Position：Home >> Abstract

Guanidinium-regulated interfacial polymerization for the preparation of
 high-flux nanofiltration membrane for hardness removal
Authors： XU Shuting1,2, YE Jianrong1, LI Junjun1, JI Genliang1,
 YUAN Diying1, ZHANG Shifeng1, ZHANG Yiming2,3, LIU Fu2,3
Units： 1. Shuiyi Environmental Protection Group Co., Ltd., Ningbo 315336, China;  2. Ningbo Institute of
 Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China; 
3. Ningbo College of Materials Technology & Engineering, University of Chinese Academy of
 Sciences, Ningbo 315201, China
KeyWords： polyamide nanofiltration membrane; interfacial polymerization; guanidinium; surfactant; hydrogen bond interaction; water softening
ClassificationCode：TQ028.8
year,volume(issue):pagination： 2026, 46(4):45-54

Abstract：

In order to enhance the rejection of hardness ions (calcium and magnesium ions) by nanofiltration membranes, this study employed a surfactant-assisted interfacial polymerization method to fabricate polyamide nanofiltration membranes. By introducing the secondary amine monomer 1,3-diaminoguanidine salt (DAG) into the aqueous phase, the interactions between DAG and the surfactant and their effects on the interfacial polymerization process were investigated. The results indicated that the addition of DAG led to a reduction in membrane thickness and surface roughness, as well as a narrowing of the pore size distribution. Compared with the membrane prepared without DAG, the DAG-incorporated membrane exhibited significantly improved rejection rate of CaCl2, increasing from 86.8% to 96.4%. Under a low operating pressure of 0.2 MPa, the membrane also demonstrated a high water permeance of 226.6 L/(m2·h·MPa). This study provides a useful reference for the fabrication of low-pressure, high-flux nanofiltration membranes for water softening applications. 

Funds：

AuthorIntro：
许舒婷（1996-），女，黑龙江哈尔滨人，主要研究方向为分离膜的制备及其性能研究. *通讯作者，E-mail:fu.liu@nimte.ac.cn

