Science China Technological Sciences

, Volume 62, Issue 9, pp 1585–1595 | Cite as

Robust superhydrophobic polyurethane sponge functionalized with perfluorinated graphene oxide for efficient immiscible oil/water mixture, stable emulsion separation and crude oil dehydration

  • Ning CaoEmail author
  • JingYu Guo
  • Rabah Boukherroub
  • QingGuo Shao
  • XiaoBei Zang
  • Jin Li
  • XueQiang Lin
  • Hong Ju
  • EnYang Liu
  • ChaoFan Zhou
  • HuiPing Li


In recent years, graphene oxide (GO), prepared by the modified Hummers’ method, and its derivatives have become a focus of research owing to their outstanding physical and chemical properties and low cost. Drawing inspiration from the mussel protein, a facile and environmentally-friendly method was employed to fabricate superhydrophobic/superoleophilic reduced graphene oxide (rGO) derivative. The preparation comprises two steps: coating GO nanosheets with polydopamine (PDA) and subsequent reaction with 1H,1H,2H,2H-perfluorodecanethiol. Due to the excellent adhesive ability of PDA, the resulting fPDA modified rGO nanosheets (rGO-fPDA) were firmly immobilized onto polyurethane (PU) sponge skeleton by a simple drop-coating method. The as-prepared rGO-fPDA functionalized sponge exhibited superhydrophobic behavior with a water contact angle of 162°±2°, high organic adsorption capacity, recyclability and stable oil/water separation behavior under different acidic/alkaline conditions. Due to its facile fabrication technique and outstanding properties, the superhydrophobic-superoleophilic PU-rGO-fPDA sponge holds great promise as an oil adsorbent for cleaning up large-scale pollution of oil and organic solvents, and dehydrating crude oil.


graphene oxide superhydrophobic sponge adsorption oil/water separation emulsion 


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Robust superhydrophobic polyurethane sponge functionalized with perfluorinated graphene oxide for efficient immiscible oil/water mixture, stable emulsion separation and crude oil dehydration


