Please wait a minute...

Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2019, Vol. 13 Issue (6) : 81
G-CNTs/PVDF mixed matrix membranes with improved antifouling properties and filtration performance
Xiaoyan Guo1,2, Chunyu Li1,2, Chenghao Li1,2, Tingting Wei1, Lin Tong1,2, Huaiqi Shao3, Qixing Zhou1, Lan Wang1, Yuan Liao2()
1. Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Technology for Complex Trans-Media Pollution, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China
2. Sino-Canada Joint R&D Centre for Water and Environmental Safety, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China
3. College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin 300457, China
Download: PDF(1819 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

A novel nanocomposite OMWCNT-A-GO was synthesized by conjugating OMWCNT and GO.

The P-OMWCNT-A-GO membrane was fabricated by non-solvent induced phase inversion.

The P-OMWCNT-A-GO exhibits the best water flux, BSA rejection and flux recovery.

It should be due to the enhanced membrane pore size, porosity and hydrophilicity.

Although carbon nanomaterials have been widely used as effective nanofillers for fabrication of mixed matrix membranes (MMMs) with outstanding performances, the reproducibility of the fabricated MMMs is still hindered by the non-homogenous dispersion of these carbon nanofillers in membrane substrate. Herein, we report an effective way to improve the compatibility of carbon-based nanomaterials with membrane matrixes. By chemically conjugating the oxidized CNTs (o-CNTs) and GO using hexanediamine as cross-linker, a novel carbon nanohybrid material (G-CNTs) was synthesized, which inherited both the advanced properties of multi-walled carbon nanotubes (CNTs) and graphene oxide (GO). The G-CNTs incorporated polyvinylidene fluoride (PVDF) MMMs (G-CNTs/PVDF) were fabricated via a non-solvent induced phase separation (NIPS) method. The filtration and antifouling performances of G-CNTs/PVDF were evaluated using distillate water and a 1 g/L bovine serum albumin (BSA) aqueous solution under 0.10 MPa. Compared to the MMMs prepared with o-CNTs, GO, the physical mixture of o-CNTs and GO and pure PVDF membrane, the G-CNTs/PVDF membrane exhibited the highest water flux up to 220 L/m2/h and a flux recovery ratio as high as 90%, as well as the best BSA rejection rate. The excellent performances should be attributed to the increased membrane pore size, porosity and hydrophilicity of the resulted membrane. The successful synthesis of the novel nanohybrid G-CNTs provides a new type of nanofillers for MMMs fabrication.

Keywords carbon nanotubes      graphene oxide      mixed matrix membrane      nanohybrid      antifouling membrane      membrane hydrophilicity     
This article is part of themed collection: China Urban Water Environment and Water Ecology (Responsible Editors: Shubo Deng & Huijuan Liu)
Corresponding Author(s): Yuan Liao   
Issue Date: 27 August 2019
 Cite this article:   
Xiaoyan Guo,Chunyu Li,Chenghao Li, et al. G-CNTs/PVDF mixed matrix membranes with improved antifouling properties and filtration performance[J]. Front. Environ. Sci. Eng., 2019, 13(6): 81.
E-mail this article
E-mail Alert
Articles by authors
Xiaoyan Guo
Chunyu Li
Chenghao Li
Tingting Wei
Lin Tong
Huaiqi Shao
Qixing Zhou
Lan Wang
Yuan Liao
Fig.1  Schematic of the laboratory-scale dead-end filtration system (Millipore 8200).
Fig.2  The chemical reactions involved for preparation of carbon nanohybrid material (G-CNTs).
Fig.3  FTIR spectra of (a) o-CNTs; (b) GO; (c) G-CNTs.
Fig.4  XPS survey spectrum of G-CNTs nanohybrids.
Fig.5  TEM images of the G-CNTs nanohybrids.
Fig.6  SEM images of the top surfaces of membranes (a) plain PVDF; (b) P-o-CNTs; (c) P-GO; (d) P-GO-CNTs; (e) P-G-CNTs.
Fig.7  Pore size and porosity of the various membranes.
Fig.8  Contact angles of different MMMs prepared without any filler (pure PVDF) and with o-CNTs, GO, GO-CNTs, G-CNTs.
