异质结构g-C3N4@AM层状膜构筑及纳滤性能研究

doi:10.11949/0438-1157.20210869

摘要/Abstract

摘要：

随着化工行业的迅速发展，利用纳滤膜对有机溶剂进行高效分离受到了越来越多的关注，但有机溶剂纳滤膜通量和选择性之间普遍存在 trade-off 效应的限制。以相对疏水的g-C₃N₄纳米片和亲水的直链淀粉（amylose，AM）为构筑单元，利用双针头静电雾化技术制备了异质结构的g-C₃N₄@AM 层状膜。亲水的直链淀粉促进了极性溶剂的溶解，相对疏水的g-C₃N₄纳米片实现了通道对极性溶剂的低阻力扩散；两者协同，极大地增强了膜对极性溶剂的渗透性能，而不降低分离能力。与纯g-C₃N₄层状膜相比，g-C₃N₄@AM 层状膜对极性溶剂的渗透系数提高了1~2倍，对于尺寸大于 1.5 nm 的染料分子可以实现 99% 以上的截留率。在操作稳定性、压力循环和耐酸碱测试后，膜的渗透性能和截留能力基本保持不变，衰减 < 6%，具有较好的操作稳定性。

关键词: 异质结构, 静电雾化, 直链淀粉, 膜, 纳滤, 分离

Abstract:

With the rapid development of industry, increasing attention has been paid to the efficient separation of organic solvents by nanofiltration membranes. However, nanofiltration membranes are difficult to be further industrialized because of the trade-off effect between flux and selectivity. In this paper, hydrophobic g-C₃N₄ nanosheets and hydrophilic amylose (AM) were used as building units to prepare heterostructure g-C₃N₄@AM lamellar membrane by double needle electrostatic atomization. The hydrophilic amylose promotes the dissolution of polar solvents and the hydrophobic g-C₃N₄ nanosheets provide the low resistance diffusion of polar solvents. Therefore, this heterostructure structure greatly enhances the permeation of the membrane to polar solvents without reducing the separation ability. Compared with g-C₃N₄ membrane, the g-C₃N₄@AM membranes show 1—2 times higher polar solvent permeance. Simultaneously, the g-C₃N₄@AM membranes accomplish 99% rejections towards dye molecules with sizes above 1.5 nm. After long-term operation, pressure cycle and acid-base stability test, the variation of solvent permeance and dye rejection is below 6%, which demonstrate that this hydrophilic/hydrophobic heterostructured lamellar membrane shows great operating stability.

Key words: heterostructure, electrostatic atomization, amylose, membrane, nanofiltration, separation

中图分类号:

TQ 028.8

周国莉, 韩项珂, 武文佳, 王景涛, 张毛娃, 李凤丽. 异质结构g-C₃N₄@AM层状膜构筑及纳滤性能研究[J]. 化工学报, 2022, 73(2): 941-950.

Guoli ZHOU, Xiangke HAN, Wenjia WU, Jingtao WANG, Maowa ZHANG, Fengli LI. Construction heterostructure g-C₃N₄@AM lamellar membrane and its performance of organic solvent nanofiltation[J]. CIESC Journal, 2022, 73(2): 941-950.

图/表 11

图1 g-C3N4@AM层状膜制备示意图

Fig.1 Schematic illustration of the fabrication of g-C3N4@AM membrane

图2 g-C3N4纳米片的 AFM 图、SEM 图和TEM 图

Fig.2 AFM，SEM and TEM images of g-C3N4 nanosheet

图3 g-C3N4 纳米片以及直链淀粉的红外光谱和水接触角

Fig.3 FTIR curves and contact angles of g-C3N4 nanosheet and amylose

图4 纯g-C3N4 膜和g-C3N4@AM 膜的 SEM、断面以及AFM图像

Fig.4 Surface,cross-section SEM images, AFM images of g-C3N4 membrane and g-C3N4 @AM membrane

图5 纯g-C3N4膜(A)和g-C3N4@AM膜(B)的XRD、N2 吸附等温线、FTIR和 XPS谱图

Fig.5 XRD,N2 sorption isotherms,FTIR and XPS spectrum of g-C3N4 membrane(A) and g-C3N4 @AM membrane(B)

图6 纯 g-C3N4 膜和 g-C3N4@AM 膜的溶剂渗透通量和跨膜阻力

Fig.6 Solvent permeance and solvent resistance comparison for g-C3N4 membrane and g-C3N4 @AM membrane

图7 纯g-C3N4 膜和 g-C3N4@AM 膜对染料的截留率

Fig.7 Dye rejection of g-C3N4 membrane and g-C3N4 @AM membrane

图8 g-C3N4@AM 膜的操作稳定性、渗透与截留的压力循环以及酸碱稳定性实验

Fig.8 Long-term operation performances, pressure cycle and acid-base stability of g-C3N4 @AM membrane

图9 g-C3N4@AM 膜对印染废水的截留率

Fig.9 Dye rejection of g-C3N4 @AM membrane

图10 g-C3N4@AM 膜的长期操作稳定性、渗透与截留的压力循环以及酸碱稳定性实验

Fig.10 Long-term operation performances,pressure cycle and acid-base stability of g-C3N4 @AM membrane

表1 所制备膜与文献报道膜有机溶剂纳滤性能比较

Table 1 The comparison of performance of organic solvent nanofiltration membranes

分离膜名称	分离染料	溶剂	渗透通量/(L·m^-2·h^-1·bar^-1)	截留率/ %	文献
MXene	伊文思蓝	水	1084	90	[16]
GO	伊文思蓝	水	71	85	[29]
MoS₂	伊文思蓝	水	245	89	[17]
WS₂	伊文思蓝	水	450	89	[30]
GO/PC	伊文思蓝	水	71	85	[31]
COF	亚甲基蓝	水	125	98	[32]
rGO	亮黄	水	88.3	99.2	[21]
rGO-SWCNT	细胞色素C	水	720	98	[33]
PES	考马斯亮蓝	水	100	65	[16]
rGO/PVDF	亚甲基蓝	水	21.8	99.2	[34]
HPEI/S-rGO-18	碱性品红	甲醇	74.2	88.5	[21]
(PA/TiO₂)/PAN	聚乙二醇	异丙醇	0.3	95	[35]
PEI-DBX/PBI	四环素	乙醇	4.5	99	[36]

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异质结构g-C₃N₄@AM层状膜构筑及纳滤性能研究

Construction heterostructure g-C₃N₄@AM lamellar membrane and its performance of organic solvent nanofiltation

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