基于分子互作设计的MOF-525复合海绵用于水中新烟碱类农药吸附性去除

doi:10.19894/j.issn.1000-0518.250072

摘要/Abstract

摘要：

基于分子间相互作用筛选了对新烟碱类农药分子有强亲和力的卟吩基金属有机框架材料（MOF）配体。新烟碱类农药分子与中-四（4-羧基苯基）卟吩（H₄TCPP）配体主要通过π-π相互作用、CH···π和Cl···π等弱相互作用结合。以八水合氯氧化锆、中-四（4-羧基苯基）卟吩和苯甲酸为原料采用溶剂热法制备了MOF-525，再通过聚乙烯醇（PVA）将MOF-525固定在三聚氰胺海绵（MS）上得到MOF-525复合三聚氰胺海绵（MOF-525@MS）。使用扫描电子显微镜（SEM）、能量色散X射线光谱（XPS）、X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）和热重分析（TG）多种方法对MOF-525@MS的结构进行了表征。将MOF-525@MS作为吸附剂对水中4种新烟碱类农药（烯啶虫胺、噻虫嗪、啶虫脒和吡虫啉）进行吸附实验条件优化、实际样品测定和可重复利用性测定。结果表明，pH=5、吸附时间15 min和NaCl质量分数为8%是MOF-525@MS对4种新烟碱农药的最佳吸附去除条件。取黄浦江水、田间水和湖水3种水样进行不同浓度的农药加标（100、200和300 mg/L），MOF-525@MS在这3种水样中对农药均有80.61%~97.82%的去除率。最后，经过吸附-洗脱-干燥-再吸附重复5个循环后MOF-525@MS的去除率仍有75.41%~81.20%，具有较好的可重复利用性，是可用于水中新烟碱类农药去除的良好吸附材料。

关键词: 金属有机框架, 复合材料, 新烟碱类农药, 吸附性去除

Abstract:

Porphyrin based-metal organic framework （MOF） with strong affinity for neonicotinoid pesticide molecules were screened based on intermolecular interactions. Neonicotinoid pesticide molecules bind to meso-tetrakis（4-carboxyphenyl）porphyrin （H₄TCPP） ligands mainly through weak interactions such as π-π interactions， CH…π and Cl…π. MOF-525 was prepared by solvothermal method using zirconium chloride octahydrate， meso-tetra（4-carboxyphenyl）porphin， and benzoic acid as the raw materials. MOF-525 was immobilized on a melamine sponge （MS） by poly （vinyl alcohol）（PVA） to obtain MOF-525 composite melamine sponge （MOF-525@MS）. The structure of MOF-525@MS was characterized by using scanning electron microscopy （SEM）， energy dispersive X-ray spectroscopy （EDS）， X-ray diffraction （XRD）， Fourier-transform infrared spectroscopy （FT-IR）， and thermogravimetric （TG）， respectively. MOF-525@MS was used as an adsorbent for the optimization of adsorption experimental conditions， determination of actual samples and determination of reusability of four neonicotinoid pesticides （nitenpyram， thiamethoxam， acetamiprid and imidacloprid） in water. The results showed that the removal rate of MOF-525@MS for the above four neonicotinoid pesticides was over 87.49% at pH=5， adsorption time of 15 min and 8% NaCl. Three kinds of water samples from Huangpu River， field water and lake water were spiked with different concentrations of pesticides （100， 200 and 300 mg/L）， and MOF-525@MS showed 80.61%~97.82% removal of pesticides in all three kinds of water samples. Finally， the removal rate was still 75.41%~81.20% after five cycles of adsorption-elution-drying-re-adsorption repetition， which has good reusability and is a good adsorbent material that can be used for the removal of neonicotinoid pesticides in water.

Key words: Metal-organic framework, Composite materials, Neonicotinoid pesticides, Adsorptive removal

中图分类号:

O647.3

张馨煜, 黄剑辉, 黄磊, 张大铭, 徐斐, 吴秀秀. 基于分子互作设计的MOF-525复合海绵用于水中新烟碱类农药吸附性去除[J]. 应用化学, 2025, 42(8): 1144-1154.

Xin-Yu ZHANG, Jian-Hui HUANG, Lei HUANG, Da-Ming ZHANG, Fei XU, Xiu-Xiu WU. Adsorptive Removal of Neonicotinoid Pesticides in Water by MOF-525 Composite Sponge Designed by Perspective of Molecular Interactions[J]. Chinese Journal of Applied Chemistry, 2025, 42(8): 1144-1154.

图/表 11

图1 4种新烟碱类农药和MOF-525配体中-四（4-羧基苯基）卟吩（H4TCPP）的化学结构

Fig.1 Chemical structures of four neonicotinoid pesticides and the ligand meso-tetra（4-carboxyphenyl） porphine （H4TCPP） of MOF-525

图2 MOF-525@MS制备流程示意图

Fig.2 Schematic of the synthesis flow of MOF-525@MS

图3 4种新烟碱类农药和MOF-525配体H4TCPP的静电势图

Fig.3 The electrostatic potential diagrams of four neonicotinoid pesticides and the ligand H4TCPP of MOF-525

图4 新烟碱类农药与H4TCPP结合的IGMH分析和结合能（ΔE）

Fig.4 The IGMH and binding energy （ΔE）of neonicotinoid pesticides with the ligand H4TCPP

图5 MOF-525（A）、MS（B）和MOF-525@MS（C）的SEM图； MOF-525@MS的SEM元素映射图（D）及EDS图（E）

Fig.5 SEM of MOF-525 （A）， MS （B） and MOF-525@MS （C）； SEM mappings （D） and EDS （E） of MOF-525@MS

图6 MOF-525、MS和MOF-525@MS的XRD谱线（A）、FT-IR谱线（B）和热重谱线（C）

Fig.6 XRD （A）， FT-IR （B） and thermogravimetry curves （C） of MOF-525， MS， MOF-525@MS

图7 4种新烟碱类农药的标准曲线

Fig.7 Standard curves of four neonicotinoid pesticides

表1 4种新烟碱类农药的标准方程和R2值

Table 1 Standard equations and R2 of four neonicotinoid pesticides

Pesticides	Standard equations	R²	LOD/（mg·L^-1）	RSD/%
Nitenpyram	y=25587.66x-33952.41	0.999 0	0.042 1	1.43
Thiamethoxam	y=44439.14x-35652.92	0.999 6	0.053 2	2.09
Acetamiprid	y=47040.26x-47425.61	0.999 2	0.023 4	4.69
Imidaclo	y=51678.63x-43019.07	0.999 0	0.092 5	2.46

图8 MOF-525@MS颗粒使用数量（A）、吸附时间（B）、pH值（C）和NaCl质量浓度（D）对新烟碱类农药的去除率的影响

Fig.8 Effect of number of MOF-525@MS particles used （A）， adsorption time （B）， pH （C） and mass concentration of NaCl （D） on removal of neonicotinoid pesticides

图9 MOF-525@MS测定在实际水样中加标4种新烟碱农药的去除率A. Huangpu River water； B. Field water； C. Campus lake water

Fig.9 Determination of the removal rate of four neonicotinoid pesticides spiked in real water samples by MOF-525@MS

图10 MOF-525@MS的可重复使用性

Fig.10 Reusability of MOF-525@MS

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