负载羧基化球状介孔纳米颗粒TFN膜的研究

doi:10.11949/0438-1157.20190920

化工学报 ›› 2020, Vol. 71 ›› Issue (S1): 454-460.DOI: 10.11949/0438-1157.20190920

• 材料化学工程与纳米技术 • 上一篇下一篇

负载羧基化球状介孔纳米颗粒TFN膜的研究

孙艳^1,^2,³(),刘士涛¹,邓尚⁴,余丽芸²,吕东伟³,马军³(),刘献斌⁴()

^1.南京大学昆山创新研究院，江苏昆山 215347
^2.黑龙江八一农垦大学生命科学技术学院，黑龙江大庆 163319
^3.哈尔滨工业大学环境学院, 城市水资源与环境国家重点实验室，黑龙江哈尔滨 150090
^4.哈尔滨理工大学化学与环境工程学院, 黑龙江哈尔滨 150040

收稿日期:2019-08-12 修回日期:2019-09-15 出版日期:2020-04-25 发布日期:2020-04-25
通讯作者: 马军,刘献斌
作者简介:孙艳(1974—)，女，副教授，25180510@qq.com
基金资助:
中国博士后科学基金资助项目(2014M561359);江苏省科技项目(BE2016695)

Research of thin film nanocomposite (TFN) membranes incorporated spherical mesoporous silica nanoparticles with carboxyl group

Yan SUN^1,^2,³(),Shitao LIU¹,Shang DENG⁴,Liyun YU²,Dongwei LYU³,Jun MA³(),Xianbin LIU⁴()

^1.Kunshan Innovation Institute of Nanjing University, Kunshan 215347, Jiangsu, China
^2.College of Life Sciences and Technology, Heilongjiang Bayi Agricultural University, Daqing 163319, Heilongjiang, China
^3.State Key Laboratory of Urban Water Resource and Environment, School of Environmental, Harbin Institute of Technology, Harbin 150090, Heilongjiang, China
^4.School of Chemistry and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, Heilongjiang, China

Received:2019-08-12 Revised:2019-09-15 Online:2020-04-25 Published:2020-04-25
Contact: Jun MA,Xianbin LIU

摘要/Abstract

摘要：

在薄层复合膜(thin-film composite membrane, TFC膜)中引入无机纳米颗粒，形成薄层纳米复合膜(thin-film nanocomposite membrane, TFN膜)，近几年作为反渗透膜开始应用于水处理研究。但是无机纳米颗粒在TFC膜中的性能的不稳定性和膜的机械强度等变成了突出问题。合成制备了粒径约为110 nm修饰羧基的介孔氧化硅球状纳米颗粒(MSN—COOH)，并将其成功地化学键合在TFC膜的表面功能层交联网络中。与TFC膜相比，键合有MSN—COOH的TFN膜，水通量提高了56.2%，保持高脱盐率；由于单分散介孔纳米颗粒表面亲水官能团的引入，使膜表面的亲水性有很大程度提高，单分散介孔纳米颗粒在基体中的有序排列，使膜表面粗糙度降低，提高了膜的抗污染能力。与普通TFN膜相比较，具有更好的稳定性和柔韧性，可以在长时间高压过滤操作下保持稳定。

关键词: 纳米粒子, 膜, 二氧化硅, TFN, 羧基修饰, 界面聚合

Abstract:

Thin film composite (TFC) membranes incorporated with inorganic nanoparticles to form thin film nanocomposite (TFN) membranes, which had attracted much attention recently. However, the instability of nanoparticles in the TFC membranes and the insufficient mechanical strength of the membranes became the main challenges. Mesoporous silica nanoparticles with an average particle size of ca. 110 nm were modified with carboxyl groups, noted as MSN—COOH and further immobilized on the functional layer of the TFC membranes. The carboxyl groups were successfully incorporated into the mesoporous channels of MSN by characterization techniques, MSN—COOH nanoparticles were successfully bonded to the surface functional layer of the TFC film and formed the crosslinked network. Our experimental results revealed that the TFN membrane hybridized with MSN—COOH demonstrated up to 56.2% improvement in water ?ux, higher salt rejection, and improved mechanical strength compared to the control TFC membranes. Due to the addition of hydrophilic functional groups in monodisperse mesoporous nanoparticles, the hydrophilicity of the membrane surface was increased. Because of the ordered arrangement of monodisperse mesoporous nanoparticles in the matrix, the roughness of the membrane was lowered to a great extent, which was beneficial for enhancing water molecular transfer and fouling resistance of the membranes. Compared with plain TFN membranes, it had better stability and flexibility which kept the stabilization of membranes under high pressure filtration operation.

