改性金属有机框架对甲基苯丙胺吸附及机理分析

doi:10.19965/j.cnki.iwt.2023-0658

摘要/Abstract

摘要：

将低共熔溶剂（DES）接枝到金属有机框架ZIF/磁性还原氧化石墨烯（MG）制备了一种复合吸附剂（DES@ZIF@MG），用于吸附水中甲基苯丙胺。采用SEM、FT-IR、BET、VSM、TGA等表征研究复合材料的微观形貌及理化性质。通过吸附动力学、吸附等温线以及吸附影响实验（pH、离子浓度和腐殖酸）探究吸附剂对甲基苯丙胺的吸附性能及机理。结果表明：吸附剂DES@ZIF@MG对甲基苯丙胺的吸附符合准二级动力学模型和Langmuir等温模型，说明吸附过程是以化学吸附为主导的能量均匀吸附。结合XPS表征进一步分析，DES@ZIF@MG对甲基苯丙胺的吸附过程中主要存在氢键作用、π-π作用、静电作用以及螯合作用。

关键词: 吸附, 低共熔溶剂, 金属有机框架, 甲基苯丙胺

Abstract:

A new adsorbent(DES@ZIF@MG) was prepared by grafting deep eutectic solvents(DES) onto metal organic framework ZIF/magnetic reduced graphene oxide(MG) for the adsorption of methamphetamine. A series of structural characterization analyses (SEM, FT-IR, BET, VSM, TGA) were facilitated to explore the microscopic morphology and physicochemical properties of DES@ZIF@MG. The adsorption performances of methamphetamine onto the adsorbent were investigated by adsorption kinetics, isotherms, and adsorption effect experiments(pH, ionic strengths, and humic acid). The results showed that the adsorption of methamphetamine onto DES@ZIF@MG was consistent with the pseudo-second-order model and the Langmuir model, indicating that the adsorption process was an energetically homogeneous adsorption dominated by chemisorption. The XPS characterization illustrated that the adsorption process of methamphetamine by DES@ZIF@MG mainly involved hydrogen bonding, π-π interaction, electrostatic interaction, and chelation.

Key words: adsorption, deep eutectic solvents, metal-organic framework, methamphetamine

中图分类号:

TB333
X703

宋凤娇, 刘正宏, 曹淑瑞, 田洁, 游嘉德, 张磊. 改性金属有机框架对甲基苯丙胺吸附及机理分析[J]. 工业水处理, 2024, 44(7): 96-104.

Fengjiao SONG, Zhenghong LIU, Shurui CAO, Jie TIAN, Jiade YOU, Lei ZHANG. Adsorption performance and mechanism analysis of modified metal-organic frame composites towards methamphetamine[J]. Industrial Water Treatment, 2024, 44(7): 96-104.

https://www.iwt.cn/CN/Y2024/V44/I7/96

图/表 13

图1 DES@ZIF@MG的SEM（a）~（c）和EDS（d）

Fig.1 SEM（a）-（c） and EDS（d） of DES@ZIF@MG

图2 不同材料的FT-IR图谱

Fig.2 FT-IR spectra of different materials

图3 DES@ZIF@MG的氮气吸附-脱附曲线及孔径分布曲线

Fig.3 N₂ adsorption-desorption curves and pore size distribution of DES@ZIF@MG

图4 DES@ZIF@MG的VSM磁性曲线

Fig.4 The magnetization curve of DES@ZIF@MG

图5 DES@ZIF@MG的TGA热重曲线

Fig.5 TGA curve of DES@ZIF@MG

图6 DES@ZIF@MG对甲基苯丙胺的吸附动力学的准一级动力学、准二级动力学、Elovich模型拟合曲线（a），粒子内扩散（b）和液膜扩散（c）模型拟合曲线

Fig.6 Adsorption kinetics of methamphetamine onto DES@ ZIF@MG fitted by pseudo-first-order，pseudo-second-order kinetic，Elovich models（a），intraparticle diffusion（b） and boyd film diffusion（c）

表1 DES@ZIF@MG吸附甲基苯丙胺的动力学参数

Table 1 Kinetic parameters of DES@ZIF@MG for the methamphetamine adsorption

Q _e/

（μg·g^-1）

K ₁

R ²

Q _e/

（μg·g^-1）

K ₂

表2 DES@ZIF@MG吸附MAMP的等温吸附参数

Table 2 Isotherms parameters of DES@ZIF@MG for the methamphetamine

Langmuir			Freundlich			Dubinin-Radushkevich
Q _m/（μg·g^-1）	K _L	R ²	K _F	n _F	R ²	Q _D-R/（μg·g^-1）	β _D-R	R ²
2 122.304	0.046 77	0.998	208.382	0.467	0.974	1 825.931	0.003	0.973

图7 溶液pH的影响（a），DES@ZIF@MG零电荷点（b）

Fig.7 Effects of solution pH（a），the point of zero charge detection of DES@ZIF@MG（b）

图8 离子强度的影响

Fig.8 Effects of ionic strength

图9 腐殖酸质量浓度的影响

Fig.9 Effects of humic acid mass concentration

图10 DES@ZIF@MG吸附甲基苯丙胺前后的XPS全谱（a），C 1s峰光谱（b），O 1s峰光谱（c），N 1s峰光谱（d）

Fig.10 The XPS spectra of DES@ZIF@MG before and after adsorption of methamphetamine：full scans（a），peaks for C 1s（b），peaks for O 1s（c） and peaks for N 1s（d）

图11 DES@ZIF@MG的循环使用性能

Fig.11 Reusability of DES@ZIF@MG

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