Frontiers of Chemical Science and Engineering

, Volume 12, Issue 3, pp 390–399 | Cite as

Superhydrophobic, mechanically flexible and recyclable reduced graphene oxide wrapped sponge for highly efficient oil/water separation

  • Lijuan Qiu
  • Ruiyang Zhang
  • Ying Zhang
  • Chengjin Li
  • Qian Zhang
  • Ying ZhouEmail author
Research Article


Water pollution has become an urgent issue for our modern society, and it is highly desirable to rapidly deal with the water pollution without secondary pollution. In this paper, we have prepared a reduced graphene oxide (RGO) wrapped sponge with superhydrophobicity and mechanically flexibility via a facile low-temperature thermal treatment method under a reducing atmosphere. The skeleton of this sponge is completely covered with RGO layers which are closely linked to the skeleton. This sponge has an abundant pore structure, high selectivity, good recyclability, low cost, and outstanding adsorption capacity for floating oil or heavy oil underwater. In addition, this sponge can maintain excellent adsorption performance for various oils and organic solvents over 50 cycles by squeezing, and exhibits extremely high separation efficiencies, up to 6 × 106 and 3.6 × 106 L·m–3·h–1 in non-turbulent and turbulent water/oil systems, respectively. This superhydrophobic adsorbent with attractive properties may find various applications, especially in large-scale removal of organic contaminants and oil spill cleanup.


superhydrophobicity mechanically flexibility water/oil separation reduced graphene oxide wrapped sponge 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



We thank the Sichuan Provincial International Cooperation Project (2017HH0030), the Scientific Research Starting project of SWPU (2014QHZ021), the Training funds for academic and technological leaders in Sichuan and the Innovative Research Team of Sichuan Province (2016TD0011) for financial support.

Supplementary material

Supplementary material, approximately 362 KB.

11705_2018_1751_MOESM2_ESM.avi (720 kb)
Supplementary material, approximately 720 KB.

Supplementary material, approximately 2.32 MB.

11705_2018_1751_MOESM4_ESM.avi (2.9 mb)
Supplementary material, approximately 2.86 MB.
11705_2018_1751_MOESM5_ESM.avi (4.5 mb)
Supplementary material, approximately 4.46 MB.
11705_2018_1751_MOESM6_ESM.pdf (1.8 mb)
Superhydrophobic, mechanically flexible and recyclable reduced graphene oxide wrapped sponge for highly efficient oil/water separation