Key words: nanoparticles, membrane, silica, TFN, modified with carboxyl groups, interfacial polymerization

中图分类号:

TQ 051.893

孙艳, 刘士涛, 邓尚, 余丽芸, 吕东伟, 马军, 刘献斌. 负载羧基化球状介孔纳米颗粒TFN膜的研究[J]. 化工学报, 2020, 71(S1): 454-460.

Yan SUN, Shitao LIU, Shang DENG, Liyun YU, Dongwei LYU, Jun MA, Xianbin LIU. Research of thin film nanocomposite (TFN) membranes incorporated spherical mesoporous silica nanoparticles with carboxyl group[J]. CIESC Journal, 2020, 71(S1): 454-460.

图/表 8

图1 纳米颗粒的FTIR谱图

Fig.1 FTIR spectra for nanoparticlesa—as-MSN；b—MSN；c—MSN—NH2；d—MSN—COOH

表1 介孔纳米颗粒的结构性质

Table 1 Textural properties of nanoparticles

样品	孔径/nm	比表面积/(m²/g)	孔容/(cm³/g)
MSN	2.84	832	0.87
MSN—NH₂	2.52	586	0.74
MSN—COOH	2.53	493	0.75

图2 MSN和MSN—COOH的XRD谱图

Fig.2 XRD patterns of MSN and MSN—COOH

图3 MSN(a)和MSN—COOH(b)的SEM图与TEM图(插图)

Fig.3 SEM and TEM (inset) images of MSN (a) and MSN—COOH (b)

图4 膜的ATR-FTIR谱图

Fig.4 ATR-FTIR spectra of membranesa—TFC；b—TFN-MSN-0.1；c—TFN-MSN-0.4；d—TFN-MSN—COOH-0.1；e—TFN-MSN—COOH-0.4

图5 反渗透膜的SEM图(a),(b) 普通TFC膜；(c),(d) TFN-MSN—COOH-0.1；(e),(f) TFN-MSN—COOH-0.2

Fig.5 SEM images of fabricated membranes

图6 膜的水通量与盐截留率（2.0685 MPa，25°C）

Fig.6 Membrane water flux and salt rejection（2.0685 MPa，25°C）

图7 TFN-MSN—COOH-0.2膜运行100 h的性能参数

Fig.7 Separation performances of TFN TFN-MSN—COOH-0.2 membrane during 100 h stability test