Fig.9  Pure water fluxes and rejections to BSA at an operating pressure of 0.1 MPa for various MMMs.
Fig.10  Anti-fouling performance of various membranes evaluated with BSA solution at an operating pressure of 0.1 MPa.
Fig.11  Flux recovery ratio (FRR), reversible fouling ratio (Rr) and irreversible fouling ratio (Rir) of the MMMs developed in this work.
1 L Ao, W Liu, Y Qiao, C Li, X Wang (2018). Comparison of membrane fouling in ultrafiltration of down-flow and up-flow biological activated carbon effluents. Frontiers of Environmental Science & Engineering, 12(6): 9
2 N Awanis Hashim, F Liu, M R Moghareh Abed, K Li (2012). Chemistry in spinning solutions: Surface modification of PVDF membranes during phase inversion. Journal of Membrane Science, 415–416: 399–411
3 J Ayyavoo, T P N Nguyen, B M Jun, I C Kim, Y N Kwon (2016). Protection of polymeric membranes with antifouling surfacing via surface modifications. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 506: 190–201
4 T S Chung, L Y Jiang, Y Li, S Kulprathipanja (2007). Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation. Progress in Polymer Science, 32(4): 483–507
5 Z Cui, E Drioli, Y M Lee (2014). Recent progress in fluoropolymers for membranes. Progress in Polymer Science, 39(1): 164–198
6 J L Delgado, P De La Cruz, A Urbina, J T López Navarrete, J Casado, F Langa (2007). The first synthesis of a conjugated hybrid of C60–fullerene and a single-wall carbon nanotube. Carbon, 45(11): 2250–2252
7 Q Ding, H Yamamura, N Murata, N Aoki, H Yonekawa, A Hafuka, Y Watanabe (2016). Characteristics of meso-particles formed in coagulation process causing irreversible membrane fouling in the coagulation-microfiltration water treatment. Water Research, 101: 127–136 pmid: 27262117
8 Y Ding, B Ma, H Liu, J Qu (2019). Effects of protein properties on ultrafiltration membrane fouling performance in water treatment. Journal of Environmental Sciences (China), 77: 273–281 pmid: 30573091
9 M R Esfahani, S A Aktij, Z Dabaghian, M D Firouzjaei, A Rahimpour, J Eke, I C Escobar, M Abolhassani, L F Greenlee, A R Esfahani, A Sadmani, N Koutahzadeh (2019). Nanocomposite membranes for water separation and purification: Fabrication, modification, and applications. Separation and Purification Technology, 213: 465–499
10 A R Fajardo, L C Lopes, A F Rubira, E C Muniz (2012). Development and application of chitosan/poly(vinyl alcohol) films for removal and recovery of Pb(II). Chemical Engineering Journal, 183: 253–260
11 E Fontananova, V Grosso, S A Aljlil, M A Bahattab, D Vuono, F P Nicoletta, E Curcio, E Drioli, G Di Profio (2017). Effect of functional groups on the properties of multiwalled carbon nanotubes/polyvinylidenefluoride composite membranes. Journal of Membrane Science, 541: 198–204
12 F Fornasiero (2017). Water vapor transport in carbon nanotube membranes and application in breathable and protective fabrics. Current Opinion in Chemical Engineering, 16: 1–8
13 J Z Hamad, R Dua, N Kurniasari, M D Kennedy, P Wang, G L Amy (2014). Irreversible membrane fouling abatement through pre-deposited layer of hierarchical porous carbons. Water Research, 65: 245–256 pmid: 25128660
14 G Han, S Zhang, X Li, T S Chung (2015). Progress in pressure retarded osmosis (PRO) membranes for osmotic power generation. Progress in Polymer Science, 51: 1–27
15 J K Holt, H G Park, Y Wang, M Stadermann, A B Artyukhin, C P Grigoropoulos, A Noy, O Bakajin (2006). Fast mass transport through sub-2-nanometer carbon nanotubes. Science, 312(5776): 1034–1037 pmid: 16709781
16 K Hu, D D Kulkarni, I Choi, V V Tsukruk (2014). Graphene-polymer nanocomposites for structural and functional applications. Progress in Polymer Science, 39(11): 1934–1972
17 G Huang, A P Isfahani, A Muchtar, K Sakurai, B B Shrestha, D Qin, D Yamaguchi, E Sivaniah, B Ghalei (2018a). Pebax/ionic liquid modified graphene oxide mixed matrix membranes for enhanced CO2 capture. Journal of Membrane Science, 565: 370–379
