介孔纳米二氧化硅改性纳滤膜的研究
作者： 于小淇1, 王小娟1*, 宋越1， 王新艳2， 张伟政2， 高学理1
单位： 1. 中国海洋大学  化学化工学院， 海洋化学理论与工程技术教育部重点实验室， 青岛  266100；
2.  山东招金膜天股份有限公司， 招远  265400
关键词： 界面聚合； 纳滤膜； 介孔二氧化硅纳米颗粒； 分离性能； 抗污染性能
DOI号： 10.16159/j.cnki.issn1007-8924.2026.03.007
分类号：  TQ028.8
出版年,卷(期):页码： 2026, 46(3):65-77

摘要：

为提升聚酰胺纳滤（NF）膜的渗透选择性和抗污染能力，以介孔二氧化硅纳米颗粒（MSN）作为水相添加剂，采用哌嗪（PIP）和均苯三甲酰氯（TMC）作为反应单体，通过界面聚合反应制备了NF膜，系统研究了MSN对PIP向有机相扩散速率、NF膜的微观形貌以及理化性质的影响。结果表明，MSN的引入抑制了PIP的扩散速率，诱导形成了更薄的分离层，同时显著增强了NF膜表面的亲水性、粗糙程度与荷电性。其中，NF-0.010膜具有优异的渗透性、离子选择性及抗污染性能，其水通量较NF-0膜提高了61.37%，对硫酸钠截留率维持在98%以上，对Cl-/SO2-4的分离因子提升至116.86，且对牛血清白蛋白的抗污染性能有所增强，充分验证了MSN对NF膜综合性能的有效提升。

To improve the permeability-selectivity and anti-fouling performance of polyamide nanofiltration (NF) membranes, NF membranes were fabricated via interfacial polymerization (IP) using piperazine (PIP) and trimesoyl chloride (TMC) as monomers, and mesoporous silica nanoparticles (MSN) as the aqueous phase additive. The study systematically investigated the effects of MSN on the diffusion rate of PIP into the organic phase, as well as the microstructure and physicochemical properties of resulting NF membranes. Results demonstrated that the introduction of MSN inhibited the diffusion rate of PIP, inducing the formation of a thinner separation layer while significantly enhancing the surface hydrophilicity, roughness, and negative charges of NF membranes. Specifically, the NF-0.010 membrane exhibited superior permeability, ion sieving performance, and anti-fouling performance. Its water flux increased by 61.37% compared to NF-0 membrane, with the Na2SO4 rejection above 98%. Furthermore, the separation factor for Cl-/SO2-4 increased to 116.86, and the anti-fouling performance against bovine serum albumin (BSA) was significantly enhanced. These findings fully validated that the incorporation of MSN effectively enhanced the comprehensive performance of NF membranes. 

基金项目：

山东省重点研发计划项目（2023CXGC010902）； 中国工程科技发展战略山东研究院咨询研究项目（202402SDZD02）； 泰山产业领军人才工程项目（tscx202408154）

