Skip to main content
SpringerLink
Log in

G-CNTs/PVDF mixed matrix membranes with improved antifouling properties and filtration performance

  • Research Article
  • Published:
Frontiers of Environmental Science & Engineering Aims and scope Submit manuscript

Abstract

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 (GCNTs/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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Ao L, Liu W, Qiao Y, Li C, Wang X (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

    Article  Google Scholar 

  • Awanis Hashim N, Liu F, Moghareh Abed M R, Li K (2012). Chemistry in spinning solutions: Surface modification of PVDF membranes during phase inversion. Journal of Membrane Science, 415–416: 399–411

    Article  Google Scholar 

  • Ayyavoo J, Nguyen T P N, Jun B M, Kim I C, Kwon Y N (2016). Protection of polymeric membranes with antifouling surfacing via surface modifications. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 506: 190–201

    Article  CAS  Google Scholar 

  • Chung T S, Jiang L Y, Li Y, Kulprathipanja S (2007). Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation. Progress in Polymer Science, 32(4): 483–507

    Article  CAS  Google Scholar 

  • Cui Z, Drioli E, Lee Y M (2014). Recent progress in fluoropolymers for membranes. Progress in Polymer Science, 39(1): 164–198

    Article  CAS  Google Scholar 

  • Delgado J L, De La Cruz P, Urbina A, López Navarrete J T, Casado J, Langa F (2007). The first synthesis of a conjugated hybrid of C60—fullerene and a single-wall carbon nanotube. Carbon, 45(11): 2250–2252

    Article  CAS  Google Scholar 

  • Ding Q, Yamamura H, Murata N, Aoki N, Yonekawa H, Hafuka A, Watanabe Y (2016). Characteristics of meso-particles formed in coagulation process causing irreversible membrane fouling in the coagulation-microfiltration water treatment. Water Research, 101: 127–136

    Article  CAS  Google Scholar 

  • Ding Y, Ma B, Liu H, Qu J (2019). Effects of protein properties on ultrafiltration membrane fouling performance in water treatment. Journal of Environmental Sciences (China), 77: 273–281

    Article  Google Scholar 

  • Esfahani M R, Aktij S A, Dabaghian Z, Firouzjaei M D, Rahimpour A, Eke J, Escobar I C, Abolhassani M, Greenlee L F, Esfahani A R, Sadmani A, Koutahzadeh N (2019). Nanocomposite membranes for water separation and purification: Fabrication, modification, and applications. Separation and Purification Technology, 213: 465–499

    Article  CAS  Google Scholar 

  • Fajardo A R, Lopes L C, Rubira A F, Muniz E C (2012). Development and application of chitosan/poly(vinyl alcohol) films for removal and recovery of Pb(II). Chemical Engineering Journal, 183: 253–260

    Article  CAS  Google Scholar 

  • Fontananova E, Grosso V, Aljlil S A, Bahattab MA, Vuono D, Nicoletta F P, Curcio E, Drioli E, Di Profio G (2017). Effect of functional groups on the properties of multiwalled carbon nanotubes/polyvinylidenefluoride composite membranes. Journal of Membrane Science, 541: 198–204

    Article  CAS  Google Scholar 

  • Fornasiero F (2017). Water vapor transport in carbon nanotube membranes and application in breathable and protective fabrics. Current Opinion in Chemical Engineering, 16: 1–8

    Article  Google Scholar 

  • Hamad J Z, Dua R, Kurniasari N, Kennedy M D, Wang P, Amy G L (2014). Irreversible membrane fouling abatement through predeposited layer of hierarchical porous carbons. Water Research, 65: 245–256

    Article  CAS  Google Scholar 

  • Han G, Zhang S, Li X, Chung T S (2015). Progress in pressure retarded osmosis (PRO) membranes for osmotic power generation. Progress in Polymer Science, 51: 1–27

    Article  Google Scholar 

  • Holt J K, Park H G, Wang Y, Stadermann M, Artyukhin A B, Grigoropoulos C P, Noy A, Bakajin O (2006). Fast mass transport through sub-2-nanometer carbon nanotubes. Science, 312(5776): 1034–1037

    Article  CAS  Google Scholar 

  • Hu K, Kulkarni D D, Choi I, Tsukruk V V (2014). Graphene-polymer nanocomposites for structural and functional applications. Progress in Polymer Science, 39(11): 1934–1972

    Article  CAS  Google Scholar 

  • Huang G, Isfahani A P, Muchtar A, Sakurai K, Shrestha B B, Qin D, Yamaguchi D, Sivaniah E, Ghalei B (2018a). Pebax/ionic liquid modified graphene oxide mixed matrix membranes for enhanced CO2 capture. Journal of Membrane Science, 565: 370–379