18 S Huang, R H A Ras, X Tian (2018b). Antifouling membranes for oily wastewater treatment: Interplay between wetting and membrane fouling. Current Opinion in Colloid & Interface Science, 36: 90–109
19 Ihsanullah (2019). Carbon nanotube membranes for water purification: Developments, challenges, and prospects for the future. Separation and Purification Technology, 209: 307–337
20 A Inurria, P Cay-Durgun, D Rice, H Zhang, D K Seo, M L Lind, F Perreault (2019). Polyamide thin-film nanocomposite membranes with graphene oxide nanosheets: Balancing membrane performance and fouling propensity. Desalination, 451: 139–147
21 G D Kang, Y M Cao (2012). Development of antifouling reverse osmosis membranes for water treatment: A review. Water Research, 46(3): 584–600 pmid: 22154112
22 N F M Khairuddin, A Idris, L W Hock (2019). Harvesting Nannochloropsis sp. using PES/MWCNT/LiBr membrane with good antifouling properties. Separation and Purification Technology, 212: 1–11
23 H Koulivand, A Shahbazi, V Vatanpour (2019). Fabrication and characterization of a high-flux and antifouling polyethersulfone membrane for dye removal by embedding Fe3O4-MDA nanoparticles. Chemical Engineering Research & Design, 145: 64–75
24 B Kwon, N Park, J Cho (2010). Effects of a dynamic membrane formed with polyethylene glycol on the ultrafiltration of natural organic matter. Frontiers of Environmental Science & Engineering, 4(2): 172–182
25 B S Lalia, V Kochkodan, R Hashaikeh, N Hilal (2013). A review on membrane fabrication: Structure, properties and performance relationship. Desalination, 326: 77–95
26 P Le-Clech, V Chen, T A G Fane (2006). Fouling in membrane bioreactors used in wastewater treatment. Journal of Membrane Science, 284(1): 17–53
27 C Li, X Guo, X Wang, S Fan, Q Zhou, H Shao, W Hu, C Li, L Tong, R R Kumar, J Huang (2018). Membrane fouling mitigation by coupling applied electric field in membrane system: Configuration, mechanism and performance. Electrochimica Acta, 287: 124–134
28 D Li, Y Yan, H Wang (2016). Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes. Progress in Polymer Science, 61: 104–155
29 S Li, G Liao, Z Liu, Y Pan, Q Wu, Y Weng, X Zhang, Z Yang, O K C Tsui (2014). Enhanced water flux in vertically aligned carbon nanotube arrays and polyethersulfone composite membranes. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2(31): 12171–12176
30 X Li, A Sotto, J Li, B Van Der Bruggen (2017). Progress and perspectives for synthesis of sustainable antifouling composite membranes containing in situ generated nanoparticles. Journal of Membrane Science, 524: 502–528
31 Y Liao, A Bokhary, E Maleki, B Liao (2018a). A review of membrane fouling and its control in algal-related membrane processes. Bioresource Technology, 264: 343–358 pmid: 29983228
32 Y Liao, C H Loh, M Tian, R Wang, A G Fane (2018b). Progress in electrospun polymeric nanofibrous membranes for water treatment: Fabrication, modification and applications. Progress in Polymer Science, 77: 69–94
33 M Majumder, N Chopra, R Andrews, B J Hinds (2005). Nanoscale hydrodynamics: Enhanced flow in carbon nanotubes. Nature, 438(7064): 44–44 pmid: 16267546
34 F Meng, S Zhang, Y Oh, Z Zhou, H S Shin, S R Chae (2017). Fouling in membrane bioreactors: An updated review. Water Research, 114: 151–180 pmid: 28237783
35 V D Punetha, S Rana, H J Yoo, A Chaurasia, J T Mcleskey Jr, M S Ramasamy, N G Sahoo, J W Cho (2017). Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene. Progress in Polymer Science, 67: 1–47
36 M Qasim, N N Darwish, S Mhiyo, N A Darwish, N Hilal (2018). The use of ultrasound to mitigate membrane fouling in desalination and water treatment. Desalination, 443: 143–164
37 Q She, R Wang, A G Fane, C Y Tang (2016). Membrane fouling in osmotically driven membrane processes: A review. Journal of Membrane Science, 499: 201–233
38 L D Tijing, Y C Woo, J S Choi, S Lee, S H Kim, H K Shon (2015). Fouling and its control in membrane distillation: A review. Journal of Membrane Science, 475: 215–244