  1. 1.
    Schrope M. Oil spill: Deep wounds. Nature, 2011, 472(7342): 152–154CrossRefPubMedGoogle Scholar
  2. 2.
    Joye S B. Marine Science. Deepwater Horizon, 5 years on. Science, 2015, 349(6248): 592–593PubMedGoogle Scholar
  3. 3.
    Ivshina I B, Kuyukina M S, Krivoruchko A V, Elkin A A, Makarov S O, Cunningham C J, Peshkur T A, Atlas R M, Philp J C. Oil spill problems and sustainable response strategies through new technologies. Environmental Science: Processes & Impacts, 2015, 17(7): 1201–1219Google Scholar
  4. 4.
    Gupta S, Tai N H. Carbon materials as oil sorbents: A review on the synthesis and performance. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(5): 1550–1565CrossRefGoogle Scholar
  5. 5.
    Sun Y R, Yang M X, Yu F, Chen J H, Ma J. Synthesis of graphene aerogel adsorbents and their applications in water treatment. Progress in Chemistry, 2015, 27(8): 1133–1146Google Scholar
  6. 6.
    Sun H Y, Xu Z, Gao C. Multifunctional, ultra-flyweight, synergistically assembled carbon aerogels. Advanced Materials, 2013, 25(18): 2554–2560CrossRefPubMedGoogle Scholar
  7. 7.
    Hu H, Zhao Z B, Wan W B, Gogotsi Y, Qiu J S. Ultralight and highly compressible graphene aerogels. Advanced Materials, 2013, 25(15): 2219–2223CrossRefPubMedGoogle Scholar
  8. 8.
    Wan W C, Lin Y H, Prakash A, Zhou Y. Three-dimensional carbonbased architectures for oil remediation: From synthesis and modification to functionalization. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(48): 18687–18705CrossRefGoogle Scholar
  9. 9.
    Xu L M, Xiao G Y, Chen C B, Li R, Mai Y Y, Sun G M, Yan D Y. Superhydrophobic and superoleophilic graphene aerogel prepared by facile chemical reduction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(14): 7498–7504CrossRefGoogle Scholar
  10. 10.
    Li J, Kang R M, Tang X H, She H D, Yang Y X, Zha F. Superhydrophobic meshes that can repel hot water and strong corrosive liquids used for efficient gravity-driven oil/water separation. Nanoscale, 2016, 8(14): 7638–7645CrossRefPubMedGoogle Scholar
  11. 11.
    Xiao J L, Zhang J F, Lv W Y, Song Y H, Zheng Q. Multifunctional graphene/poly (vinyl alcohol) aerogels: In situ hydrothermal preparation and applications in broad-spectrum adsorption for dyes and oils. Carbon, 2017, 123: 354–363CrossRefGoogle Scholar
  12. 12.
    Wu C, Huang X Y, Wu X F, Qian R, Jiang P K. Mechanically flexible and multifunctional polymer-based graphene foams for elastic conductors and oil-water separators. Advanced Materials, 2013, 25(39): 5658–5662CrossRefPubMedGoogle Scholar
  13. 13.
    Xu Y X, Sheng K X, Li C, Shi G Q. Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano, 2010, 4 (7): 4324–4330Google Scholar
  14. 14.
    Kuang J, Dai Z H, Liu L Q, Yang Z, Jin M, Zhang Z. Synergistic effects from graphene and carbon nanotubes endow ordered hierarchical structure foams with a combination of compressibility, super-elasticity and stability and potential application as pressure sensors. Nanoscale, 2015, 7(20): 9252–9260CrossRefPubMedGoogle Scholar
  15. 15.
    He Y L, Li J H, Luo K, Li L F, Chen J B, Li J Y. Engineering reduced graphene oxide aerogel produced by effective g-ray radiation-induced self-assembly and its application for continuous oil-water separation. Industrial & Engineering Chemistry Research, 2016, 55(13): 3775–3781CrossRefGoogle Scholar
  16. 16.
    Dong X C, Chen J, Ma Y W, Wang J, Chan-Park M B, Liu X M, Wang L H, Huang W, Chen P. Superhydrophobic and superoleophilic hybrid foam of graphene and carbon nanotube for selective removal of oils or organic solvents from the surface of water. Chemical Communications, 2012, 48(86): 10660–10662CrossRefPubMedGoogle Scholar
  17. 17.
    Li R, Chen C B, Li J, Xu L M, Xiao G Y, Yan D Y. A facile approach to superhydrophobic and superoleophilic graphene/polymer aerogels. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(9): 3057–3064CrossRefGoogle Scholar
  18. 18.
