机高分子材料, 铁负载, 纤维素复合气凝胶, 氟硅诺酮类抗生素, 单宁, 吸附

Abstract：

The absorbent of Fe-loaded cellulose/bayberry tannin (Fe-CBT) was prepared via impregnation and in-situ reduction process, with cellulose/tannin composite aerogel (CBT) as the carrier, which then was characterized by means of scanning electron microscopy, Fourier infrared spectroscopy and X-ray energy dispersive spectroscopy. Afterwards, the adsorption characteristic of the Fe-CBT was comparatively assessed for three typical fluoroquinolones (FQs) antibiotics, i.e., norfloxacin (NOR), lomefloxacin hydrochloride (LOM) and levofloxacin hydrochloride (LVX). The results show that the coexistence of cations Na⁺, K⁺, Mg²⁺ and Ca²⁺ all interferes significantly with the adsorption process. Moreover, the adsorption process is an exothermic reaction that proceeds spontaneously, mainly as single-molecule layer adsorption, of which chemisorption is the main rate-limiting step. The quasi-secondary and Langmuir models are demonstrated to fit this adsorption behavior, and the maximum theoretical adsorption capacity of 99.07, 74.17 and 40.14 mg/g can be achieved for NOR, LOM and LVX at 298 K, respectively. Both NaOH and NaCl show superior elution effect on Fe-CBT, namely, after re-generation for four times with NaOH and NaCl solutions, the adsorption capacity of Fe-CBT on NOR could even be maintained > 70%. In addition, it is found that the removal of FQs by Fe-CBT is caused by the synergy between electrostatic gravitation, surface complexation, hydrogen bonding and π-π stacking.

Key words： organic polymer materials Fe-loaded cellulose composite aerogel fluoroquinolones antibiotics tannin adsorption

收稿日期: 2023-04-17

ZTFLH:

TQ424

基金资助:国家自然科学基金(22278082)

通讯作者: 刘明华，教授，mhliu2000@fzu.edu.cn，研究方向为生物质基材料和水污染控制新材料的制备及应用

Corresponding author: LIU Minghua, Tel: 13305022089, E-mail: mhliu2000@fzu.edu.cn

作者简介: 翁鑫，男，1999年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.229 或 https://www.cjmr.org/CN/Y2024/V38/I2/92

图1 CBT和Fe-CBT的扫描电镜照片

图2 Fe-CBT的扫描电镜照片、EDS元素分布分析及EDS图谱

图3 CP、CBT和Fe-CBT的XRD谱

图4 BT、CP、CBT和Fe-CBT的FT-IR谱

图5 CBT和Fe-CBT的N2吸附-脱附等温曲线

图6 CP，BT，CBT和Fe-CBT的热重曲线

图7 硼氢化钠还原前后吸附剂的XPS高分辨谱

图8 初始溶液的pH值对NOR、LOM和LVX在Fe-CBT上的吸附性能的影响

图9 在不同pH值条件下NOR的分子形态和Fe-CBT的Zeta电位

图10 NOR的分子结构

图11 Fe-CBT在不同温度下对FQs的吸附等温模型拟合

表1 在不同温度下Fe-CBT对NOR、LOM和LVX的等温吸附模型拟合参数

表2 与其它吸附剂对FQs类抗生素吸附能力的对比

表3 Fe-CBT对NOR、LOM和LVX的吸附热力学参数

图12 Van't Hoff热力学方程拟合结果

图13 Fe-CBT对NOR、LOM和LVX的吸附动力学

表4 Fe-CBT对NOR、LOM和LVX的吸附动力学参数

图14 无机阳离子对Fe-CBT的NOR吸附性能的影响

图15 Fe-CBT对NOR吸附的循环再生性能

图16 Fe-CBT吸附NOR、LOM和LVX前后的FT-IR谱

图17 Fe-CBT吸附NOR前后的XPS谱

图18 Fe-CBT吸附TCs前后的XPS高分辨谱

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