39 V Vatanpour, S S Madaeni, R Moradian, S Zinadini, B Astinchap (2011). Fabrication and characterization of novel antifouling nanofiltration membrane prepared from oxidized multiwalled carbon nanotube/polyethersulfone nanocomposite. Journal of Membrane Science, 375(1): 284–294
40 J Wang, X Gao, H Yu, Q Wang, Z Ma, Z Li, Y Zhang, C Gao (2019a). Accessing of graphene oxide (GO) nanofiltration membranes for microbial and fouling resistance. Separation and Purification Technology, 215: 91–101
41 S Wang, T Li, C Chen, B Liu, J C Crittende (2018). PVDF ultrafiltration membranes of controlled performance via blending PVDF-g-PEGMA copolymer synthesized under different reaction times. Frontiers of Environmental Science & Engineering, 12(2): 3
42 X Wang, M Feng, Y Liu, H Deng, J Lu (2019b). Fabrication of graphene oxide blended polyethersulfone membranes via phase inversion assisted by electric field for improved separation and antifouling performance. Journal of Membrane Science, 577: 41–50
43 X Wang, M Zhou, X Meng, L Wang, D Huang (2016). Effect of protein on PVDF ultrafiltration membrane fouling behavior under different pH conditions: Interface adhesion force and XDLVO theory analysis. Frontiers of Environmental Science & Engineering, 10(4): 12
44 R N Wenzel (1936). Resistance of Solid Surfaces to Wetting by Water. Industrial & Engineering Chemistry, 28(8): 988–994
45 D Yang, C Cheng, M Bao, L Chen, Y Bao, C Xue (2019). The pervaporative membrane with vertically aligned carbon nanotube nanochannel for enhancing butanol recovery. Journal of Membrane Science, 577: 51–59
46 G Zhang, M Zhou, Z Xu, C Jiang, C Shen, Q Meng (2019). Guanidyl-functionalized graphene/polysulfone mixed matrix ultrafiltration membrane with superior permselective, antifouling and antibacterial properties for water treatment. Journal of Colloid and Interface Science, 540: 295–305 pmid: 30660082
47 J Zhang, Z Xu, W Mai, C Min, B Zhou, M Shan, Y Li, C Yang, Z Wang, X Qian (2013a). Improved hydrophilicity, permeability, antifouling and mechanical performance of PVDF composite ultrafiltration membranes tailored by oxidized low-dimensional carbon nanomaterials. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 1(9): 3101–3111
48 J Zhang, Z Xu, M Shan, B Zhou, Y Li, B Li, J Niu, X Qian (2013b). Synergetic effects of oxidized carbon nanotubes and graphene oxide on fouling control and anti-fouling mechanism of polyvinylidene fluoride ultrafiltration membranes. Journal of Membrane Science, 448: 81–92
49 F Zhao, H Chu, Y Zhang, S Jiang, Z Yu, X Zhou, J Zhao (2017). Increasing the vibration frequency to mitigate reversible and irreversible membrane fouling using an axial vibration membrane in microalgae harvesting. Journal of Membrane Science, 529: 215–223
50 J Zhao, Y Yang, C Li, L A Hou (2019). Fabrication of GO modified PVDF membrane for dissolved organic matter removal: Removal mechanism and antifouling property. Separation and Purification Technology, 209: 482–490
51 J Zhao, X Zhao, Z Jiang, Z Li, X Fan, J Zhu, H Wu, Y Su, D Yang, F Pan, J Shi (2014). Biomimetic and bioinspired membranes: Preparation and application. Progress in Polymer Science, 39(9): 1668–1720
52 X Zhao, R Zhang, Y Liu, M He, Y Su, C Gao, Z Jiang (2018). Antifouling membrane surface construction: Chemistry plays a critical role. Journal of Membrane Science, 551: 145–171
53 S Zinadini, A A Zinatizadeh, M Rahimi, V Vatanpour, H Zangeneh (2014). Preparation of a novel antifouling mixed matrix PES membrane by embedding graphene oxide nanoplates. Journal of Membrane Science, 453: 292–301
Related articles from Frontiers Journals
[1] Bei Ye, Zhuo Chen, Xinzheng Li, Jianan Liu, Qianyuan Wu, Cheng Yang, Hongying Hu, Ronghe Wang. Inhibition of bromate formation by reduced graphene oxide supported cerium dioxide during ozonation of bromide-containing water[J]. Front. Environ. Sci. Eng., 2019, 13(6): 86-.