    Article  CAS  Google Scholar 

  • Huang S, Ras R H A, Tian X (2018b). Antifouling membranes for oily wastewater treatment: Interplay between wetting and membrane fouling. Current Opinion in Colloid & Interface Science, 36: 90–109

    Article  CAS  Google Scholar 

  • Ihsanullah (2019). Carbon nanotube membranes for water purification: Developments, challenges, and prospects for the future. Separation and Purification Technology, 209: 307–337

    Article  CAS  Google Scholar 

  • Inurria A, Cay-Durgun P, Rice D, Zhang H, Seo D K, Lind M L, Perreault F (2019). Polyamide thin-film nanocomposite membranes with graphene oxide nanosheets: Balancing membrane performance and fouling propensity. Desalination, 451: 139–147

    Article  CAS  Google Scholar 

  • Kang G D, Cao Y M (2012). Development of antifouling reverse osmosis membranes for water treatment: A review. Water Research, 46(3): 584–600

    Article  CAS  Google Scholar 

  • Khairuddin N F M, Idris A, Hock L W (2019). Harvesting Nannochloropsis sp. using PES/MWCNT/LiBr membrane with good antifouling properties. Separation and Purification Technology, 212: 1–11

    Article  CAS  Google Scholar 

  • Koulivand H, Shahbazi A, Vatanpour V (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

    Article  CAS  Google Scholar 

  • Kwon B, Park N, Cho J (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

    Article  CAS  Google Scholar 

  • Lalia B S, Kochkodan V, Hashaikeh R, Hilal N (2013). A review on membrane fabrication: Structure, properties and performance relationship. Desalination, 326: 77–95

    Article  CAS  Google Scholar 

  • Le-Clech P, Chen V, Fane T A G (2006). Fouling in membrane bioreactors used in wastewater treatment. Journal of Membrane Science, 284(1): 17–53

    Article  CAS  Google Scholar 

  • Li C, Guo X, Wang X, Fan S, Zhou Q, Shao H, Hu W, Li C, Tong L, Kumar R R, Huang J (2018). Membrane fouling mitigation by coupling applied electric field in membrane system: Configuration, mechanism and performance. Electrochimica Acta, 287: 124–134

    Article  CAS  Google Scholar 

  • Li D, Yan Y, Wang H (2016). Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes. Progress in Polymer Science, 61: 104–155

    Article  Google Scholar 

  • Li S, Liao G, Liu Z, Pan Y, Wu Q, Weng Y, Zhang X, Yang Z, Tsui O K C (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

    Article  CAS  Google Scholar 

  • Li X, Sotto A, Li J, Van Der Bruggen B (2017). Progress and perspectives for synthesis of sustainable antifouling composite membranes containing in situ generated nanoparticles. Journal of Membrane Science, 524: 502–528

    Article  CAS  Google Scholar 

  • Liao Y, Bokhary A, Maleki E, Liao B (2018a). A review of membrane fouling and its control in algal-related membrane processes. Bioresource Technology, 264: 343–358

    Article  CAS  Google Scholar 

  • Liao Y, Loh C H, Tian M, Wang R, Fane A G (2018b). Progress in electrospun polymeric nanofibrous membranes for water treatment: Fabrication, modification and applications. Progress in Polymer Science, 77: 69–94

    Article  CAS  Google Scholar 

  • Majumder M, Chopra N, Andrews R, Hinds B J (2005). Nanoscale hydrodynamics: Enhanced flow in carbon nanotubes. Nature, 438(7064): 44–44

    Article  CAS  Google Scholar 

  • Meng F, Zhang S, Oh Y, Zhou Z, Shin H S, Chae S R (2017). Fouling in membrane bioreactors: An updated review. Water Research, 114: 151–180

    Article  CAS  Google Scholar 

  • Punetha V D, Rana S, Yoo H J, Chaurasia A, Mcleskey J T Jr, Ramasamy M S, Sahoo N G, Cho J W (2017). Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene. Progress in Polymer Science, 67: 1–47

    Article  CAS  Google Scholar 

  • Qasim M, Darwish N N, Mhiyo S, Darwish N A, Hilal N (2018). The use of ultrasound to mitigate membrane fouling in desalination and water treatment. Desalination, 443: 143–164

    Article  CAS  Google Scholar 

  • She Q, Wang R, Fane A G, Tang C Y (2016). Membrane fouling in osmotically driven membrane processes: A review. Journal of Membrane Science, 499: 201–233

