层状Mg/Al氢氧化物/聚乙烯醇复合膜的制备及染料截留性能的研究

doi:10.11949/0438-1157.20210566

摘要/Abstract

摘要：

二维膜因其可控的结构和通道特有的物理化学性质，在气体分离、海水淡化、污水处理等诸多分离领域展现出巨大的应用潜力。通过层状Mg/Al氢氧化物（LDH）单片与聚乙烯醇（PVA）高分子链之间的氢键相互作用，层层堆叠构建了PVA/LDH复合膜。利用SEM、XRD考察了PVA与LDH的配比对于复合膜层状结构与层间距高度的影响规律。考察了PVA/LDH复合膜的纯水通量及染料模型分子的截留率。结果表明，不同PVA混合量的复合膜断面都具有层状结构。由于氢键作用导致复合膜较之于纯LDH膜的层间距有所缩小，随着PVA含量增加复合膜层间距先减小后增加；在PVA含量为15%时达到最小值，PVA含量超过15%后复合膜层间距有所增加。不同比例复合膜，以PVA质量分数为25%的复合膜的纯水通量最大；同时，该复合膜对分子量在300~800的染料分子具有优异的截留性能，截留率均超过97%。该工作为PVA/LDH复合膜在印染废水处理提供了新思路。

关键词: 膜, 二维材料, 复合材料, 废水

Abstract:

Due to its controllable structure and unique physical and chemical properties of the channel, the two-dimensional membrane has shown great application potential in many separation fields such as gas separation, seawater desalination, and sewage treatment. In this paper, the PVA/LDH composite membrane is constructed by layers stacking, in which layered Mg/Al hydroxide (LDH) monolayer and polyvinyl alcohol (PVA) polymer chain form hydrogen bond interaction. The effects of the ratio of PVA to LDH on the lamellar structure and the height of the lamellar spacing of the composite membranes are investigated by SEM and XRD. The water flux and dyes rejection of PVA/LDH composite membranes are investigated. The results show that the cross-sections of the composite membranes with different PVA mass fractions have lamellar structures. Compared with the LDH membrane, the interlayer spacing of the composite membranes is decreased due to the hydrogen bonding interaction. With the increase of PVA content, the interlayer spacing of the composite membranes decreased firstly and then increased, in which the content of PVA is 15%, the value of spacing is minimum, while the content of PVA exceeds 15%, the interlayer spacing increased. The pure water flux of the composite membrane with a PVA mass fraction of 25% is the largest. The composite membrane has excellent rejection performance for the molecular weight of dye molecules in the range of 300—800, and the rejection rate is more than 97%. This work provides a novel path for the treatment of printing and dyeing wastewater.

Key words: membrane, two-dimensional materials, composites, wastewater

中图分类号:

TQ 028.8

张杰, 刘壮, 巨晓洁, 谢锐, 汪伟, 褚良银. 层状Mg/Al氢氧化物/聚乙烯醇复合膜的制备及染料截留性能的研究[J]. 化工学报, 2021, 72(9): 4941-4949.

Jie ZHANG, Zhuang LIU, Xiaojie JU, Rui XIE, Wei WANG, Liangyin CHU. Fabrication and dye separation performance study of layered Mg/Al hydroxide/polyvinyl alcohol composite membrane[J]. CIESC Journal, 2021, 72(9): 4941-4949.

图/表 9

图1 膜通量测量装置

Fig.1 Membrane flux measuring device

图2 不同PVA质量分数PVA/LDH复合膜断面扫描电镜图

Fig.2 SEM images of cross-sections of composite membranes with different PVA mass fraction

图3 不同PVA质量分数PVA/LDH复合膜的X射线衍射谱图(a)和复合膜层间距(b)

Fig.3 XRD patterns (a) and interlamellar spacing (b) of PVA/LDH composite membranes with different PVA mass fraction

图4 不同PVA质量分数PVA/LDH复合膜红外谱图

Fig.4 FTIR spectra of PVA/LDH composite membranes with different PVA mass fraction

图5 不同PVA质量分数PVA/LDH复合膜的热重分析曲线(a)和复合膜实际混合比(b)

Fig.5 Thermogravimetric analysis (a) and real PVA mass fraction (b) of PVA/LDH composite membrane with different PVA mass fraction

图6 PVA质量分数50%复合膜元素能谱图

Fig.6 EDX mapping of composite membrane with PVA mass fraction 50%

图7 不同PVA质量分数PVA/LDH复合膜纯水通量

Fig.7 Water flux of PVA/LDH composite membrane with different PVA mass fraction

图8 PVA质量分数25%复合膜染料截留性能

Fig.8 Intercepting performance of different dyes of 25% PVA/LDH composite membrane