参考文献 33

1	Elimelech M, Phillip W A. The future of seawater desalination: energy, technology, and the environment[J]. Science, 2011, 333: 712-717.
2	Shannon M A, Bohn P W, Elimelech M, et al. Science and technology for water purification in the coing decades[J]. Nature, 2008, 452: 301-310.
3	华怀玉. 现阶段反渗透膜研究进展[J]. 环境与发展, 2018, 30(6): 95-96.
	Hua H Y. Research progress on reverse osmosis membrane at present[J]. Environment and Development, 2018, 30(6): 95-96.
4	曹震, 魏杨扬, 赵曼, 等. 反渗透复合膜研究进展与展望[J]. 水处理技术, 2016, 42(9): 10-16+21.
	Cao Z, Wei Y Y, Zhao M, et al. Progress and prospect in the development of reverse osmosis composite membrane technology[J]. Technology of Water Treatment, 2016, 42(9): 10-16+21
5	Soltanieh M, Gill W N. Review of reverse osmosis membrane and transport models[J]. Chem. Eng. Commun., 1981, 12: 279-363.
6	Otitoju T A, Saari R A, Ahmad A L. Progress in the modification of reverse osmosis (RO) membranes for enhanced performance[J]. J. Ind. Eng. Chem., 2018, 67: 52-71.
7	Al-Mayyahi A. Important approaches to enhance reverse osmosis (RO) thin film composite (TFC) membranes performance[J]. Membranes, 2018, 8: 68.
8	赵海洋, 张林. 聚酰胺反渗透膜的分子动力学模拟研究进展[J]. 化工进展, 2017, 36(12): 4319-4328.
	Zhao H Y, Zhang L. Molecular dynamic simulation of polyamide reverse osmosis membrane[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4319-4328.
9	潘春佑, 徐国荣, 李露, 等. 聚酰胺反渗透复合膜改性技术研究进展[J]. 膜科学与技术, 2016, 36(6): 133-138.
	Pan C Y, Xu G R, Li L, et al. Developments and perspectives on the polyamide-based reverse osmosis desalination membranes[J]. Membrane Science and Technology, 2016, 36(6): 133-138.
10	Hermans S, Mariën H, van Goethem C, et al. Recent developments in thin film (nano) composite membranes for solvent resistant nanofiltration[J]. Curr. Opin. Chem. Eng., 2015, 8: 45-54.
11	Pendergast M M, Hoek E M V. A review of water treatment membrane nanotechnologies[J]. Energy Environ. Sci., 2011, 4: 1946-1971.
12	许中煌, 雷萍萍, 洪昱斌, 等. 氧化石墨烯/碱式硫酸铝掺杂聚醚砜/聚酰胺复合纳滤膜的制备及其性能[J]. 化工学报, 2018, 69(9): 4066-4074.
	Xu Z H, Lei P P, Hong Y B, et al. Preparation and performance of graphene oxide/basic aluminum sulfate doped polyethersulfone/polyamide composite nanofiltration membrane[J]. CIESC Journal, 2018, 69(9): 4066-4074.
13	周丰, 黄慧敏, 钱飞跃, 等. 碳纳米管负载层结构对复合膜分离性能的影响研究[J]. 化工学报, 2018, 69(5): 2318-2326.
	Zhou F, Huang H M, Qian F Y, et al. Effects of carbon nanotubes mats structure on rejection performance of composite membranes[J]. CIESC Journal, 2018, 69(5): 2318-2326.
14	陈贤鸿, 傅倍佳, 钟明强, 等. 氧化石墨烯掺杂反渗透混合基质膜制备及性能[J]. 化工学报, 2018, 69(1): 429-434.
	Chen X J, Fu B J, Zhong M Q, et al. Preparation and performance of graphene oxide doped reverse osmosis mixed matrix membrane[J]. CIESC Journal, 2018, 69(1): 429-434.
15	Yin J, Kim E S, Yang J, et al. Fabrication of a novel thin-film nanocomposite (TFN) membrane containing MCM-41 silica nanoparticles (NPs) for water purification[J]. J. Membr. Sci., 2012, 423: 238-246.
16	Zargar M, Hartanto Y, Jin B, et al. Polyethylenimine modified silica nanoparticles enhance interfacial interactions and desalination performance of thin film nanocomposite membranes[J]. J. Membr. Sci., 2017, 541: 19-28.
17	Lu X, Romero-Vargas C S, Shaffer D, et al. In situ surface chemical modification of thin-film composite forward osmosis membranes for enhanced organic fouling resistance[J]. Energy Environ. Sci., 2012, 47: 12219-12228.
18	Liu X, Sun H, Yang Y. Rapid synthesis of highly ordered Si-MCM-41[J]. J. Colloid Interf. Sci., 2008, 319: 377-380.
19	Deng H, Xu Y, Chen Q, et al. High flux positively charged nanofiltration membranes prepared by UV-initiated graft polymerization of methacrylatoethyl trimethyl ammonium chloride (DMC) onto polysulfone membranes[J]. J. Membr. Sci., 2011, 366: 363-372.
