氧化石墨烯杂化分子印迹复合膜制备及性能研究

doi:10.11949/0438-1157.20200002

摘要/Abstract

摘要：

采用改进的Hummers法，通过冷冻干燥制备了氧化石墨烯(GO)。以辛弗林盐酸盐为模板分子，水溶性的丙烯酰胺为功能单体，离子液体(溴代1-丁基-3-甲基咪唑)为致孔剂，把GO加入聚合液中，制备了GO杂化的分子印迹复合膜(GO-MIM)。利用透射电镜、扫描电镜、X射线衍射和红外光谱等方法对GO及GO-MIM进行了表征。通过将分子印迹膜技术与GO相结合，明显提高了分子印迹膜的力学性能。吸附及渗透实验表明，GO-MIM可在纯水溶剂体系，对辛弗林盐酸盐具有很好的选择性吸附能力和优先透过能力，体现了明显的分子印迹效果。

关键词: 分子印迹膜, 氧化石墨烯, 吸附, 分离, 辛弗林盐酸盐

Abstract:

Graphene oxide (GO) was prepared by the improved Hummers method and freeze-drying method. With synephrine hydrochloride as the template molecule, water-soluble acrylamide as the functional monomer, and ionic liquid (1-butyl-3-methylimidazole bromide) as the porogen, GO was added to the polymerization solution to prepare graphene oxide hybrid molecularly imprinted composite membrane (GO-MIM). Transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and infrared spectroscopy were used to characterize GO and GO-MIM. By combining molecularly imprinted membrane technology with GO, the mechanical properties of MIM are significantly improved. Adsorption and permeation experiments show that GO-MIM can be used in pure water solvent system and has a good selective adsorption capacity and preferential permeability for synephrine hydrochloride.

Key words: molecularly imprinted membrane, graphene oxide, adsorption, separation, synephrine hydrochloride

中图分类号:

TQ 028.8

毛东阳, 杨丹, 范杰平. 氧化石墨烯杂化分子印迹复合膜制备及性能研究[J]. 化工学报, 2020, 71(6): 2900-2911.

Dongyang MAO, Dan YANG, Jieping FAN. Preparation and properties of graphene oxide hybrid molecularly imprinted composite membranes[J]. CIESC Journal, 2020, 71(6): 2900-2911.

图/表 18

图1 GO的透射电镜图[(a)、(b)]及选区电子衍射图[(c)、(d)]

Fig.1 TEM [(a), (b)] and selected area electron diffraction pattern[(c), (d)] of GO

图2 GO的IR图

Fig.2 IR of GO

图3 GO的XRD谱图

Fig.3 XRD pattern of GO

图4 GO-MIM与NGO-MIM的水接触角

Fig.4 Water contact angle of GO-MIM and NGO-MIM

图5 GO含量不同的MIM洗脱前及相应洗脱后的MIM的SEM图

Fig.5 SEM of MIM with different amount of GO before and after washing

图6 GO、GO-MIM和MIM的IR图

Fig.6 IR of GO, GO-MIM and MIM

图7 GO-MIM的应力-应变曲线

Fig.7 Stress-strain curves of GO-MIM

图8 吸附动力学曲线及拟合曲线

Fig.8 Adsorption kinetic data and the fitting curves

表1 动力学方程回归参数值

Table 1 Regression parameter of kinetic equation

Membrane	一级动力学模型			二级动力学模型
Membrane	Q_e，cal	K₁×10^-2	R2	Q_e,cal	K₂×10^-4	R2
GO-MIM	200.19	7.125	0.9791	219.28	4.136	0.9526
NGO-MIM	210.83	6.947	0.9797	231.52	3.800	0.9590
GO-NIM	49.73	12.043	0.9692	49.64	31.849	0.9634
NGO-NIM	53.05	13.122	0.9652	56.19	34.009	0.9510