Reference：

  [1] Zhao F Y, An Q F, Ji Y L, et al. A novel type of polyelectrolyte complex/MWCNT hybrid nanofiltration membranes for water softening［J］. J Membr Sci, 2015, 492: 412-421.
［2］Li Q, Zhang T, Dai Z, et al. A novel positively charged nanofiltration membrane stimulated by amino-functionalized mxene Ti3C2Tx for high rejection of water hardness ions［J］. J Membr Sci, 2023, 671: 121385.
［3］Wang Z, You X, Yang C, et al. Ultrathin polyamide nanofiltration membranes with tunable chargeability for multivalent cation removal［J］. J Membr Sci, 2022, 642: 119971.
［4］Yuan B, Jiang C, Li P, et al. Ultrathin polyamide membrane with decreased porosity designed for outstanding water-softening performance and superior antifouling properties［J］. ACS Appl Mater Interfaces, 2018, 10(49): 43057-43067.
［5］Wang K, Wang X, Januszewski B, et al. Tailored design of nanofiltration membranes for water treatment based on synthesis-property-performance relationships［J］. Chem Soc Rev, 2022, 51(2): 672-719.
［6］Zhao Y, Tong X, Chen Y. Fit-for-purpose design of nanofiltration membranes for simultaneous nutrient recovery and micropollutant removal［J］. Environ Sci Technol, 2021, 55(5): 3352-3361.
［7］Mohammad A W, Teow Y H, Ang W L, et al. Nanofiltration membranes review: Recent advances and future prospects［J］. Desalination, 2015, 356: 226-254.
［8］Guo S, Wan Y, Chen X, et al. Loose nanofiltration membrane custom-tailored for resource recovery［J］. Chem Eng J, 2021, 409: 127376.
［9］Guo H, Li X, Yang W, et al. Nanofiltration for drinking water treatment: A review［J］. Front Chem Sci Eng, 2022, 16(5): 681-698.
［10］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.
［11］Liu C, Zhu C Y, Zhang C, et al. Thermodynamic and kinetic understanding for managing the controllability of interfacial polymerization［J］. Prog Polym Sci, 2024, 152: 101815.
［12］Imbrogno A, Calvo J I, Breida M, et al. Molecular weight cut off (MWCO) determination in ultra- and nanofiltration: Review of methods and implications on organic matter removal［J］. Sep Purif Technol, 2025, 354: 128612.
［13］Tan Z, Chen S, Peng X, et al. Polyamide membranes with nanoscale turing structures for water purification［J］. Science, 2018, 360: 518-521.
［14］Ren Y, Qi P, Han Y, et al. Mix-charged nanofiltration membrane for efficient organic removal from high-salinity wastewater: The role of charge spatial distribution［J］. Environ Sci Technol, 2025, 59(2): 1434-1447.
［15］Geise G M, Park H B, Sagle A C, et al. Water permeability and water/salt selectivity tradeoff in polymers for desalination［J］. J Membr Sci, 2011, 369(1/2): 130-138.
［16］Yang Z, Guo H, Tang C Y. The upper bound of thin-film composite (TFC) polyamide membranes for desalination［J］. J Membr Sci, 2019, 590: 117297.
［17］王若湲，杨天祥，张会书，等. 聚酰胺薄膜界面聚合动态观测与微观机制研究［J］. 膜科学与技术, 2025, 45(4): 32-42.
［18］Zhao C, Zhang Y, Jia Y, et al. Polyamide membranes with nanoscale ordered structures for fast permeation and highly selective ion-ion separation［J］. Nat Commun, 2023, 14(1): 1112.
［19］Zhu Y, Xie W, Gao S, et al. Single-walled carbon nanotube film supported nanofiltration membrane with a nearly 10 nm thick polyamide selective layer for high-flux and high-rejection desalination［J］. Small, 2016, 12(36): 5034-5041.
［20］Yang Z, Zhou Z W, Guo H, et al. Tannic acid/Fe3+ nanoscaffold for interfacial polymerization: Toward enhanced nanofiltration performance［J］. Environ Sci Technol, 2018, 52(16): 9341-9349.
［21］You X, Xiao K, Wu H, et al. Electrostatic-modulated interfacial polymerization toward ultra-permselective nanofiltration membranes［J］. iScience, 2021, 24(4): 102369.
［22］Liang Y, Zhu Y, Liu C, et al. Polyamide nanofiltration membrane with highly uniform sub-nanometre pores for sub-1 a precision separation［J］. Nat Commun, 2020, 11(1): 2015.
［23］Zhang R, Zhu Y, Zhang L, et al. Polyamide nanofiltration membranes from surfactant-assembly regulated interfacial polymerization: The effect of alkyl chain［J］. Macromol Chem Phys, 2021, 222(20): 2100222.
［24］Liang Y, Teng X, Chen R, et al. Polyamide nanofiltration membranes from emulsion-mediated interfacial polymerization［J］. ACS ES&T Engineering, 2021, 1(3): 533-542.