    Cong H P, Ren X C, Wang P, Yu S H. Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal ion induced selfassembly process. ACS Nano, 2012, 6(3): 2693–2703CrossRefPubMedGoogle Scholar
  19. 19.
    Bi H C, Xie X, Yin K B, Zhou Y L, Wan S, Ruoff R S, Sun L T. Highly enhanced performance of spongy graphene as an oil sorbent. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(6): 1652–1656CrossRefGoogle Scholar
  20. 20.
    Pham V H, Dickerson J H. Superhydrophobic silanized melamine sponges as high efficiency oil absorbent materials. ACS Applied Materials & Interfaces, 2014, 6(16): 14181–14188CrossRefGoogle Scholar
  21. 21.
    Ji C H, Zhang K, Li L, Chen X X, Hu J L, Yan D Y, Xiao G Y, He X H. High performance graphene-based foam fabricated by a facile approach for oil absorption. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(22): 11263–11270CrossRefGoogle Scholar
  22. 22.
    Wan W C, Zhang R Y, Li W, Liu H, Lin Y H, Li L N, Zhou Y. Graphene-carbon nanotube aerogel as an ultralight, compressible and recyclable highly efficient absorbent for oil and dyes. Environmental Science: Nano, 2016, 3(1): 107–113Google Scholar
  23. 23.
    Wan W C, Zhang F, Yu S, Zhang R Y, Zhou Y. Hydrothermal formation of graphene aerogel for oil sorption: The role of reducing agent, reaction time and temperature. New Journal of Chemistry, 2016, 40(4): 3040–3046CrossRefGoogle Scholar
  24. 24.
    Paredes J I, Villar-Rodil S, Martínez-Alonso A, Tascón J M D. Graphene oxide dispersions in organic solvents. Langmuir, 2008, 24 (19): 10560–10564Google Scholar
  25. 25.
    Bosch-Navarro C, Coronado E, Martí-Gastaldo C, Sánchez-Royo J F, Gómez M G. Influence of the pH on the synthesis of reduced graphene oxide under hydrothermal conditions. Nanoscale, 2012, 4 (13): 3977–3982Google Scholar
  26. 26.
    Stolz A, Floch S L, Reinert L, Ramos S M M, Tuaillon-Combes J, Soneda Y, Chaudet P, Baillis D, Blanchard N, Duclaux L, et al.. Melamine-derived carbon sponges for oil-water separation. Carbon, 2016, 107: 198–208CrossRefGoogle Scholar
  27. 27.
    Hang Z S, Tan L H, Ju F Y, Zhou B, Ying S J. Non-isothermal kinetic studies on the thermal decomposition of melamine by thermogravimetric analysis. Journal of Analytical Science, 2011, 27 (3): 279–283Google Scholar
  28. 28.
    Cheng Y, Dong Y Y, Wu J H, Yang X R, Bai H, Zheng H Y, Ren D M, Zou Y D, Li M. Screening melamine adulterant in milk powder with laser Raman spectrometry. Journal of Food Composition and Analysis, 2010, 23(2): 199–202CrossRefGoogle Scholar
  29. 29.
    Yang D X, Velamakanni A, Bozoklu G, Park S, Stoller M, Piner R D, Stankovich S, Jung I, Field D A, Ventrice C A Jr, Ruoff R S. Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy. Carbon, 2009, 47(1): 145–152CrossRefGoogle Scholar
  30. 30.
    Ge J, Shi L A, Wang Y C, Zhao H Y, Yao H B, Zhu Y B, Zhang Y, Zhu H W, Wu H A, Yu S H. Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spill. Nature Nanotechnology, 2017, 12(5): 434–440CrossRefPubMedGoogle Scholar
  31. 31.
    Stankovich S, Dikin D A, Piner R D, Kohlhaas K A, Kleinhammes A, Jia Y Y, Wu Y, Nguyen S T, Ruoff R S. Synthesis of graphenebased nanosheets via chemical reduction of exfoliated graphite oxide. Carbon, 2007, 45(7): 1558–1565CrossRefGoogle Scholar
  32. 32.
    Wang Z T, Xiao C F, Zhao J, Hu X, Xu N K. Preparation of reduced graphene oxide-based melamine sponge and its absorption properties. Chemical Journal of Chinese Universities, 2014, 35: 2410–2417Google Scholar
  33. 33.
    Periasamy A P, Wu WP, Ravindranath R, Roy P, Lin G L, Chang H T. Polymer/reduced graphene oxide functionalized sponges as superabsorbents for oil removal and recovery. Marine Pollution Bulletin, 2017, 114(2): 888–895CrossRefPubMedGoogle Scholar
  34. 34.
    Ganguly A, Sharma S, Papakonstantinou P, Hamilton J. Probing the thermal deoxygenation of graphene oxide using high-resolution in situ X-ray-based spectroscopies. Journal of Physical Chemistry C, 2011, 115(34): 17009–17019CrossRefGoogle Scholar
  35. 35.