[2] Xuemin Hao, Guanlong Wang, Shuo Chen, Hongtao Yu, Xie Quan. Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants[J]. Front. Environ. Sci. Eng., 2019, 13(5): 77-.
[3] Zhichao Wu, Chang Zhang, Kaiming Peng, Qiaoying Wang, Zhiwei Wang. Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation[J]. Front. Environ. Sci. Eng., 2018, 12(3): 15-.
[4] Fenghe Lv, Hua Wang, Zhangliang Li, Qi Zhang, Xuan Liu, Yan Su. Fabrication and photocatalytic ability of an Au/TiO2/reduced graphene oxide nanocomposite[J]. Front. Environ. Sci. Eng., 2018, 12(1): 4-.
[5] Yu YANG,Zhicheng YU,Takayuki NOSAKA,Kyle DOUDRICK,Kiril HRISTOVSKI,Pierre HERCKES,Paul WESTERHOFF. Interaction of carbonaceous nanomaterials with wastewater biomass[J]. Front. Environ. Sci. Eng., 2015, 9(5): 823-831.
[6] Shubo DENG,Yue BEI,Xinyu LU,Ziwen DU,Bin WANG,Yujue WANG,Jun HUANG,Gang YU. Effect of co-existing organic compounds on adsorption of perfluorinated compounds onto carbon nanotubes[J]. Front. Environ. Sci. Eng., 2015, 9(5): 784-792.
[7] Li SHENG,Shuhang HUANG,Minghao SUI,Lingdian ZHANG,Lei SHE,Yong CHEN. Deposition of copper nanoparticles on multiwalled carbon nanotubes modified with poly (acrylic acid) and their antimicrobial application in water treatment[J]. Front. Environ. Sci. Eng., 2015, 9(4): 625-633.
[8] Shaoxia YANG,Yu SUN,Hongwei YANG,Jiafeng WAN. Catalytic wet air oxidation of phenol, nitrobenzene and aniline over the multi-walled carbon nanotubes (MWCNTs) as catalysts[J]. Front. Environ. Sci. Eng., 2015, 9(3): 436-443.
[9] Liqin JI, Xue BAI, Lincheng ZHOU, Hanchang SHI, Wei CHEN, Zulin HUA. One-pot preparation of graphene oxide magnetic nanocomposites for the removal of tetrabromobisphenol A[J]. Front Envir Sci Eng, 2013, 7(3): 442-450.
[10] Yue PENG, Junhua LI. Ammonia adsorption on graphene and graphene oxide: a first-principles study[J]. Front Envir Sci Eng, 2013, 7(3): 403-411.
[11] Yuanting LI, Dawei LI, Wei SONG, Meng LI, Jie ZOU, Yitao LONG. Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor[J]. Front Envir Sci Eng, 2012, 6(6): 831-838.
[12] Huilong WANG, Shuqin LIU, Hui WANG, Wenfeng JIANG, . Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO 2 composites[J]. Front.Environ.Sci.Eng., 2010, 4(3): 311-320.
[13] Jiaxi LI , Xianghua WEN , . Noncovalent immobilization of MnP from on carbon nanotubes[J]. Front.Environ.Sci.Eng., 2009, 3(3): 294-299.
Full text