具有高选择性吸附的表面分子印迹磁性纤维素微球的制备与性能

doi:10.7503/cjcu20160248

摘要/Abstract

摘要：

以纤维素和纳米Fe₃O₄为原料制得磁性纤维素微球, 在纤维素微球表面选择合适的模板分子, 以甲基丙烯酸、丙烯酰胺和N,N'-亚甲基双丙烯酰胺为功能单体, 采用水溶液聚合法制得表面分子印迹磁性纤维素微球. 采用傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)和振动样品磁强计(VSM)等表征了分子印迹聚合物微球的结构. 以罗丹明B(RhB)为模板分子, 通过吸附动力学与吸附热力学实验研究了表面分子印迹磁性纤维素微球对RhB的吸附性能, 结果表明, 制备的表面分子印迹磁性纤维素微球对罗丹明B具有特异性识别作用, 饱和吸附量达到0.542 mg/mg, 吸附平衡时间为10 h左右. 表面分子印迹磁性纤维素微球大大降低了对吸附环境的依赖, 并可重复利用.

关键词: 纤维素微球, 四氧化三铁, 分子印迹聚合物, 罗丹明B, 选择性吸附

Abstract:

Molecularly imprinted magnetic composite microspheres(MIP-MCM) were prepared by a surface functional monomer-directing system. Cellulose and Fe₃O₄composite microsphere was the core and then was coated a layer of MIP on the surface. Fourier transform Infrared spectra(FTIR), X-ray powder diffraction(XRD), vibrating sample magnetometry(VSM) methods were used to characterize the structure of MIP-MCM. In this article, Rhodamine B(RhB) was chosen as the template molecule. The adsorption abilities of MIP-MCM toward RhB were studied through adsorption kinetics and adsorption thermodynamics. The adsorption kinetics curves met pseudo-second-order model more. The adsorption isotherms could be described by both Langmuir and Freundlich isotherm models. The maximum adsorption amount was calculated to be 0.542 mg/mg, much higher than the common adsorbents. MIP-MCM was also adsorption-selective to RhB with highly regenerate and kept stable in a wild pH and temperature range. In brief, MIP-MCM is very potential in the application of removal of dye and sewage treatment.

Key words: Cellulose, Fe3O4, Molecularly imprinted polymer, Rhodamine B, Selective adsorption

中图分类号:

O631

TrendMD:

葛昊, 黄海龙, 徐敏. 具有高选择性吸附的表面分子印迹磁性纤维素微球的制备与性能. 高等学校化学学报, 2016, 37(8): 1551.

GE Hao,HUANG Hailong,XU Min. Preparation and Properties of Surface Imprinted Magnetic Cellulose Microsphere with Highly Selective Adsorption^†. Chem. J. Chinese Universities, 2016, 37(8): 1551.

图/表 15

Scheme 1 Preparation process of MIP-MCM

Fig.1 FTIR spectra of Fe3O4(a), cellulose(b), MCM(c), NIP-MCM(d) and MIP-MCM(e)

Fig.2 XRD of MIP-MCM(a), MCM(b), cellulose(c) and Fe3O4(d)

Fig.3 SEM images of MCM(A) and MIP-MCM(B) Insets: magnifications images of (A) and (B).

Fig.4 DLS(A) and microscope image(B) of MIP-MCM

Fig.5 Hysteresis loops of the Fe3O4(a), MCM(b) and MIP-MCM(c) Inset: magnetic separation picture of MIP-MCM.

Fig.6 Adsorption kinetic of MIP-MCM(■), NIP-MCM(◆) and fitting model(—) of RhB on the MIP-MCM and NIP-MCM

Table 1 Kinetic parameters of the adsorption of RhB by MIP-MCM and NIP-MMCl

Adsorption	Q_e/ (mg·mg^-1)	Pseudo-first-order			Pseudo-second-order			α_MIP/NIP
Adsorption	Q_e/ (mg·mg^-1)	Q_e1/(mg·mg^-1)	k₁/h^-1		R²	Q_e2/(mg·mg^-1)	k₂/h^-1	R²
MIP-MCM	0.479	0.454	3.33	0.959	0.482	10.1	0.993	15.1
NIP-MCM	0.0317	0.0310	1.44	0.967	0.0336	60.2	0.989

Fig.7 Static adsorption isotherms of MIP-MCM(■) and NIP-MCM(◆)

Table 2 Langmuir and Freundlich data for the adsorption of RhB on the MIP-MCM at 25 ℃

Adsorption	Langmuir model			Freundlich model
Adsorption	Q_m/(mg·mg^-1)	b	R²	1/n	K_F	R²
MIP-MCM	0.542	6.47	0.997	0.261	0.486	0.986
NIP-MCM	0.0390	3.13	0.994	0.338	0.0285	0.960

Table 3 Kinetic parameters of the adsorption of RhB and Rh6G by MIP-MCM(*) and NIP-MCM(**)

Adsorbents	Q_c/(mg·mg^-1)	Q_e/(mg·mg^-1)
RhB	0.542^*	0.492^*	4.59
	0.0390^**	0.032^**
Rh6G	0.118^*	0.096^*
	0.0351^**	0.027^**

Fig.8 Adsorption selectivity of MIP-MCM toward different targets

Fig.9 Effect of solution pH on RhB adsorption on MIP-MCM at 298 K

Fig.10 Effect of solution temperature on RhB adsorption of MIP-MCM

Fig.11 Regeneration cycles for MIP-MCM

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