    Lei Z W, Zhang G Z, Deng Y H, Wang C Y. Thermoresponsive melamine sponges with switchable wettability by interface-initiated atom transfer radical polymerization for oil/water separation. ACS Applied Materials & Interfaces, 2017, 9(10): 8967–8974CrossRefGoogle Scholar
  36. 36.
    Sheng Z H, Shao L, Chen J J, Bao W J, Wang F B, Xia X H. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano, 2011, 5(6): 4350–4358CrossRefPubMedGoogle Scholar
  37. 37.
    Ding Q, Song X Y, Yao X J, Qi X S, Au C T, Zhong W, Du Y W. Large-scale and controllable synthesis of metal-free nitrogen-doped carbon nanofibers and nanocoils over water-soluble Na2CO3. Nanoscale Research Letters, 2013, 8(1): 545CrossRefPubMedPubMedCentralGoogle Scholar
  38. 38.
    Kuang J, Liu L Q, Gao Y, Zhou D, Chen Z, Han B H, Zhang Z. A hierarchically structured graphene foam and its potential as a largescale strain-gauge sensor. Nanoscale, 2013, 5(24): 12171–12177CrossRefPubMedGoogle Scholar
  39. 39.
    Yao H B, Huang G, Cui C H, Wang X H, Yu S H. Macroscale elastomeric conductors generated from hydrothermally synthesized metal-polymer hybrid nanocable sponges. Advanced Materials, 2011, 23(32): 3643–3647CrossRefPubMedGoogle Scholar
  40. 40.
    Yu C L, Yu C M, Cui L Y, Song Z Y, Zhao X Y, Ma Y, Jiang L. Facile preparation of the porous PDMS oil-absorbent for oil/water separation. Advanced Materials Interfaces, 2017, 4(3): 1600862CrossRefGoogle Scholar
  41. 41.
    Qiu L J, Wan W C, Tong Z Q, Zhang R Y, Li L N, Zhou Y. Controllable and green synthesis of robust graphene aerogels with tunable surface properties for oil and dye adsorption. New Journal of Chemistry, 2018, 42(2): 1003–1009CrossRefGoogle Scholar
  42. 42.
    Barthlott W, Neinhuis C. Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta, 1997, 202(1): 1–8CrossRefGoogle Scholar
  43. 43.
    Hu H, Zhao Z B, Wan W B, Gogotsi Y, Qiu J S. Polymer/graphene hybrid aerogel with high compressibility, conductivity, and “sticky” superhydrophobicity. ACS Applied Materials & Interfaces, 2014, 6 (5): 3242–3249CrossRefGoogle Scholar
  44. 44.
    Si Y, Fu Q X, Wang X Q, Zhu J, Yu J Y, Sun G, Ding B. Superelastic and superhydrophobic nanofiber-assembled cellular aerogels for effective separation of oil/water emulsions. ACS Nano, 2015, 9(4): 3791–3799CrossRefPubMedGoogle Scholar
  45. 45.
    Kabiri S, Tran D N H, Altalhi T, Losic D. Outstanding adsorption performance of graphene–carbon nanotube aerogels for continuous oil removal. Carbon, 2014, 80: 523–533CrossRefGoogle Scholar
  46. 46.
    Tran D N H, Kabiri S, Sim T R, Losic D. Selective adsorption of oilwater mixtures using polydimethylsiloxane (PDMS)-graphene sponges. Environmental Science: Water Research & Technology, 2015, 1(3): 298–305Google Scholar
  47. 47.
    Cao N, Yang B, Barras A, Szunerits S, Boukherroub R. Polyurethane sponge functionalized with superhydrophobic nanodiamond particles for efficient oil/water separation. Chemical Engineering Journal, 2017, 307: 319–325CrossRefGoogle Scholar
  48. 48.
    Song S, Yang H, Su C P, Jiang Z B, Lu Z. Ultrasonic-microwave assisted synthesis of stable reduced graphene oxide modified melamine foam with superhydrophobicity and high oil adsorption capacities. Chemical Engineering Journal, 2016, 306: 504–511CrossRefGoogle Scholar
  49. 49.
    Luo Y Z, Jiang S L, Xiao Q, Chen C L, Li B Y. Highly reusable and superhydrophobic spongy graphene aerogels for efficient oil/water separation. Scientific Reports, 2017, 7(1): 7162CrossRefPubMedPubMedCentralGoogle Scholar

Copyright information

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Lijuan Qiu
    • 1
    • 2
  • Ruiyang Zhang
    • 2
  • Ying Zhang
    • 2
  • Chengjin Li
    • 2
  • Qian Zhang
    • 2
  • Ying Zhou
    • 1
    • 2
    Email author
  1. 1.State Key Laboratory of Oil and Gas Reservoir Geology and ExploitationSouthwest Petroleum UniversityChengduChina
  2. 2.The Center of New Energy Materials and Technology, School of Materials Science and EngineeringSouthwest Petroleum UniversityChengduChina

Personalised recommendations