作者简介：
第一作者简介： 于小淇（2001-），女，山东临沂人，硕士研究生，研究方向为膜分离.*通讯作者，E-mail：safiya0524@163.com

参考文献：

［1］Dashtbozorg A, Saljoughi E, Mousavi S M, et al. Synergistic effect of MXene loading into the support and polyamide layer of TFNC membranes: Improved permeability and rejection of salt and dye in nanofiltration［J］. Adv Mater Technol, 2025, 11(3): e01335.
［2］Wang Y J, Wang T, Li S H, et al. Novel poly(piperazinamide)/poly(m-phenylene isophthalamide) composite nanofiltration membrane with polydopamine coated silica as an interlayer for the splendid performance［J］. Sep Purif Technol, 2022, 285: 120390.
［3］Zarrabi H, Yekavalangi M E, Vatanpour W, et al. Improvement in desalination performance of thin film nanocomposite nanofiltration membrane using amine-functionalized multiwalled carbon nanotube［J］. Desalination, 2016, 394: 83-90.
［4］宋刚福, 胡智媛, 高亚伟, 等. 胺化哌嗪羧酸聚酰胺纳滤膜的制备及性能研究［J］. 膜科学与技术, 2025, 45(3): 44-53.
［5］Liu S Q, Wang Z G, Zhao L, et al. Trger’s base-regulated interfacial polymerization of polyamide nanofiltration membranes with enhanced performance［J］. J Membr Sci, 2023, 682: 121787.
［6］Guo Z W, Zhang K F, Guan H, et al. Improved separation efficiency of polyamide-based composite nanofiltration membrane by surface modification using 3-aminopropyltriethoxysilane［J］. Sep Purif Technol, 2021, 274: 119142.
［7］Lu Z Q, Zhang X Y, Hua L, et al. Highly permeable and fouling-resistant polyamide nanofiltration membranes with embedded boron nitride nanosheets for the purification of water［J］. ACS Appl Nano Mater, 2024, 7(15): 17958-17966.
［8］Lin W T, Zhu C Y, Zhou D, et al. Functionalized g-C3N4 nanosheet interlayer enables enhanced separation performance of nanofiltration membranes［J］. Sep Purif Technol, 2023, 324: 124543.
［9］代新雷, 马文中, 钟璟, 等. 聚酰亚胺/UIO-66薄层纳米复合膜的制备及其纳滤性能［J］. 膜科学与技术, 2024, 44(2): 89-96.
［10］Yin Y H, Xu H, Zhang C Y, et al. Fabrication of polyamide/zwitterion functionalized mesoporous silica nanofiltration membrane with highly enhanced antifouling performance［J］. J Taiwan Inst Chem Eng, 2023, 147: 104892.
［11］Peng H W, Tang Q Q, Tang S H, et al. Surface modified polyamide nanofiltration membranes with high permeability and stability［J］. J Membr Sci, 2019, 592: 117386.
［12］鲁艺文, 吕晓龙, 任凯, 等. 多羟基单体调控分离层结构制备高性能净水用纳滤膜［J］. 膜科学与技术, 2024, 44(5): 108-116.
［13］Sun Y, Yang W Y, Zou L C, et al. Thin film nanocomposite membranes with tannic acid functionalized MXene nanosheets for high-performance nanofiltration［J］. ACS Appl Polym Mater, 2023, 5(10): 8099-8107.
［14］Bai L M, Liu Y T, Bossa N, et al. Incorporation of cellulose nanocrystals (CNCs) into the polyamide layer of thin-film composite (TFC) nanofiltration membranes for enhanced separation performance and antifouling properties［J］. Environ Sci Technol, 2018, 52(19): 11178-11187.
［15］Li X J, Janke A, Formanek P, et al. High permeation and antifouling polysulfone ultrafiltration membranes with in situ synthesized silica nanoparticles［J］. Mater Today Commun, 2020, 22: 100784.
［16］Yu L Y, Xu Z L, Shen H M, et al. Preparation and characterization of PVDF-SiO2 composite hollow fiber UF membrane by sol-gel method［J］. J Membr Sci, 2009, 337(1/2): 257-265.
［17］Waleed H, Hudaib B, Al-Harahsheh M, et al. Synthesis and characterization of a modified silica/cellulose acetate nanocomposite ultrafiltration membrane for phenol removal from wastewater［J］. Sep Purif Technol, 2025, 353: 128391. 
［18］Huang Q Y, Ding Z W, Lu H R, et al. Honeycomb-like SBA-15 parceled in 2D GO for ultrafiltration membranes fabrication with ultrahigh permeability and enhanced anti-fouling performance［J］. Sep Purif Technol, 2023, 325: 124694.
［19］Li C, Li J, Zhang W H, et al. Enhanced permeance for PDMS organic solvent nanofiltration membranes using modified mesoporous silica nanoparticles［J］. J Membr Sci, 2020, 612: 118257.