    Article  CAS  Google Scholar 

  • Tijing L D, Woo Y C, Choi J S, Lee S, Kim S H, Shon H K (2015). Fouling and its control in membrane distillation: A review. Journal of Membrane Science, 475: 215–244

    Article  CAS  Google Scholar 

  • Vatanpour V, Madaeni S S, Moradian R, Zinadini S, Astinchap B (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

    Article  CAS  Google Scholar 

  • Wang J, Gao X, Yu H, Wang Q, Ma Z, Li Z, Zhang Y, Gao C (2019a). Accessing of graphene oxide (GO) nanofiltration membranes for microbial and fouling resistance. Separation and Purification Technology, 215: 91–101

    Article  CAS  Google Scholar 

  • Wang S, Li T, Chen C, Liu B, Crittende J C (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

    Article  Google Scholar 

  • Wang X, Feng M, Liu Y, Deng H, Lu J (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

    Article  CAS  Google Scholar 

  • Wang X, Zhou M, Meng X, Wang L, Huang D (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

    Article  Google Scholar 

  • Wenzel R N (1936). Resistance of Solid Surfaces to Wetting by Water. Industrial & Engineering Chemistry, 28(8): 988–994

    Article  CAS  Google Scholar 

  • Yang D, Cheng C, Bao M, Chen L, Bao Y, Xue C (2019). The pervaporative membrane with vertically aligned carbon nanotube nanochannel for enhancing butanol recovery. Journal of Membrane Science, 577: 51–59

    Article  CAS  Google Scholar 

  • Zhang G, Zhou M, Xu Z, Jiang C, Shen C, Meng Q (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

    Article  CAS  Google Scholar 

  • Zhang J, Xu Z, Mai W, Min C, Zhou B, Shan M, Li Y, Yang C, Wang Z, Qian X (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

    Article  CAS  Google Scholar 

  • Zhang J, Xu Z, Shan M, Zhou B, Li Y, Li B, Niu J, Qian X (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

    Article  CAS  Google Scholar 

  • Zhao F, Chu H, Zhang Y, Jiang S, Yu Z, Zhou X, Zhao J (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

    Article  CAS  Google Scholar 

  • Zhao J, Yang Y, Li C, Hou L A (2019). Fabrication of GO modified PVDF membrane for dissolved organic matter removal: Removal mechanism and antifouling property. Separation and Purification Technology, 209: 482–490

    Article  CAS  Google Scholar 

  • Zhao J, Zhao X, Jiang Z, Li Z, Fan X, Zhu J, Wu H, Su Y, Yang D, Pan F, Shi J (2014). Biomimetic and bioinspired membranes: Preparation and application. Progress in Polymer Science, 39(9): 1668–1720

    Article  CAS  Google Scholar 

  • Zhao X, Zhang R, Liu Y, He M, Su Y, Gao C, Jiang Z (2018). Antifouling membrane surface construction: Chemistry plays a critical role. Journal of Membrane Science, 551: 145–171

    Article  CAS  Google Scholar 

  • Zinadini S, Zinatizadeh A A, Rahimi M, Vatanpour V, Zangeneh H (2014). Preparation of a novel antifouling mixed matrix PES membrane by embedding graphene oxide nanoplates. Journal of Membrane Science, 453: 292–301

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the financial support by the Key Program of Natural Science Foundation of Tianjin City (Grant No. 18JCZDJC39700), the Science and Technology Project of Binhai District of Tianjin (Grant No. BHXQKJXM-PT-ZJSHJ-2017004), the National Key Research and Development Program of China (Grant No. 2017YFC0404002) and the 111 Program, Ministry of Education of China (Grant No. T2017002).

Author information

Authors and Affiliations

  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

    Xiaoyan Guo, Chunyu Li, Chenghao Li, Tingting Wei, Lin Tong, Qixing Zhou & Lan Wang

  2. Sino-Canada Joint R&D Centre for Water and Environmental Safety, College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, China

    Xiaoyan Guo, Chunyu Li, Chenghao Li, Lin Tong & Yuan Liao

  3. College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin, 300457, China

    Huaiqi Shao

Authors
  1. Xiaoyan Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chunyu Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chenghao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tingting Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Lin Tong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Huaiqi Shao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qixing Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yuan Liao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuan Liao.

Additional information

Highlights

• 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.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, X., Li, C., Li, C. et al. G-CNTs/PVDF mixed matrix membranes with improved antifouling properties and filtration performance. Front. Environ. Sci. Eng. 13, 81 (2019). https://doi.org/10.1007/s11783-019-1165-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11783-019-1165-9

Keywords

Search

Navigation