ZIF-8/CMC杂化泡沫吸附TC和Cu<sup>2+</sup>研究

李微; 郭孟雅; 刘宁; 刘水

doi:10.13205/j.hjgc.202504018

ZIF-8/CMC杂化泡沫吸附TC和Cu²⁺研究

doi: 10.13205/j.hjgc.202504018

李微^1, ,,
郭孟雅¹,
刘宁²,
刘水³

1. 沈阳建筑大学市政与环境工程学院,沈阳 110168;
2. 沈阳碧桂园房地产开发有限公司,沈阳 110003;
3. 佛山水务环保股份有限公司技术创新中心,广东佛山 518000

基金项目:

辽宁省高校基本科研项目（LJ212410153029；辽宁省应用基础研究计划项目（2023030002-JH2/1013）；沈阳市科技计划项目（22-322-3-10

详细信息

作者简介:
李微（1982-），女，博士，教授，主要研究方向为水污染控制理论与技术。lw02315@sjzu.edu.cn

通讯作者:
李微（1982-），女，博士，教授，主要研究方向为水污染控制理论与技术。lw02315@sjzu.edu.cn

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出版历程
- 收稿日期: 2023-05-09
- 录用日期: 2023-08-16
- 修回日期: 2023-07-13
- 刊出日期: 2025-04-01

Research on adsorption of TC and copper ions by ZIF-8/CMC hybrid foam

LI Wei^{1
, ,},
GUO Mengya¹,
LIU Ning²,
LIU Shui³

1. School of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang 110168, China;
2. Shenyang Country Garden Real Estate Development Co., Ltd., Shenyang 110003, China;
3. Foshan Water and Environmental Protection Co., Ltd., Foshan 518000, China

摘要

摘要: 以提高金属有机骨架材料吸附有机物和重金属混合污染稳定性为目标，采用冰模版-冷冻干燥法，以羧甲基纤维素作为交联剂制备金属有机骨架杂化泡沫ZIF-8/CMC，利用扫描电子显微镜（SEM）、X射线衍射（XRD）、氮气吸附-脱附实验和热重分析（TG）对其结构和性能进行表征，深入研究了ZIF-8/CMC对四环素（TC）和Cu²⁺的吸附性能、吸附机理及循环再生稳定性。实验结果表明：CMC成功负载到ZIF-8孔道中，形成了不规则的立体结构，提高了对污染物的吸附和循环使用性能。ZIF-8/CMC最佳吸附条件为吸附时间16h、污染物初始浓度30 mg/L、pH=6、吸附剂投加量50 mg，该条件下其对TC和Cu²⁺的吸附容量分别为78.75 mg/g和79.71 mg/g。ZIF-8/CMC的吸附等温线符合 Langmuir 模型，吸附动力学符合拟一级动力学模型，吸附热力学研究表明，ZIF-8/CMC吸附TC和Cu²⁺的热力学行为是一个自发、放热、趋于有序的过程。ZIF-8/CMC循环利用5次，去除率仍保持在75%以上。ZIF-8/CMC吸附剂对TC和Cu²⁺具有高效的选择吸附性能及良好的循环再生性能，在处理医药废水方面具有广阔的应用前景。
- ZIF-8/CMC材料 /
- 冰模板-冷冻干燥法 /
- 羧甲基纤维素（CMC） /
- 四环素 /
- Cu²⁺
Abstract: To improve the stability of metal-organic framework （MOF） materials for the adsorption of organic compounds and heavy metal mixed pollutants， this study applied the ice-templating and freeze-drying method to prepare a hybrid foam of ZIF-8/CMC， with carboxymethyl cellulose （CMC） acting as the crosslinking agent. The structural and functional properties of ZIF-8/CMC were thoroughly characterized using advanced analytical techniques， including scanning electron microscopy （SEM）， X-ray diffraction （XRD）， nitrogen adsorption-desorption tests， and thermogravimetric analysis （TG）. Additionally， the adsorption performance， adsorption mechanisms， and recycling stability of ZIF-8/CMC for tetracycline （TC） and Cu²⁺ were systematically investigated. The results demonstrated that CMC was successfully loaded into the channels of ZIF-8， forming an irregular three-dimensional structure that significantly enhanced the material's adsorption capacity for pollutants and the recycling performance. The optimal adsorption conditions for ZIF-8/CMC were determined as follows： an adsorption time of 16 hours， an initial pollutant concentration of 30 mg/L，a pH value of 6， and an adsorbent dosage of 50 mg. Under these conditions， the adsorption capacities of ZIF-8/CMC for TC and Cu²⁺ reached remarkable levels of 78.75 mg/g and 79.71 mg/g， respectively. The adsorption isotherm process of ZIF-8/CMC was found to comply well with the Langmuir model， indicating monolayer adsorption on a homogeneous surface. Furthermore， thermodynamic studies revealed that the adsorption of TC and Cu²⁺ by ZIF-8/CMC was a spontaneous， exothermic， and orderly process， suggesting a thermodynamically favorable and orderly adsorption mechanism.In terms of reusability， ZIF-8/CMC exhibited excellent cyclic stability， maintaining a removal rate of 75% above for both TC and Cu²⁺ even after five consecutive adsorption cycles. This highlights the material's robust performance and potential for repeated use in practical applications. The ZIF-8/CMC adsorbent demonstrated high selective adsorption performance for TC and Cu²⁺， along with exceptional reusability in cyclic adsorption processes. These properties make it a highly promising candidate for the treatment of pharmaceutical wastewater， where the removal of organic pollutants and heavy metals is critical. Moreover， the unique structural and functional characteristics of ZIF-8/CMC suggest its potential for broader environmental applications， such as the remediation of industrial effluents containing complex pollutants mixtures. Future research sould focus on scaling up the synthesis of ZIF-8/CMC， optimizing its performance in real-world conditions， and exploring its effectiveness in removing other emerging contaminants. The findings of this study not only advance the understanding of MOF-based hybrid materials but also pave the way for their practical implementation in sustainable water treatment technologies.
- ZIF-8/CMC materials /
- ice-templating freeze-drying method /
- CMC /
- tetracycline /
- Cu²⁺