20	Tarboush B J A, Rana D, Matsuura T, et al. Preparation of thin-film-composite polyamide membranes for desalination using novel hydrophilic surface modifying macromolecules[J]. J. Membr. Sci., 2008, 325: 166-175.
21	Jimenez-Solomon M F, Bhole Y, Livingston A G J. High flux membranes for organic solvent nanofiltration (OSN)—interfacial polymerization with solvent activation[J]. J. Membr. Sci., 2012, 423: 371-382.
22	Jadav G L, Singh P S. Synthesis of novel silica-polyamide nanocomposite membrane with enhanced properties[J]. J. Membr. Sci., 2009, 328: 257-267.
23	Pacheco F A, Pinnau I, Reinhard M, et al. Characterization of isolated polyamide thin films of RO and NF membranes using novel TEM techniques[J]. J. Membr. Sci., 2010, 358: 51-59.
24	Chai G Y, Krantz W B. Formation and characterization of polyamide membranes via interfacial polymerization[J]. J. Membr. Sci., 1994, 93: 175-192.
25	Freger V. Nanoscale heterogeneity of polyamide membranes formed by interfacial polymerization[J]. Langmuir, 2003, 19: 4791-4797.
26	Xie W, Geise G M, Freeman B D, et al. Polyamide interfacial composite membranes prepared from m-phenylene diamine, trimesoyl chloride and a new disulfonated diamine[J]. J. Membr. Sci., 2012, 403: 152-161.
27	Hegab M, ElMekawy A, Barclay T G, et al. Fine-tuning the surface of forward osmosis membranes via grafting graphene oxide: performance patterns and biofouling propensity[J]. ACS Appl. Mater. Interfaces, 2015, 7: 18004-18016.
28	Zhou Y, Yu S, Gao C, et al. Surface modification of thin film composite polyamide membranes by electrostatic self deposition of polycations for improved fouling resistance[J]. Sep. Purif. Technol., 2009, 66: 287-294.
29	Castrillón S R V, Lu X, Shaffer D L, et al. Amine enrichment and poly(ethylene glycol) (PEG) surface modification of thin-film composite forward osmosis membranes for organic fouling control[J]. J. Membr. Sci., 2014, 450: 331-339.
30	Kang G, Cao Y. Development of antifouling reverse osmosis membranes for water treatment: a review[J]. Water Res., 2012, 46: 584-600.
31	Liu L, Zhu G R, Liu Z F, et al. Effect of MCM-48 nanoparticles on the performance of thin film nanocomposite membranes for reverse osmosis application[J]. Desalination, 2016, 394: 72-82.
32	Van Goethem C, Verbeke R, Pfanmoller M, et al. The role of MOFs in thin-film nanocomposite (TFN) membranes[J]. J. Membr. Sci., 2018, 563: 938-948.
33	张润楠, 李亚飞, 苏延磊, 等. 氨基化氧化石墨烯界面聚合制备超薄复合纳滤膜[J]. 化工学报, 2018, 69(1): 435-445.
	Zhang R N, Li Y F, Su Y L, et al. Preparation of thin-film composite nanofiltration membranes with amino-functionalized graphene oxide by interfacial polymerization[J]. CIESC Journal, 2018, 69(1): 435-445.

[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]	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.
[4]	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.
[5]	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.
[6]	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.
[7]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[8]	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.
[9]	仪显亨, 周骛, 蔡小舒, 蔡天意. 光纤后向动态光散射测量纳米颗粒的浓度适用范围研究[J]. 化工学报, 2023, 74(8): 3320-3328.
[10]	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.
[11]	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.
[12]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.
[13]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[14]	李勇, 高佳琦, 杜超, 赵亚丽, 李伯琼, 申倩倩, 贾虎生, 薛晋波. Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢[J]. 化工学报, 2023, 74(6): 2458-2467.
[15]	陈朝光, 贾玉香, 汪锰. 以低浓度废酸驱动中和渗析脱盐的模拟与验证[J]. 化工学报, 2023, 74(6): 2486-2494.

负载羧基化球状介孔纳米颗粒TFN膜的研究

Research of thin film nanocomposite (TFN) membranes incorporated spherical mesoporous silica nanoparticles with carboxyl group

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价