图9 不同染料分子三维尺寸

Fig.9 Three dimensional dimensions of different dye molecules

参考文献 38

1	Novoselov K S, Geim A K, Morozov S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696): 666-669.
2	Zhan H L, Xiong Z Y, Cheng C, et al. Solvation-involved nanoionics: new opportunities from 2D nanomaterial laminar membranes[J]. Advanced Materials, 2020, 32(18): 1904562.
3	Liu G P, Jin W Q, Xu N P. Two-dimensional-material membranes: a new family of high-performance separation membranes[J]. Angewandte Chemie International Edition, 2016, 55(43): 13384-13397.
4	Liu G P, Jin W Q, Xu N P. Graphene-based membranes[J]. Chemical Society Reviews, 2015, 44(15): 5016-5030.
5	Yang X D, Yang Y B, Fu L N, et al. An ultrathin flexible 2D membrane based on single-walled nanotube-MoS₂ hybrid film for high-performance solar steam generation[J]. Advanced Functional Materials, 2018, 28(3): 1704505.
6	Ding L, Wei Y Y, Li L B, et al. MXene molecular sieving membranes for highly efficient gas separation[J]. Nature Communications, 2018, 9(1): 1-7.
7	Pendse A, Cetindag S, Lin M H, et al. Charged layered boron nitride-nanoflake membranes for efficient ion separation and water purification[J]. Small, 2019, 15(49): 1904590.
8	Wang Y, Wu N N, Wang Y, et al. Graphite phase carbon nitride based membrane for selective permeation[J]. Nature Communications, 2019, 10: 2500.
9	Lu P, Liu Y, Zhou T T, et al. Recent advances in layered double hydroxides (LDHs) as two-dimensional membrane materials for gas and liquid separations[J]. Journal of Membrane Science, 2018, 567: 89-103.
10	Razmjou A, Eshaghi G, Orooji Y, et al. Lithium ion-selective membrane with 2D subnanometer channels[J]. Water Research, 2019, 159: 313-323.
11	Prozorovska L, Kidambi P R. State-of-the-art and future prospects for atomically thin membranes from 2D materials[J]. Advanced Materials, 2018, 30(52): 1801179.
12	Wang L D, Boutilier M S H, Kidambi P R, et al. Fundamental transport mechanisms, fabrication and potential applications of nanoporous atomically thin membranes[J]. Nature Nanotechnology, 2017, 12(6): 509-522.
13	Wang Q, O'Hare D. Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets[J]. Chemical Reviews, 2012, 112(7): 4124-4155.
14	王瑞瑞, 赵有璟, 邵明飞, 等. 层状双金属氢氧化物用于催化水氧化的研究进展[J]. 化工学报, 2016, 67(1): 54-72.
	Wang R R, Zhao Y J, Shao M F, et al. Recent progresses in water oxidation over layered double hydroxide catalysts[J]. CIESC Journal, 2016, 67(1): 54-72.
15	Wang J Y, Zhang T P, Li M, et al. Arsenic removal from water/wastewater using layered double hydroxide derived adsorbents, a critical review[J]. RSC Advances, 2018, 8(40): 22694-22709.
16	Asiabi H, Yamini Y, Shamsayei M. Highly selective and efficient removal of arsenic(V), chromium(Ⅵ) and selenium(Ⅵ) oxyanions by layered double hydroxide intercalated with zwitterionic glycine[J]. Journal of Hazardous Materials, 2017, 339: 239-247.
17	马嘉壮, 陈颖, 李凯涛, 等. 镁基插层结构功能材料研究进展[J]. 化工学报, 2021, 72(6): 2922-2933.
	Ma J Z, Chen Y, Li K T, et al. Research progress on magnesium-based intercalated functional materials[J]. CIESC Journal, 2021, 72(6): 2922-2933.
18	Zhang G H, Zhang X Q, Meng Y, et al. Layered double hydroxides-based photocatalysts and visible-light driven photodegradation of organic pollutants: a review[J]. Chemical Engineering Journal, 2020, 392: 123684.
19	Chen C, Tao L, Du S Q, et al. Advanced exfoliation strategies for layered double hydroxides and applications in energy conversion and storage[J]. Advanced Functional Materials, 2020, 30(14): 1909832.
20	Sun Z Y, Jin L, Shi W Y, et al. Controllable photoluminescence properties of an anion-dye-intercalated layered double hydroxide by adjusting the confined environment[J]. Langmuir, 2011, 27(11): 7113-7120.
21	Ameena Shirin V K, Sankar R, Johnson A P, et al. Advanced drug delivery applications of layered double hydroxide[J]. Journal of Controlled Release, 2021, 330: 398-426.
22	Gao Y S, Wu J W, Wang Q, et al. Flame retardant polymer/layered double hydroxide nanocomposites[J]. Journal of Materials Chemistry A, 2014, 2(29): 10996.
23	Liu Y, Wang N Y, Caro J. In situ formation of LDH membranes of different microstructures with molecular sieve gas selectivity[J]. Journal of Materials Chemistry A, 2014, 2(16): 5716-5723.
24	Liu Y, Wang N Y, Cao Z W, et al. Molecular sieving through interlayer galleries[J]. Journal of Materials Chemistry A, 2014, 2(5): 1235-1238.
25	Wang N X, Huang Z, Li X T, et al. Tuning molecular sieving channels of layered double hydroxides membrane with direct intercalation of amino acids[J]. Journal of Materials Chemistry A, 2018, 6(35): 17148-17155.
26	Sun P, Ma R, Bai X, et al. Single-layer nanosheets with exceptionally high and anisotropic hydroxyl ion conductivity[J]. Science Advances, 2017, 3(4): e1602629.
27	Zhu H, Huang S, Yang Z, et al. Oriented printable layered double hydroxide thin films via facile filtration[J]. Journal of Materials Chemistry, 2011, 21(9): 2950.
28	Han J B, Xu X Y, Rao X Y, et al. Layer-by-layer assembly of layered double hydroxide/cobalt phthalocyanine ultrathin film and its application for sensors[J]. J. Mater. Chem., 2011, 21(7): 2126-2130.
29	He X Y, Cao L, He G W, et al. A highly conductive and robust anion conductor obtained via synergistic manipulation in intra- and inter-laminate of layered double hydroxide nanosheets[J]. Journal of Materials Chemistry A, 2018, 6(22): 10277-10285.
30	Li L, Ma R Z, Ebina Y, et al. Positively charged nanosheets derived via total delamination of layered double hydroxides[J]. Chemistry of Materials, 2005, 17(17): 4386-4391.
31	Dikin D A, Stankovich S, Zimney E J, et al. Preparation and characterization of graphene oxide paper[J]. Nature, 2007, 448(7152): 457-460.
32	Dong Y P, Lin C, Gao S J, et al. Single-layered GO/LDH hybrid nanoporous membranes with improved stability for salt and organic molecules rejection[J]. Journal of Membrane Science, 2020, 607: 118184.
33	Zhan Y Q, Wan X Y, He S J, et al. Design of durable and efficient poly(arylene ether nitrile)/bioinspired polydopamine coated graphene oxide nanofibrous composite membrane for anionic dyes separation[J]. Chemical Engineering Journal, 2018, 333: 132-145.
34	Zhao S, Zhu H T, Wang Z, et al. A loose hybrid nanofiltration membrane fabricated via chelating-assisted in situ growth of Co/Ni LDHs for dye wastewater treatment[J]. Chemical Engineering Journal, 2018, 353: 460-471.
35	Huang Z, Wang N X, Li X T, et al. Calcination of layered double hydroxide membrane with enhanced nanofiltration performance[J]. Journal of Industrial and Engineering Chemistry, 2020, 89: 368-374.
36	Xu Y C, Wang Z X, Cheng X Q, et al. Positively charged nanofiltration membranes via economically mussel-substance-simulated co-deposition for textile wastewater treatment[J]. Chemical Engineering Journal, 2016, 303: 555-564.
37	Zhang P, Gong J L, Zeng G M, et al. Cross-linking to prepare composite graphene oxide-framework membranes with high-flux for dyes and heavy metal ions removal[J]. Chemical Engineering Journal, 2017, 322: 657-666.
38	Lu T, Chen F W. Multiwfn: a multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.