  1. 1.
    Song S K, Shon Z H, Kim Y K, et al. An oil spill accident and its impact on ozone levels in the surrounding coastal regions. Atmos Environ, 2011, 45: 1312–1322CrossRefGoogle Scholar
  2. 2.
    Baig U, Matin A, Gondal M A, et al. Facile fabrication of superhydrophobic, superoleophilic photocatalytic membrane for efficient oil-water separation and removal of hazardous organic pollutants. J Clean Prod, 2019, 208: 904–915CrossRefGoogle Scholar
  3. 3.
    Venkataraman P, Tang J, Frenkel E, et al. Attachment of a hydrophobically modified biopolymer at the oil-water interface in the treatment of oil spills. ACS Appl Mater Interfaces, 2013, 5: 3572–3580CrossRefGoogle Scholar
  4. 4.
    Zhu Q, Pan Q, Liu F. Facile removal and collection of oils from water surfaces through superhydrophobic and superoleophilic sponges. J Phys Chem C, 2011, 115: 17464–17470CrossRefGoogle Scholar
  5. 5.
    Chu Y, Pan Q. Three-dimensionally macroporous Fe/C nanocomposites as highly selective oil-absorption materials. ACS Appl Mater Interfaces, 2012, 4: 2420–2425CrossRefGoogle Scholar
  6. 6.
    Yuan S J, Zhang J J, Fan H X, et al. Facile and sustainable shear mixing/carbonization approach for upcycling of carton into superhydrophobic coating for efficient oil-water separation. J Clean Prod, 2018, 196: 644–652CrossRefGoogle Scholar
  7. 7.
    Wang J, Zheng Y. Oil/water mixtures and emulsions separation of stearic acid-functionalized sponge fabricated via a facile one-step coating method. Sep Purif Technol, 2017, 181: 183–191CrossRefGoogle Scholar
  8. 8.
    Yao X, Song Y, Jiang L. Applications of bio-inspired special wettable surfaces. Adv Mater, 2011, 23: 719–734CrossRefGoogle Scholar
  9. 9.
    Gui X, Wei J, Wang K, et al. Carbon nanotube sponges. Adv Mater, 2010, 22: 617–621CrossRefGoogle Scholar
  10. 10.
    Feng L, Zhang Z, Mai Z, et al. A super-hydrophobic and superoleophilic coating mesh film for the separation of oil and water. Angew Chem Int Ed, 2004, 43: 2012–2014CrossRefGoogle Scholar
  11. 11.
    Wang S, Li M, Lu Q. Filter paper with selective absorption and separation of liquids that differ in surface tension. ACS Appl Mater Interfaces, 2010, 2: 677–683CrossRefGoogle Scholar
  12. 12.
    Bi H, Xie X, Yin K, et al. Spongy graphene as a highly efficient and recyclable sorbent for oils and organic solvents. Adv Funct Mater, 2012, 22: 4421–4425CrossRefGoogle Scholar
  13. 13.
    Novoselov K S, Geim A K, Morozov S V, et al. Two-dimensional gas of massless dirac fermions in graphene. Nature, 2005, 438: 197–200CrossRefGoogle Scholar
  14. 14.
    Lee H, Dellatore S M, Miller W M, et al. Mussel-inspired surface chemistry for multifunctional coatings. Science, 2007, 318: 426–430CrossRefGoogle Scholar
  15. 15.
    Liu Y, Ai K, Lu L. Polydopamine and its derivative materials: Synthesis and promising applications in energy, environmental, and biomedical fields. Chem Rev, 2014, 114: 5057–5115CrossRefGoogle Scholar
  16. 16.
    Cao N, Miao Y, Zhang D, et al. Preparation of mussel-inspired perfluorinated polydopamine film on brass substrates: Superhydrophobic and anti-corrosion application. Prog Org Coat, 2018, 125: 109–118CrossRefGoogle Scholar
  17. 17.
    Wang H, Wang E, Liu Z, et al. A novel carbon nanotubes reinforced superhydrophobic and superoleophilic polyurethane sponge for selective oil-water separation through a chemical fabrication. J Mater Chem A, 2014, 3: 266–273CrossRefGoogle Scholar
  18. 18.
    Fei B, Qian B, Yang Z, et al. Coating carbon nanotubes by spontaneous oxidative polymerization of dopamine. Carbon, 2008, 46: 1795–1797CrossRefGoogle Scholar
  19. 19.
    Cao N, Yang B, Barras A, et al. Polyurethane sponge functionalized with superhydrophobic nanodiamond particles for efficient oil/water separation. Chem Eng J, 2017, 307: 319–325CrossRefGoogle Scholar
  20. 20.
    Cao N, Lyu Q, Li J, et al. Facile synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide composite aerogel for efficient oil/water separation. Chem Eng J, 2017, 326: 17–28CrossRefGoogle Scholar
  21. 21.