图9 GO-MIM和NGO-MIM的等温吸附数据及拟合曲线

Fig.9 Isothermal adsorption data and fitting curves of GO-MIM and NGO-MIM

表2 GO-MIM和NGO-MIM对辛弗林盐酸盐水溶液的Langmuir和Freundlich回归数据

Table 2 Langmuir and Freundlich regression data of GO-MIM and NGO-MIM with synephrine hydrochloride aqueous solution

Membrane	温度/ ℃	Langmuir等温吸附方程			Freundlich等温吸附方程
Membrane	温度/ ℃	Q_m/(μmol/g)	K_L	R²	n	K_F	R²
GO-MIM	20	311.17	4.567	0.9776	2.936	278.47	0.9560
	30	293.26	4.175	0.9825	2.843	259.36	0.9870
	40	286.39	3.484	0.9863	2.634	239.69	0.9364
NGO-MIM	20	320.82	4.653	0.9747	2.911	269.08	0.9664
	30	306.32	4.137	0.9808	2.831	248.054	0.9448
	40	291.87	3.630	0.9683	2.582	232.96	0.9560

表3 GO-MIM和NGO-MIM吸附辛弗林盐酸盐的热力学参数

Table 3 Thermodynamic parameters of synephrine hydrochloride adsorbed by GO-MIM and NGO-MIM

Membrane	T/℃	ΔG°/(kJ/mol)	ΔS°/(kJ/(mol·K))	ΔH°/(kJ/mol)
GO-MIM	20	-3.702	0.0226	-10.37
	30	-3.602
	40	-3.250
NGO-MIM	20	-3.747	0.0195	-9.47
	30	-3.579
	40	-3.357

图10 辛弗林盐酸盐(a)、章胺盐酸盐(b)和酪胺(c)的分子结构式

Fig.10 Molecular structural formula of synephrine hydrochloride (a), octopamine hydrochloride (b), and tyramine (c)

表4 不同底物在MIM和NIM上的吸附量

Table 4 Adsorption capacity of different substrates on MIM and NIM

Membrane	Q/(μmol/g)
Membrane	辛弗林盐酸盐	章胺盐酸盐	酪胺
GO-MIM	200.48	60.51	61.61
NGO-MIM	206.49	61.38	60.40
GO-NIM	61.09	58.59	57.27
NGO-NIM	58.65	57.72	56.54

图11 GO-MIM吸附前(a)、后(b)混合液的HPLC图

Fig.11 HPLC of the mixture before (a) and after (b) adsoption by GO-MIM1—synephrine hydrochloride; 2—octopamine hydrochloride; 3—tyramine

图12 供给池中初始样品HPLC图(a)、透过GO-MIM(b)和GO-NIM(c)后接收池混合溶液HPLC相图

Fig.12 HPLC chromatograms of the standard mixtures in the initial donor solution (a), receptor solutions through GO-MIM (b) and GO-NIM (c)1—synephrine hydrochloride; 2—octopamine hydrochloride; 3—tyramine

图13 三种物质的混合液透过GO-MIM和GO-NIM的时间-透过液浓度图1—辛弗林盐酸盐分子透过GO-MIM；2—酪胺分子透过GO-MIM；3—章胺盐酸盐分子透过GO-MIM；4—辛弗林盐酸盐分子透过GO-NIM；5—酪胺分子透过GO-NIM；6—章胺盐酸盐分子透过GO-NIM

Fig.13 Time-transmission of the mixtures through GO-NIM and GO-NIM

表5 三种物质通过GO-MIM和GO-NIM的相关参数

Table 5 Permeation factors of three substrates through GO-MIM and GO-NIM

Membrane	P/(μmol/cm²)			TF			SF
Membrane	SYN	TYR	OTC	SYN	TYR	OTC	SF₁	SF₂
GO-MIM	8.50	4.49	4.25	2.06	1.16	1.15	1.89	2.00
GO-NIM	4.13	3.87	3.68	2.06	1.16	1.15	1.07	1.12

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