磁和CO<sub>2</sub>双响应型可降解微凝胶对阴离子染料的可逆吸附与释放

张银山; 毛曦; 刘通; 郭赞如; 熊乐艳; 刘永鑫

doi:10.14133/j.cnki.1008-9357.20210322003

磁和CO₂双响应型可降解微凝胶对阴离子染料的可逆吸附与释放

doi: 10.14133/j.cnki.1008-9357.20210322003

华东交通大学材料科学与工程学院，高分子材料与工程系，南昌 330013

基金项目: 国家自然科学基金（21802041，51563009，21865009）；江西省杰出青年基金（20202ACBL214001）；江西省研究生创新基金（YC 2019-S266）

详细信息

作者简介:
张银山（1994—），男，硕士，主要研究方向为功能高分子材料。E-mail：993871361@qq.com

通讯作者:
郭赞如，E-mail：guozanru@ecjtu.edu.cn

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出版历程
- 收稿日期: 2021-03-22
- 网络出版日期: 2021-05-17

Reversible Adsorption/Release for Anionic Dyes of Magnetic and CO₂ Dual-Responsive Degradable Microgels

Department of Polymer Materials and Engineering,School of Materials Science and Engineering, East China Jiao Tong University, Nanchang 330013, China

摘要

摘要: 首先以甲基丙烯酸二乙氨基乙酯为单体，通过反相悬浮聚合制备了CO₂响应型可降解微凝胶；然后在该微凝胶中原位合成Fe₃O₄磁性纳米粒子，制备了磁和CO₂双响应型可降解微凝胶。通过傅里叶变换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等对微凝胶的组成和结构进行了表征。结果表明：CO₂响应之后的微凝胶对阴离子染料可进行选择性吸附，对茜素红的最大吸附量为1413 mg/g；微凝胶的磁响应性使其能够得到便捷的分离回收，被吸附的染料能够通过碱洗释放，并且在CO₂刺激下微凝胶又能够重复使用。
- 可降解微凝胶 /
- CO₂响应 /
- 阴离子染料 /
- 吸附
Abstract: Degradable magnetic and CO₂ dual-responsive microgels were prepared by inverse suspension polymerization and in-situ synthesis of nanoparticles. The structure and morphology of microgels were characterized by Fourier-transformed infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM). The microgels exhibited magnetic and CO₂ responsiveness, and could be degraded upon the treatment of DL-dithiothreitol (DTT). After treating with the stimulus of CO₂, the microgels exhibited a selective adsorption for anionic dyes. The maximum adsorption capacity was up to 1413 mg g^-1 for Alizarin red (AR). The microgels with adsorbates could be separated from solution under the help of an external magnetic field. Besides, the adsorbates could be desorbed by treating with solution of pH 12. Microgels regenerated with CO₂ trigger exhibited high adsorption ability (>90%) after three consecutive recycling trials.
- degradable microgel /
- CO₂ responsiveness /
- anionic dyes /
- adsorption

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图 1 （a）微凝胶样品的FT-IR谱图和（b）样品的TGA曲线

Figure 1. （a）FT-IR spectra and（b）TGA curves of microgels samples

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图 2 m-MG的（a）光学显微镜、（b）SEM和（c）TEM照片

Figure 2. （a）Optical microscope, （b）SEM and （c）TEM images

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图 3 （a）光学显微镜及（b）SEM照片；（c）CO₂和N₂交替刺激后的ζ电位图

Figure 3. （a）Optical microscope and （b）SEM image of m-MG after CO₂ stimulation;（c）ζ Potential of m-MG during cycling CO₂/N₂ stimulation

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图 4 （a）MG与m-MG的磁滞回曲线图（插图为微凝胶在磁场中的表现，黑色样品为m-MG，白色样品为MG）；（b）m-MG的降解曲线；（c）降解过程中的微凝胶形貌

Figure 4. （a）Magnetization curves of MG and m-MG （Inset is photo of m-MG（black）and MG（white）in external magnetic field ）;（b）Degradation curves of m-MG; （c）Appearance of m-MG during degradation process

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图 5 （a）m-MG对混合染料溶液的选择性吸附的UV-Vis光谱图；（b）染料在溶液中浓度和比例的变化；（c）染料的热力学等温吸附曲线；（d）Langmuir等温吸附模型拟合线；（e）Freundlich等温吸附模型拟合线；（f）染料的动力学吸附曲线；（g）准1级动力学拟合；（h）准2级动力学拟合；（i）Weber-Morris内扩散模型拟合

Figure 5. （a）UV-Vis spectra of m-MG selective adsorption of mixed dyes solution;（b）Variation of the concentration of dyes and its ratio;（c）Thermodynamic isothermal adsorption curves of dyes;（d）Langmuir isothermal adsorption model;（e）Freundlich isothermal adsorption model;（f）Kinetic adsorption curves of dyes;（g）Pseudo-first-order kinetics;（h）Pseudo-second-order kinetics;（i）Weber-Morris internal diffusion model

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图 6 （a）磁力分离吸附染料后的m-MG；（b）m-MG的循环吸附/释放性；（c）m-MG在DTT作用下降解释放AR

Figure 6. （a）Separation of m-MG under external magnetic field after adsorption of dyes;（b）Reusability performance of m-MG;（c）Release of AR by degradation of m-MG upon the treatment of DTT

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表 1 m-MG吸附染料的等温吸附拟合参数

Table 1. Isotherm adsorgtion fitting parameters of m-MG adsorption dyes

Dyes	Q_max,exp/（mg·g^-1）	Langmuir				Freundlich
Dyes	Q_max,exp/（mg·g^-1）	Q_max,cal/（mg·g^-1）	K_L	R_L	R²	K_F	n	R²
AR	1413	1 460.726	0.044 628	0.0695	0.976 22	100.1	2.98829	0.93348
ARAC	823	877.193	0.026 016	0.1137	0.996 29	54.85	2.42966	0.95973
MEB	734	826.446	0.011743	0.2211	0.997 3	26.99	0.54724	0.82175
PS	673	699.301	0.044369	0.0699	0.988 26	88.44	2.63262	0.96144

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表 2 m-MG吸附染料的吸附动力学拟合参数

Table 2. Fitting parameters of adsorption kinetics of m-MG adsorbed dyes

Dyes	Pseudo-first-order model		Pseudo-second -order model		Weber-Morris model
Dyes	Q_e/（mg·g⁻¹）	R²	Q_e/（mg·g⁻¹）	R²	R²
AR	1314.6690	0.94483	1550.4620	0.99075	0.95129
ARAC	693.9223	0.96111	970.8738	0.99483	0.90852
MEB	391.1065	0.87950	854.7009	0.99890	0.75012
PS	674.7215	0.96617	819.6721	0.99507	0.92160

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