石墨烯量子点纳滤膜的仿生修饰及稳定性研究

doi:10.11949/0438-1157.20201589

摘要/Abstract

摘要：

亲水修饰是提高纳滤膜抗污染性能的重要方法。采用氯化胆碱（ChC）对石墨烯量子点（GQDs-TMC）纳滤膜进行后处理仿生修饰，模拟细胞膜上磷酰胆碱的两性离子抗污染表面。红外光谱（FTIR）和表面元素分析（EDS）表明ChC以共价键结合在纳滤膜分离层上。提高反应温度和氯化胆碱溶液浓度，可以增加纳滤膜的仿生修饰程度。ChC的季铵基团与GQDs-TMC纳滤膜分离层羧基基团形成两性离子结构，提高了仿生修饰（GQDs/ChC-TMC）纳滤膜的亲水性，降低了表面电势，提高了对染料分子和二价盐离子的截留率，并且显著增强了抗污染性能。经过酸、碱和氧化剂溶液浸泡处理及高温纳滤膜分离实验，GQDs/ChC-TMC纳滤膜的渗透率和截留率均未发生较大改变，表明仿生纳滤膜具有优异的化学稳定性和耐热稳定性。

关键词: 石墨烯量子点, 纳滤, 膜, 氯化胆碱, 仿生修饰, 抗污染, 稳定性

Abstract:

Biomimetic modification is an important method to improve the antifouling performance of nanofiltration membranes. Choline chloride (ChC) was used to post-process the graphene quantum dots (GQDs-TMC) nanofiltration membrane to mimic the zwitterionic anti-pollution surface of phosphorylcholine on the cell membrane. Fourier transform infrared spectrometer (FTIR) and energy dispersive spectrometer (EDS) measurement showed that choline chloride molecules were covalently bonded to the separation layer of nanofiltration membrane. The degree of biomimetic modification would be enhanced by increasing the reaction temperature and the concentration of choline chloride solution. The quaternary ammonium groups of ChC forms zwitterionic structure with carboxyl groups in the separation layer of nanofiltration membranes, which improved the hydrophilicity of the biomimetic nanofiltration (GQDs/ChC-TMC) membranes, reduced the surface potential, improved the rejection ratios of dye molecules and divalent salt ions, and significantly enhanced the antifouling performance. After soaking in acid, alkali and oxidant solutions and high temperature separation experiments of nanofiltration membrane, the permeability and rejection ratio of GQDs/ChC-TMC nanofiltration membranes have not changed significantly. It indicated that the biomimetic nanofiltration membrane has excellent chemical stability and thermal stability.

Key words: graphene quantum dots, nanofiltration, membrane, choline chloride, biomimetic modification, antifouling, stability

中图分类号:

TQ 028.8

刘嘉玮, 郝雨峰, 苏延磊. 石墨烯量子点纳滤膜的仿生修饰及稳定性研究[J]. 化工学报, 2021, 72(6): 3390-3398.

LIU Jiawei, HAO Yufeng, SU Yanlei. Biomimetic modification and stability of graphene quantum dots nanofiltration membranes[J]. CIESC Journal, 2021, 72(6): 3390-3398.

图/表 11

图1 GQD/ChC-TMC纳滤膜模拟细胞膜磷酰胆碱抗污染两性离子结构

Fig.1 GQD/ChC-TMC nanofiltration membrane mimics cell membrane PC anti-fouling zwitterionic structure

表1 GQDs/ChC-TMC纳滤膜的制备条件

Table 1 Preparation conditions of GQDs/ChC-TMC nanofiltration membrane

Membranes	ChC concentration/% (质量)	Solution temperature of modification/℃
0^#	0	90
1^#	0.25	90
2^#	0.50	90
3^#	0.75	90
4^#	1.00	90
5^#	0.75	50
6^#	0.75	60
7^#	0.75	70
8^#	0.75	80

图2 GQDs的TEM图

Fig.2 TEM image of GQDs

图3 GQDs/ChC-TMC纳滤膜的SEM表面图(a)、AFM图(b)、SEM断面图(c)

Fig.3 Images of the GQDs/ChC-TMC nanofiltration membranes: SEM surface image(a), AFM image(b), SEM section image(c)

表2 不同制备条件下GQDs/ChC-TMC纳滤膜样品的表面性质

Table 2 Surface properties of GQDs/ChC-TMC nanofiltration membrane prepared under different preparation conditions

Membranes	ChC concentration / %(质量)	Solution temperature of modification/℃	Surface roughness	Zeta potential/mV	Water contact angles/(°)
0^#	0	90	10.9	-45.2	68.3
1^#	0.25	90	12.3	-34.4	59.2
2^#	0.50	90	13.0	-17.6	58.7
3^#	0.75	90	13.6	-12.7	49.1
4^#	1.00	90	13.2	-9.3	52.1

