MOF-199@GO改性PVDF荷电纳滤膜的制备及其性能

doi:10.11949/0438-1157.20200277

摘要/Abstract

摘要：

采用原位生长法制备了MOF-199@氧化石墨烯（GO）纳米复合材料，并对聚偏氟乙烯（PVDF）支撑膜进行表面改性，以克服PVDF膜表面疏水性。通过界面聚合反应，制备了基于MOF-199@GO改性PVDF的聚酰胺复合荷电纳滤膜。采用XRD、SEM、TEM、AFM和zeta电位等手段表征了MOF-199@GO复合材料及MOF-199@GO改性PVDF聚酰胺复合纳滤膜的结构及微观形貌，并测试了MOF-199@GO改性PVDF聚酰胺复合纳滤膜的脱盐性能。结果表明：通过MOF-199@GO复合材料对PVDF支撑膜的表面改性，有效克服了PVDF支撑膜的疏水性，实现了表面聚酰胺薄层的均匀连续生长，荷电纳滤膜表面荷负电性能显著增强，其中经MOF-199@GO充分改性的复合荷电纳滤膜表现出优异的脱盐性能，对MgSO₄、Na₂SO₄、NaCl和MgCl₂四种盐的截留率分别达到了93.56%、93.04%、87.48%和87.11%。

关键词: MOF-199, 氧化石墨烯, 聚偏氟乙烯, 膜, 复合材料, 脱盐

Abstract:

As novel functional materials, metal-organic framework (MOF) and graphene oxide (GO) have received great attentions in recent years. In this work, MOF@GO nanocomposite (MOF-199@GO) is prepared by an in-situ growth method. A novel and highly efficient nanofiltration (NF) membrane can be facilely fabricated via surface decoration of MOF-199@GO onto poly(vinylidene fluoride) (PVDF) substrate before interfacial polymerization of m-phenylenediamine (MPD) and trimesoyl chloride (TMC) in order to overcome the hydrophobicity of PVDF membrane. The structure and morphology of MOF-199@GO and MOF-199@GO modified PVDF polyamide composite membrane are characterized by XRD, SEM, TEM, AFM and zeta potential. MOF-199@GO modified PVDF composite NF membrane which possesses dense and uniform polyamide thin-layer exhibits higher negative surface potential (up to ~37 mV) at pH 9.5. The performance of MOF-199@GO modified PVDF polyamide composite NF membrane has been investigated by determination of pure water flux and salt rejection. The prepared NF membrane MG3 exhibited highly efficient rejection of MgSO₄, Na₂SO₄, NaCl and MgCl₂, which are 93.56%, 93.04%, 87.48% and 87.11%, respectively. This work provides a worthy reference for designing highly efficient NF membranes modified by MOF and relevant materials.

Key words: MOF-199, graphene oxide, PVDF, membranes, composites, desalination

中图分类号:

TQ 028.8

奥德, 张皓冰, 吕美婵, 王海涛, 常娜. MOF-199@GO改性PVDF荷电纳滤膜的制备及其性能[J]. 化工学报, 2020, 71(S2): 297-305.

De AO, Haobing ZHANG, Meichan LYU, Haitao WANG, Na CHANG. Preparation and properties of MOF-199@GO modified PVDF charged composite nanofiltration membrane[J]. CIESC Journal, 2020, 71(S2): 297-305.

图/表 12

图1 GO、MOF-199@GO复合材料及模拟MOF-199的XRD谱图

Fig.1 XRD patterns of GO, MOF-199@GO composite material and simulated MOF-199

图2 MOF-199@GO复合材料的扫描电镜图

Fig.2 SEM image of MOF-199@GO composite material

图3 MOF-199@GO复合材料的透射电镜图

Fig.3 TEM image of MOF-199@GO composite material

图4 复合膜表面的扫描电镜图

Fig.4 SEM images of composite membranes

图5 MG3膜表面的扫描电镜图及EDS图

Fig.5 SEM and EDS images of MG3 membrane

图6 复合膜断面扫描电镜图

Fig.6 Cross-section view of composite membranes

图7 膜在不同pH条件下的zeta电位

Fig.7 Zeta potential of each membrane at different pH value

表1 膜的等电点

Table 1 Isoelectric point of each membrane

名称	等电点
MG0	7.13
MG1	4.92
MG2	4.80
MG3	4.66

图8 膜表面的原子力显微镜图

Fig.8 AFM images of each membrane

表2 膜表面粗糙度参数

Table 2 Roughness parameters of composite membrane

名称	Ra/nm	Rq/nm
MG0	122	161
MG1	116	155
MG2	86	108
MG3	91	121

图9 膜的纯水通量测试结果

Fig.9 Pure water flux of each membrane

图10 膜对4种盐的截留率

Fig.10 Salt rejection of each membrane

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