［25］Liu Y, Kong J, Bian X, et al. Positively charged poly(piperazinamide) nanofiltration membranes for the fast removal of metal ions［J］. Adv Mater Interfaces, 2022, 9(33): 2201206.
［26］Peng Q, Wang R, Zhao Z, et al. Extreme Li-Mg selectivity via precise ion size differentiation of polyamide membrane［J］. Nat Commun, 2024, 15(1): 2505.
［27］Chen Y,Niu Q J, Hou Y, et al. Effect of interfacial polymerization monomer design on the performance and structure of thin film composite nanofiltration and reverse osmosis membranes: A review［J］. Sep Purif Technol, 2024, 330: 125282.
［28］Han F, Yin C, Liu L, et al. Construction of highly cross linked defect free acid resistant nanofiltration membrane via span 80 accelerated monomer diffusion［J］. Sep Purif Technol, 2026, 384: 136293.
［29］Hou R, Wang P, Cheng C, et al. Construction of a gradient cross-linked nanofiltration membrane with quaternized surface for efficient heavy metal removal［J］. Desalination, 2025, 614: 119169.
［30］Fang W, Shi L, Wang R. Mixed polyamide-based composite nanofiltration hollow fiber membranes with improved low-pressure water softening capability［J］. J Membr Sci, 2014, 468: 52-61.
［31］Jiang Z, Dong R, Evans A M, et al. Aligned macrocycle pores in ultrathin films for accurate molecular sieving［J］. Nature, 2022, 609(7925): 58-64.
［32］Li P, Lan H, Chen K, et al. Novel high-flux positively charged aliphatic polyamide nanofiltration membrane for selective removal of heavy metals［J］. Sep Purif Technol, 2022, 280: 119949.
［33］Zhang S, Zhang R, Li R, et al. Guanidyl-incorporated nanofiltration membranes toward superior Li+/Mg2+ selectivity under weakly alkaline environment［J］. J Membr Sci, 2022, 663: 121063.
［34］Huang J, Wang H, Li X, et al. Biguanide-functionalized nanofiltration membranes for high-efficient Mg2+/ Li+ separation［J］. Sep Purif Technol, 2026, 386: 136504.
［35］Hao Z, Tian X, Mankol V, et al. Polyamide nanofiltration membrane fabricated with ultra-low concentration triaminoguanidine showing efficient desalination performance［J］. J Membr Sci, 2023, 672: 121449.
［36］Liu B, Zhang C, Cui X, et al. Aminoguanidine-based polyamide nanofiltration membranes for purifying natural surface water: Superior anti-fouling properties and ultra-high organic matter/minerals selectivity［J］. Desalination, 2025, 610: 118913.
［37］Xu S, Liu J, Wang J, et al. Guanidinium manipulated interfacial polymerization for polyamide nanofiltration membranes with ultra-high permselectivity［J］. J Membr Sci, 2023, 687: 122003.
［38］Lee C, Yang W, Parr R G. Development of the colle-salvetti correlation-energy formula into a functional of the electron density［J］. Phys Rev B, 1988, 37(2): 785-789.
［39］Lyu Y, Cao Z, Ren X, et al. Electric field-modulated dissociation of dinitrophenol pollutants adsorbed on graphene oxide: Insights from molecular dynamics simulations［J］. Chem Eng Sci, 2026, 320: 122497.
［40］Grimme S, Ehrlich S, Goerigk L. Effect of the damping function in dispersion corrected density functional theory［J］. J Comput Chem, 2011, 32(7): 1456-1465.
［41］Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer［J］. J Comput Chem, 2012, 33(5): 580-592.
［42］Weigend F, Ahlrichs R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for h to rn: Design and assessment of accuracy［J］. Phys Chem Chem Phys, 2005, 7(18): 3297-3305.
［43］Boys S F, Bernardi F. The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors［J］. Mol Phys, 1970, 19(4): 553-566.
［44］Lu T, Chen Q. Independent gradient model based on hirshfeld partition: A new method for visual study of interactions in chemical systems［J］. J Comput Chem, 2022, 43(8): 539-555.
［45］Bader R F W. Atoms in molecules［J］. Acc Chem Res, 1985, 18(1): 9-15.
［46］Emamian S, Lu T, Kruse H, et al. Exploring nature and predicting strength of hydrogen bonds: A correlation analysis between atoms-in-molecules descriptors, binding energies, and energy components of symmetry-adapted perturbation theory［J］. J Comput Chem, 2019, 40(32): 2868-2881.
［47］Humphrey W, Dalke A, Schulten K. VMD: Visual molecular dynamics［J］. J Mol Graph, 1996, 14(1): 33-38.

Service：
【Download】【Collect】

《膜科学与技术》编辑部 Address: Bluestar building, 19 east beisanhuan road, chaoyang district, Beijing; 100029 Postal code; Telephone：010-80492417/010-80485372; Fax：010-80485372 ; Email：mkxyjs@163.com

京公网安备11011302000819号