HTML全文

1 ZIF-8/CMC 制备流程示意

1. Schematic diagram of the preparation process of ZIF-8/CMC

下载: 全尺寸图片幻灯片

2 ZIF-8/CMC杂化泡沫的 SEM 图像

a—ZIF-8/CMC 1k倍镜 b—ZIF-8/CMC 5k倍镜

2. SEM images of ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

3 ZIF-8和ZIF-8/CMC杂化泡沫的X射线衍射图谱

3. X-ray diffraction patterns of ZIF-8 and ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

4 ZIF-8/CMC 杂化泡沫的氮气吸附脱附

4. Nitrogen absorption and desorption diagram of ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

5 ZIF-8/CMC杂化泡沫的热重分析

5. Thermogravimetric analysis of ZIF-8 and ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

6 ZIF-8/CMC杂化泡沫在不同吸附时间下对去除效果的影响

6. Effects of adsorption time on removal efficiency by ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

7 ZIF-8/CMC 杂化泡沫在污染物不同初始浓度下对其去除效果的影响

7. Effects of initial concentration on removal efficiency by ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

8 ZIF-8/CMC 杂化泡沫在不同投加量下对去除效果的影响

8. Effects of dosage on removal efficiency by ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

9 ZIF-8/CMC 杂化泡沫在不同 pH 下对污染物去除效果的影响

9. Effects of pH on removal efficiency by ZIF-8/CMC hybrid foam

下载: 全尺寸图片幻灯片

10 ZIF-8/CMC吸附Cu²⁺、TC 的等温吸附模型拟合曲线

10. Isothermal adsorption model fitting curves for the adsorption of Cu²⁺ and TC by ZIF-8/CMC

下载: 全尺寸图片幻灯片

11 ZIF-8/CMC吸附Cu²⁺、TC 的动力学模型拟合曲线

11. Kinetic curves for the adsorption of Cu²⁺and TC by ZIF-8/CMC

下载: 全尺寸图片幻灯片

12 不同温度下ZIF-8/CMC吸附Cu²⁺、TC 的热力学模拟曲线

12. Thermodynamic simulation curves of the adsorption of Cu²⁺ and TC by ZIF- 8/CMC at different temperatures

下载: 全尺寸图片幻灯片

13 ZIF-8/CMC循环再生性能

13. Reusability performance of ZIF-8/CMC

下载: 全尺寸图片幻灯片

1 ZIF-8/CMC吸附Cu²⁺、TC 的等温吸附模型参数

1. Isothermal adsorption model parameters for the adsorption of Cu²⁺ and TC by ZIF-8/CMC

目标污染物	Langmuir 模型			Freundlich 模型
目标污染物	K_L/（L/mg）	q_m /（mg/g）	R²	K_F/（L/g）	1/n	R²
TC	0.0357	70.7624	0.9808	6.0202	0.5878	0.9768
Cu²⁺	0.0464	67.2343	0.9563	14.5463	0.3907	0.9508

下载: 导出CSV

2 ZIF-8/CMC吸附Cu²⁺、TC 的动力学模型拟合参数

2. Kinetic adsorption model parameters for the adsorption of Cu²⁺ and TC by ZIF-8/CMC

目标污染物	拟一阶动力学模型			拟二阶动力学模型
目标污染物	q_e/（mg/g）	k₁/（1/min）	R²	q_e /（mg/g）	k₂/[g/(mg·min）	R²
TC	71.6439	0.2019	0.9918	6.0202	0.5878	0.9768
Cu²⁺	77.0571	0.2463	0.9911	14.5463	0.3907	0.9508

下载: 导出CSV

3 不同温度下目标污染物热力学模型的参数

3. Parameters of the thermodynamic model for target pollutants at different temperatures

目标污染物	温度/K	Langmuir 模型
目标污染物	温度/K	K_L/（L/mg）	q_m/（mg/g）	R²
TC	298	0.0357	70.7624	0.9808
	303	0.0344	70.0005	0.9800
	308	0.0326	69.8088	0.9935
Cu²⁺	298	0.0664	67.2343	0.9563
	303	0.0623	65.4132	0.9804
	308	0.0518	64.8520	0.9733

下载: 导出CSV

4 不同温度下吸附过程的热力学参数

4. Thermodynamic parameters of adsorption processes at different temperatures

目标污染物	温度/K	热力学参数
目标污染物	温度/K	K	ΔG/（kJ/mol）	ΔH/（kJ/mol）	ΔS/[J/(mol·K）]
TC	298	35700	-11.2795	-231.1405	-0.7377
	303	34400	-11.4282
	308	32600	-11.5570
Cu²⁺	298	66400	-11.9472	-375.3677	-1.2195
	303	62300	-12.0779
	308	51800	-12.0720

下载: 导出CSV

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