Selective adsorption of tetracycline using metal organic framework ZIF‒67

doi:10.19965/j.cnki.iwt.2021-0669

Abstract

Abstract:

Metal organic frameworks ZIF?67 was prepared by a simple and rapid method in water system to selectively adsorb tetracycline（TC） from organic wastewater，and various methods were used to characterize synthesized ZIF?67. The adsorption selectivity of ZIF?67 in the mixed system of TC and methylene blue（MB） was studied，and the effects of pH，the ratio of contaminated substrate and coexisting ion in the mixed system on the adsorption process were investigated. The results showed that the adsorption selectivity of ZIF?67 for TC could reach 93.5% at 298 K，pH=6.5，when the initial mass concentrations of MB and TC were 30 and 40 mg/L. The selective adsorption of TC by ZIF?67 in the mixed system conformed to the pseudo-second-order kinetic model and Langmuir model，and the maximum theoretical adsorption capacity of TC was 735.3 mg/g. The main mechanism of selective adsorption of TC in organic wastewater is deduced that the electropositive ZIF?67 had electrostatic repulsion to cationic dye MB，while TC had electrostatic interaction and π?π interaction with ZIF?67，and might form hydrogen bond with ZIF?67. Therefore，the adsorption amount of TC was much higher than that of MB. Compared with other adsorbents，ZIF?67 had higher adsorption capacity and shorter adsorption equilibrium time for TC.

Key words: metal organic framework materials, ZIF?67, selective adsorption, tetracycline, methylene blue

摘要：

为从有机废水中选择性吸附四环素（TC），在水系条件下采取简便快速的方法制备了金属有机骨架材料ZIF?67。采用多种手段对合成得到的ZIF?67进行了表征，研究了制备材料在TC与亚甲基蓝（MB）混合体系中的选择吸附性能，并考察了混合体系pH、污染底物配比、吸附体系中共存离子等因素对吸附过程的影响。结果表明，在温度为298 K，pH=6.5，MB和TC初始质量浓度分别为30、40 mg/L的条件下，ZIF?67对TC的吸附选择性能够达到93.5%。ZIF?67在混合体系中对TC的选择性吸附符合拟二级动力学模型和Langmuir模型，对TC的最大理论吸附量达735.3 mg/g。ZIF?67在有机废水中能够选择性吸附TC的主要机理推测为ZIF?67对阳离子染料MB具有静电排斥，而TC与ZIF?67则存在静电吸引及π?π相互作用，并且两者之间可能形成氢键，因此其对TC的吸附量远高于对MB的吸附量。与其他吸附剂相比，ZIF?67对TC具有更高的吸附量和较短的吸附平衡时间。

关键词: 金属有机骨架材料, ZIF?67, 选择性吸附, 四环素, 亚甲基蓝

CLC Number:

X787

Muhua CHEN,Shang WEI,Jingrun LI,Jiayi WU,Qixiang HU,Haopeng CHEN,Bo FU. Selective adsorption of tetracycline using metal organic framework ZIF‒67[J]. Industrial Water Treatment, 2022, 42(3): 76-81.

陈慕华,魏尚,李京润,武嘉奕,胡淇翔,陈浩鹏,付博. 金属有机骨架材料ZIF‒67对四环素选择性吸附研究[J]. 工业水处理, 2022, 42(3): 76-81.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0669

https://www.iwt.cn/EN/Y2022/V42/I3/76

Figures/Tables 10

Fig. 1 XRD pattern and SEM image of ZIF?67

Fig. 2 Zeta potentials of ZIF?67 at different pH

Fig. 3 Variation of adsorption capacity with time

Table 1 Fitting parameters of kinetic model for adsorption of ZIF?67 to TC

吸附质	拟一级动力学模型			拟二级动力学模型
吸附质	q_e	k₁	R²	q_e	k₂	R²
TC	125.7	0.042 3	0.949 7	214.6	3.957×10^-4	0.997 2

Table.2 Isotherm model fitting parameters of ZIF?67 adsorption for TC

吸附质

Langmuir模型

Freundlich模型

q_max/

（mg·g^-1）

K_L/

（L·mg^-1）

R²

1/n

K_F

R²

Table 3 Comparison of adsorption performance between ZIF?67 and other adsorbents in similar works

吸附剂	对TC吸附量/ （mg·g^-1）	吸附平衡时间/min	参考文献
污泥多孔生物炭	379.8	200	〔3〕
零价Fe改性MCM-41沸石	526.3	60	〔14〕
MOF-5	233.0	50	〔15〕
纳米ZrO₂	526.3	30	〔16〕
La掺杂Zn-Fe层状双氢氧化物	170.5	90	〔17〕
ZIF?67	735.3	90	本研究

Fig. 4 Effect of pH on adsorption capacity and selectivity of TC

Fig. 5 Effect of mass ratio of TC/MB on adsorption capacity and selectivity of TC

Fig. 6 Effect of coexisting ions on adsorption capacity and selectivity of TC

Fig. 7 FTIR spectra of ZIF?67 before and after TC adsorption

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