［20］Zhao M, Ren Z Z, Yang M B, et al. Effects of modified nano-silica on the microstructure of PVDF and its microporous membranes［J］. J Polym Res, 2019, 26: 28.
［21］Wang X J, Xu S J, Wang X Y, et al. Porous Zn-TCPP interlayer with active reaction sites modulates membrane physicochemical properties to improve nanofiltration performance［J］. Desalination, 2024, 576: 117354.
［22］Fu J Y, Jiao J Q, Song H, et al. Fractal-in-a-sphere: Confined self-assembly of fractal silica nanoparticles［J］. Chem Mater, 2019, 32(1): 341-347.
［23］Lan X B, Liu Y, Chen X R, et al. Crosslinking degree of polyamide membranes: From determination to rational design［J］. Desalination, 2026, 623: 119760.
［24］Wu H H, Zhao H Y, Lin Y K, et al. Fabrication of polysulfone membrane with sponge-like structure by using different non-woven fabrics［J］. Sep Purif Technol, 2022, 297: 121553.
［25］Qi T, Chen X F, Lu T D, et al. Enhancing ion separation efficiency: Janus charged nanofiltration membrane fabricated via polyethyleneimine-manipulated interfacial polymerization［J］. J Membr Sci, 2024, 706: 122930.
［26］Wang Q Y, Wang Y Y, Huang Y X, et al. Polyethyleneimine (PEI) based positively charged thin film composite polyamide (TFC-PA) nanofiltration (NF) membranes for effective Mg2+/Li+ separation［J］. Desalination, 2023, 565: 116814.
［27］Yang H M, Dong G Y, Qin L J, et al. Polyamide nanofiltration membranes mediated by mesoporous silica nanosheet interlayers display substantial desalination performance enhancement［J］. J Membr Sci, 2024, 693: 122387.
［28］Pan L M, He Q J, Liu J N, et al. Nuclear-targeted drug delivery of TAT peptide-conjugated monodisperse mesoporous silica nanoparticles［J］. J Am Chem Soc, 2012, 134(13): 5722-5725.
［29］Breznan D, Das D D, MacKinnon-Roy C, et al. Physicochemical properties can be key determinants of mesoporous silica nanoparticle potency in vitro［J］. ACS Nano, 2018, 12(12): 12062-12079.
［30］Li T, Chen X F, Liu Y J, et al. pH-Sensitive mesoporous silica nanoparticles anticancer prodrugs for sustained release of ursolic acid and the enhanced anti-cancer efficacy for hepatocellular carcinoma cancer［J］. Eur J Pharm Sci, 2017, 96: 456-463.
［31］Pinna A, Baghbaderani M T, Hernández V V, et al. Nanoceria provides antioxidant and osteogenic properties to mesoporous silica nanoparticles for osteoporosis treatment［J］. Acta Biomater, 2021, 122: 365-376.
［32］Liang H, Jin C, Ma L, et al. Accelerated bone regeneration by gold-nanoparticle-loaded mesoporous silica through stimulating immunomodulation［J］. ACS Appl Mater Interfaces, 2019, 11(44): 41758-41769.
［33］Li Q, Sun W G, Shang B, et al. Lignin/mesoporous hollow silica nanosphere thin film nanocomposite loose nanofiltration membrane for dye/salt separation［J］. Desalination, 2024, 575: 117332.
［34］Gao F, Liu H L, Zhang Y, et al. Polyamide membrane with nanoscale stripes and internal voids for high-performance nanofiltration［J］. J Membr Sci, 2023, 671: 121406.
［35］Alicia L, Gabriel P, Felipe M. Using the Lambert-Beer law for thickness evaluation of photoconductor coatings for recording holograms［J］. Appl Surf Sci, 1995, 84: 407-411.
［36］刘佳欢, 王建强, 刘富. 单体扩散控制界面聚合制备聚酰胺薄层复合纳滤膜研究进展［J］. 膜科学与技术, 2025, 45(4): 194-205.
［37］Song Y C, Liu D M, Hu R, et al. Tailoring morphology for improved dispersibility of hydrophilic silica nanoparticles to fabricate thin-film nanocomposite membranes［J］. Sep Purif Technol, 2024, 336: 126279.
［38］Jiang C, Zhang M M, Hou Y F. Thin-film composite membrane with porous interlayer composed of dendritic mesoporous silica nanoparticles for enhanced nanofiltration［J］. Polymers, 2023, 15(19): 3912.
［39］Xue H J, Pu H K, Wang X J, et al. Synergistic emulsion effect-inspired design of starch nanoparticle-based nanofiltration membranes with nano-Turing structures for enhanced performance［J］. Sep Purif Technol, 2025, 378: 134582.