图4 GQDs-TMC和GQDs/ChC-TMC纳滤膜的红外图谱(a)，BET孔径分布图(b)、EDS分析(c)

Fig.4 Characterization of GQDs-TMC and GQDs/ChC-TMC nanofiltration membranes, FTIR spectra (a), BET pore size distribution diagram (b), EDS analysis (c)

图5 反应温度(a)和ChC浓度(b)对GQDs/ChC-TMC纳滤膜分离性能的影响

Fig.5 Effect of reaction temperature (a) and ChC concentration (b) on GQDs/ChC-TMC nanofiltration membrane separation performance

表3 高温原料液和不同溶液浸泡24 h后GQDs/ChC-TMC纳滤膜的水渗透率和截留率

Table 3 Permeability and rejection rate of GQDs/ChC-TMC nanofiltration membrane for the feed solution at high temperature and after soaking 24 h in different solutions.

Treatments	Permeability/ ( $? L · m - 2 · h - 1 · b a r - 1$ )	$N a 2 S O 4$ rejection /%	MB rejection/ %
$H 2 O$	52.4±0.5	50.2±0.8	97.8±0.8
80℃ $H 2 O$	55.2±1.4	47.1±1.6	97.1±1.2
90℃ $H 2 O$	53.8±1.2	46.8±1.1	96.8±1.3
1 $g · L - 1$ NaClO	52.4±0.8	49.2±0.7	96.4±0.8
3%(mass) $H 2 O 2$	51.8±0.6	50.2±0.8	96.6±0.7
pH=13 NaOH	52.5±0.5	51.2±0.9	93.3±0.3
pH=1 HCl	51.6±0.6	49.2±1.4	91.6±1.0

表3 高温原料液和不同溶液浸泡24 h后GQDs/ChC-TMC纳滤膜的水渗透率和截留率

Table 3 Permeability and rejection rate of GQDs/ChC-TMC nanofiltration membrane for the feed solution at high temperature and after soaking 24 h in different solutions.

Treatments	Permeability/ ( $? L · m - 2 · h - 1 · b a r - 1$ )	$N a 2 S O 4$ rejection /%	MB rejection/ %
$H 2 O$	52.4±0.5	50.2±0.8	97.8±0.8
80℃ $H 2 O$	55.2±1.4	47.1±1.6	97.1±1.2
90℃ $H 2 O$	53.8±1.2	46.8±1.1	96.8±1.3
1 $g · L - 1$ NaClO	52.4±0.8	49.2±0.7	96.4±0.8
3%(mass) $H 2 O 2$	51.8±0.6	50.2±0.8	96.6±0.7
pH=13 NaOH	52.5±0.5	51.2±0.9	93.3±0.3
pH=1 HCl	51.6±0.6	49.2±1.4	91.6±1.0

图6 GQDs/ChC-TMC纳滤膜样品在1 g·L-1?NaClO溶液浸泡后的长期稳定性

Fig.6 Long-term stability of GQDs/ChC-TMC nanofiltration membrane after soaking in 1 g·L-1 NaClO solution

图7 GQDs-TMC和GQDs/ChC-TMC纳滤膜在HA(a)和BSA(b)污染液体系中的抗污染性能。3#样品在3.0% H2O2溶液浸泡6 h后得到3#*样品

Fig.7 Anti-fouling performance of GQDs-TMC and GQDs/ChC-TMC nanofiltration membranes operated with HA (a) and BSA (b) solutions. 3#* sample was 3# sample after immersion into 3.0% H2O2 for 6 h

表4 GQDs-TMC和GQDs/ChC-TMC纳滤膜的抗污染指数

Table 4 Antifouling indexes of GQDs-TMC and GQDs/ChC-TMC nanofiltration membrane membranes

Antifouling indexes/%	HA			BSA
Antifouling indexes/%	0^#	3^#	3^#*	0^#	3^#	3^#*
FRR	84.2	94.5	94.3	71.2	83.6	83.8
$D R t$	28.2	13.8	10.9	40.7	24.4	20.8
$D R r$	12.5	8.4	5.2	11.8	8.0	4.6
$D R i r$	15.8	5.4	5.7	28.8	16.4	16.2

表4 GQDs-TMC和GQDs/ChC-TMC纳滤膜的抗污染指数

Table 4 Antifouling indexes of GQDs-TMC and GQDs/ChC-TMC nanofiltration membrane membranes

Antifouling indexes/%	HA			BSA
Antifouling indexes/%	0^#	3^#	3^#*	0^#	3^#	3^#*
FRR	84.2	94.5	94.3	71.2	83.6	83.8
$D R t$	28.2	13.8	10.9	40.7	24.4	20.8
$D R r$	12.5	8.4	5.2	11.8	8.0	4.6
$D R i r$	15.8	5.4	5.7	28.8	16.4	16.2

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