    Hong D, Bae K E, Hong S P, et al. Mussel-inspired, perfluorinated polydopamine for self-cleaning coating on various substrates. Chem Commun, 2014, 50: 11649–11652CrossRefGoogle Scholar
  22. 22.
    Huang N, Zhang S, Yang L, et al. Multifunctional electrochemical platforms based on the michael addition/schiff base reaction of polydopamine modified reduced graphene oxide: Construction and application. ACS Appl Mater Interfaces, 2015, 7: 17935–17946CrossRefGoogle Scholar
  23. 23.
    Hummers Jr W S, Offeman R E. Preparation of graphitic oxide. J Am Chem Soc, 1958, 80: 1339CrossRefGoogle Scholar
  24. 24.
    Zhu C, Guo S, Fang Y, et al. Reducing sugar: New functional molecules for the green synthesis of graphene nanosheets. ACS Nano, 2010, 4: 2429–2437CrossRefGoogle Scholar
  25. 25.
    Bose S, Kuila T, Uddin M E, et al. In-situ synthesis and characterization of electrically conductive polypyrrole/graphene nanocomposites. Polymer, 2010, 51: 5921–5928CrossRefGoogle Scholar
  26. 26.
    Liu M, Zhou J, Yang Y, et al. Surface modification of zirconia with polydopamine to enhance fibroblast response and decrease bacterial activity in vitro: A potential technique for soft tissue engineering applications. Colloid Surface B, 2015, 136: 74–83CrossRefGoogle Scholar
  27. 27.
    Yuan J, Liu X, Akbulut O, et al. Superwetting nanowire membranes for selective absorption. Nat Nanotech, 2008, 3: 332–336CrossRefGoogle Scholar
  28. 28.
    Fan Z, Wang K, Wei T, et al. An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder. Carbon, 2010, 48: 1686–1689CrossRefGoogle Scholar
  29. 29.
    Zhang B, Wang T, Liu S, et al. Structure and morphology of micro-porous carbon membrane materials derived from poly(phthalazinone ether sulfone ketone). Microporous Mesoporous Mater, 2006, 96: 79–83CrossRefGoogle Scholar
  30. 30.
    Guo L P, Sun W, Yu T, et al. Preparation and characteristics of a recycled cement-based superhydrophobic coating with dirt pickup resistance. Sci China Tech Sci, 2015, 58: 1096–1104CrossRefGoogle Scholar
  31. 31.
    Jiang L, Zhao Y, Zhai J. A lotus-leaf-like superhydrophobic surface: A porous microsphere/nanofiber composite film prepared by electro-hydrodynamics. Angew Chem Int Ed, 2004, 43: 4338–4341CrossRefGoogle Scholar
  32. 32.
    Zhang X, Shi F, Niu J, et al. Superhydrophobic surfaces: From structural control to functional application. J Mater Chem, 2008, 18: 621–633CrossRefGoogle Scholar
  33. 33.
    Phanthong P, Reubroycharoen P, Kongparakul S, et al. Fabrication and evaluation of nanocellulose sponge for oil/water separation. Carbohyd Polym, 2018, 190: 184–189CrossRefGoogle Scholar
  34. 34.
    Yang J, Xia Y, Xu P, et al. Super-elastic and highly hydrophobic/superoleophilic sodium alginate/cellulose aerogel for oil/water separation. Cellulose, 2018, 25: 3533–3544CrossRefGoogle Scholar
  35. 35.
    Wei H, Wang F, Qian X, et al. Superhydrophobic fluorine-rich conjugated microporous polymers monolithic nanofoam with excellent heat insulation property. Chem Eng J, 2018, 351: 856–866CrossRefGoogle Scholar
  36. 36.
    Wang J, Geng G. Highly recyclable superhydrophobic sponge suitable for the selective sorption of high viscosity oil from water. Mar Pollut Bull, 2015, 97: 118–124CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Ning Cao
    • 1
    • 2
    Email author
  • JingYu Guo
    • 2
  • Rabah Boukherroub
    • 3
  • QingGuo Shao
    • 2
  • XiaoBei Zang
    • 2
  • Jin Li
    • 2
  • XueQiang Lin
    • 2
  • Hong Ju
    • 2
  • EnYang Liu
    • 2
  • ChaoFan Zhou
    • 2
  • HuiPing Li
    • 4
  1. 1.Key Laboratory of Unconventional Oil & Gas Development, Ministry of EducationChina University of Petroleum (East China)QingdaoChina
  2. 2.School of Materials Science and EngineeringChina University of Petroleum (East China)QingdaoChina
  3. 3.Univ. Lille, CNRS, Centrale Lille, ISENUniv. Valenciennes, UMR 8520, IEMNLilleFrance
  4. 4.School of Materials Science and EngineeringShandong University of Science and TechnologyQingdaoChina

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