新型还原氧化石墨烯/氮化碳复合纳滤膜制备及其性能

doi:10.11949/0438-1157.20190255

摘要/Abstract

摘要：

高性能石墨烯基复合膜的制备是目前国际研究热点，但是石墨烯基纳滤膜在脱盐中水通量较低，限制其在脱盐中的应用。采用聚多巴胺(PDA)改性聚砜(PSF)膜为基膜，将还原氧化石墨烯(rGO)和超薄氮化碳(uCN)纳米片通过真空抽滤法在基膜表面自组装制备新型还原氧化石墨烯/氮化碳复合纳滤膜。通过场发射扫描电子显微镜、透射电子显微镜、X 射线衍射仪、傅里叶变换红外光谱仪和X射线光电子能谱仪等研究uCN添加对膜结构和形貌的影响，并考察不同uCN添加比例、rGO用量及压力复合纳滤膜性能变化规律。结果显示当在100 mg·L^-1的rGO中添加uCN为20 mg·L^-1时所制备的rGO/uCN复合纳滤膜不仅保持良好盐离子截留率(对Na₂SO₄截留率85.86%，对NaCl截留率30.17%)，且水渗透系数是rGO膜的2.15倍(88.50 L·m^-2·h^-1·MPa^-1)。

关键词: 还原氧化石墨烯, 氮化碳, 复合膜, 纳滤, 脱盐

Abstract:

High performance graphene-based composite membranes have attracted great attentions, however, graphene-based nanofiltration membranes usually exhibit low water flux in removing salt ions, which limits its application in water desalination. Novel reduced graphene oxide (rGO)/ultrathin carbon nitride (uCN) composite nanofiltration membrane was prepared by self-assembling rGO and nanoporous uCN nanosheets on polydopamine (PDA) modified polysulfone (PSF) support via vacuum filtration. Field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy analysis (XPS) were applied to evaluate the changes in structure and morphology of membranes by introducing uCN. The effects of addition ratios of uCN, rGO content and operating pressure on the performance of composite membranes were also investigated. With 20 mg·L^-1 uCN content in 100 mg·L^-1 of rGO, the prepared rGO/uCN composite membrane not only maintained satisfied salt rejection rates (85.86% for Na₂SO₄, 30.17% for NaCl), but also possessed 2.15 times water permeance (88.50 L·m^-2·h^-1·MPa^-1) that of pure rGO membrane.

Key words: reduced graphene oxide, ultrathin carbon nitride, composite membrane, nanofiltration, desalination

中图分类号:

TQ 028.8

徐颜军, 徐泽海, 孟琴, 沈冲, 侯蕊, 张国亮. 新型还原氧化石墨烯/氮化碳复合纳滤膜制备及其性能[J]. 化工学报, 2019, 70(9): 3565-3572.

Yanjun XU, Zehai XU, Qin MENG, Chong SHEN, Rui HOU, Guoliang ZHANG. Preparation and performance of novel rGO/uCN composite nanofiltration membrane[J]. CIESC Journal, 2019, 70(9): 3565-3572.

图/表 13

图1 rGO/uCN复合膜实验过程

Fig.1 Schematic illustration of experiment of rGO/uCN composite membranes

表1 不同膜种类

Table 1 Different types of membrane

Group	Membranes
N0	rGO NF membrane
N1	10 mg·L^-1 uCN-intercalated rGO/uCN coposite NF membrane
N2	12.5 mg·L^-1 uCN-intercalated rGO/uCN coposite NF membrane
N3	20 mg·L^-1 uCN-intercalated rGO/uCN coposite NF membrane
N4	25 mg·L^-1 uCN-intercalated rGO/uCN coposite NF membrane

图2 GO和rGO/uCN复合膜的XPS谱图

Fig.2 XPS spectra of GO and rGO/uCN composite membranes

图3 GO，uCN及不同rGO/uCN复合膜的FTIR谱图

Fig.3 FTIR spectra of GO, uCN and different rGO/uCN composite membranes

图4 GO，uCN及不同rGO/uCN复合膜的XRD谱图

Fig.4 XRD patterns of GO, uCN and different rGO/uCN composite membranes

图5 uCN的TEM图(a)和uCN的孔径分布(b)

Fig.5 TEM image of uCN (a) and nanopores size distribution of uCN (b)

图6 rGO/uCN复合膜的结构及水分子传输路径

Fig.6 Schematic representation of structure and water transport path for rGO/uCN composite membrane

图7 不同复合纳滤膜的SEM表面[(a)~(e)]、断面[(f)~(j)]图

Fig.7 Surface [(a)—(e)] and cross-section [(f)—(j)] SEM images of different composite membranes

图8 uCN含量对复合膜水通量及不同无机盐溶液截留率的影响

Fig.8 Effect of content of uCN on water flux and different salts rejection of composite membranes

图9 不同复合纳滤膜的Zeta电位随pH变化情况

Fig.9 Zeta potential versus pH curves of different composite membranes

图10 不同rGO含量对复合膜水通量和Na2SO4截留率的影响

Fig.10 Effect of content of rGO on water flux and Na2SO4 rejection of composite membranes

图11 不同压力对复合膜水通量的影响

Fig.11 Effect of pressure on water flux of composite membrane

图12 复合膜在pH=2(a)，pH=7(b)和pH=12(c)环境下的稳定性图片

Fig.12 Picture of stability of composite membranes in water at pH=2(a)，pH=7(b)和pH=12(c)

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