［40］Ahmad T, Guria C, Mubashir M, et al. Hussaine, tailoring polysulfone membranes with surface-modified silica for efficient separation of oily water［J］. J Polym Sci, 2025, 63(10): 2266-2277.
［41］Deng Y Y, Peng C S, Dai M, et al. Recent development of super-wettable materials and their applications in oil-water separation［J］. J Cleaner Prod, 2020, 266: 121624.
［42］Fang Y, Jiang B, Hao Y F, et al. Engineering highly permeable thin-film composite nanofiltration membranes by strengthening the diffusion control of amine monomer via deep eutectic solvent［J］. J Membr Sci, 2023, 678: 121689.
［43］Zhang H G, Quan X, Chen S, et al. Combined effects of surface charge and pore size on co-enhanced permeability and ion selectivity through RGO-OCNT nanofiltration membranes［J］. Environ Sci Technol, 2018, 52(8): 4827-4834.
［44］Zhang W T, Xu H, Lai C X, et al. Regulating interfacial polymerization by amino acids towards high performance polyamide nanofiltration membranes［J］. J Membr Sci, 2025, 736: 124629.
［45］Han Y, Jiang Y Q, Gao C. High-flux graphene oxide nanofiltration membrane intercalated by carbon nanotubes［J］. ACS Appl Mater Interfaces, 2015, 7: 8147-8155.
［46］Cheng X X, Lai C X, Li J Y, et al. Toward enhancing desalination and heavy metal removal of TFC nanofiltration membranes: A cost-effective interface temperature-regulated interfacial polymerization［J］. ACS App Mater Interfaces, 2021, 13(48): 57998-58010.
［47］You M, Wang P, Xu M L, et al. Fouling resistance and cleaning efficiency of stimuli-responsive reverse osmosis (RO) membranes［J］. Polymer, 2016, 103: 457-467.
［48］Pandit S, Kundu S, Aswal V K. Effect of monovalent salts on molecular interactions of globular protein (BSA) above its isoelectric point［J］. Chem Phys Lett, 2022, 804: 139916.
［49］Hao Y F, Fang Y, Zhang L F, et al. Ternary deep eutectic solvent enhanced the diffusion control of amine monomer for highly permeable and anti-fouling polyamide nanofiltration membranes［J］. Sep Purif Technol, 2024, 330: 125371.
［50］Kamari S, Shahbazi A. High-performance nanofiltration membrane blended by Fe3O4@SiO2-CS bionanocomposite for efficient simultaneous rejection of salts/heavy metals ions/dyes with high permeability, retention increase and fouling decline［J］. Chem Eng J, 2021, 417: 127930.
［51］Kim E S, Hwang G, El-Din M G, et al. Development of nanosilver and multi-walled carbon nanotubes thin-film nanocomposite membrane for enhanced water treatment［J］. J Membr Sci, 2012, 394/395: 37-48.
［52］Safarpour M, Vatanpour V, Khataee A, et al. Development of a novel high flux and fouling-resistant thin film composite nanofiltration membrane by embedding reduced graphene oxide/TiO2［J］. Sep Purif Technol, 2015, 154: 96-107.
［53］Tang Y J, Xu Z L, Huang B Q, et al. Novel polyamide thin-film composite nanofiltration membrane modified with poly(amidoamine) and SiO2 gel［J］. RSC Adv, 2016, 6 (51): 45585-45594.
［54］Liu L F, Huang X, Zhang X, et al. Modification of polyamide TFC nanofiltration membrane for improving separation and antifouling properties［J］. RSC Adv, 2018, 8 (27): 15102-15110.
［55］Bai L M, Liu Y T, Ding A, et al. Fabrication and characterization of thin-film composite (TFC) nanofiltration membranes incorporated with cellulose nanocrystals (CNCs) for enhanced desalination performance and dye removal［J］. Chem Eng J, 2019, 358: 1519-1528.
［56］Dehghanpour S B, Parvizian F, Vatanpour V, et al. Enhancing the flux and salt rejection of thin-film composite nanofiltration membranes prepared on plasma-treated polyethylene using PVA/TS-1 composite［J］. React Funct Polym, 2022, 177: 105329.

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