[1]	邵苛苛, 宋孟杰, 江正勇, 张旋, 张龙, 高润淼, 甄泽康. 水平方向上冰中受陷气泡形成和分布实验研究[J]. 化工学报, 2023, 74(S1): 161-164.
[2]	吴延鹏, 李晓宇, 钟乔洋. 静电纺丝纳米纤维双疏膜油性细颗粒物过滤性能实验分析[J]. 化工学报, 2023, 74(S1): 259-264.
[3]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[4]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[5]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[6]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.
[7]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[8]	齐聪, 丁子, 余杰, 汤茂清, 梁林. 基于选择吸收纳米薄膜的太阳能温差发电特性研究[J]. 化工学报, 2023, 74(9): 3921-3930.
[9]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[10]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[11]	张佳怡, 何佳莉, 谢江鹏, 王健, 赵鹬, 张栋强. 渗透汽化技术用于锂电池生产中N-甲基吡咯烷酮回收的研究进展[J]. 化工学报, 2023, 74(8): 3203-3215.
[12]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[13]	张贲, 王松柏, 魏子亚, 郝婷婷, 马学虎, 温荣福. 超亲水多孔金属结构驱动的毛细液膜冷凝及传热强化[J]. 化工学报, 2023, 74(7): 2824-2835.
[14]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[15]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.