Journal of Materials Science

, Volume 53, Issue 14, pp 10025–10038 | Cite as

Facile preparation of novel hydrophobic sponges coated by Cu2O with different crystal facet structure for selective oil absorption and oil/water separation

  • Jiali Li
  • Zheng-Qing Huang
  • Chao Xue
  • Yuxin Zhao
  • Wenbin Hao
  • Guidong Yang
Chemical routes to materials


In this work, a series of novel Cu2O@sponge composite materials including cubic Cu2O@sponges, octahedral Cu2O@sponges and cubo-octahedral Cu2O@sponges were prepared through a facile dip coating method to coat Cu2O particles on melamine sponge, all of which possess very highly hydrophobic and oleophilic properties. The crystal phase, microstructure and surface functional group of the as-prepared materials were characterized by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectra. The effect of different crystal facet of Cu2O on contact angle, wettability and oil absorption was systematically investigated. Meanwhile, the DFT calculation results show that the surface energy has significant influence on the hydrophobic property of Cu2O, and the calculated surface energies of Cu2O (111) and Cu2O (100) crystal surface are 0.73 and 1.29 J/m2, respectively. On basis of the DFT calculations and experimental results, the octahedral Cu2O with eight (111) crystal facet-coated sponges has the highest hydrophobic properties with the contact angle of 149°, which therefore shows very high separation efficiency in oil/water separation and quickly absorbs floating oils on the water surface. Additionally, all the Cu2O@sponges composite materials indicate excellent oil absorption performances and reusability in terms of hydrophobicity and oil absorbency, which would provide new materials for the potential application of oil/water separation.



This work was financially supported by the Natural Science Basic Research Plan in Shaanxi Province of China (Grant No. 2017JZ001), the National Natural Science Foundation of China (Grant No. 21303130) and the Fundamental Research Funds for the Central Universities (Grant No. cxtd2017004). Thanks for the technical support from International Center for Dielectric Research (ICDR), Xi’an Jiaotong University, Xi’an, China; the authors also appreciate Ms. Dai and Mr. Ma for their help in using SEM, EDX and TEM, respectively. We thank Professor Suitao Qi at Xi’an Jiaotong University for getting access to the software of Vienna Ab initio Simulation Package. The calculations were performed by using supercomputers at National Supercomputing Center in Shenzhen.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.


  1. 1.
    Zhang J, Ji K-J, Chen J, Ding Y-F, Dai Z-D (2015) A three-dimensional porous metal foam with selective-wettability for oil–water separation. J Mater Sci 50(16):5371–5377. CrossRefGoogle Scholar
  2. 2.
    Wang B, Liang W, Guo Z, Liu W (2015) Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: a new strategy beyond nature. Chem Soc Rev 44(1):336–361CrossRefGoogle Scholar
  3. 3.
    Ruan C, Ai K, Li X, Lu L (2014) A superhydrophobic sponge with excellent absorbency and flame retardancy. Angew Chem 53(22):5556–5560CrossRefGoogle Scholar
  4. 4.
    Cao Y, Liu N, Fu C, Li K, Tao L, Feng L, Wei Y (2014) Thermo and pH dual-responsive materials for controllable oil/water separation. ACS Appl Mater Interfaces 6(3):2026–2030CrossRefGoogle Scholar
  5. 5.
    Wang C-F, Lin S-J (2013) Robust superhydrophobic/superoleophilic sponge for effective continuous absorption and expulsion of oil pollutants from water. ACS Appl Mater Interfaces 5(18):8861–8864CrossRefGoogle Scholar
  6. 6.
    Liang H-W, Guan Q-F, Chen L-F, Zhu Z, Zhang W-J, Yu S-H (2012) Macroscopic-scale template synthesis of robust carbonaceous nanofiber hydrogels and aerogels and their applications. Angew Chem 124(21):5191–5195CrossRefGoogle Scholar
  7. 7.
    Lessard R-R, Demarco G (2000) The significance of oil spill dispersants. Spill Sci Technol Bull 6(1):59–68CrossRefGoogle Scholar
  8. 8.
    Broje V, Keller A-A (2006) Improved mechanical oil spill recovery using an optimized geometry for the skimmer surface. Environ Sci Technol 40(24):7914–7918CrossRefGoogle Scholar
  9. 9.
    Gui X, Zeng Z, Lin Z, Gan Q, Xiang R, Zhu Y, Cao A, Tang Z (2013) Magnetic and highly recyclable macroporous carbon nanotubes for spilled oil sorption and separation. ACS Appl Mater Interfaces 5(12):5845–5850CrossRefGoogle Scholar
  10. 10.
    Buist I, Potter S, Nedwed T, Mullin J (2011) Herding surfactants to contract and thicken oil spills in pack ice for in situ burning. Cold Reg Sci Technol 67(1):3–23CrossRefGoogle Scholar
  11. 11.
    Wang S, Li M, Lu Q (2010) Filter paper with selective absorption and separation of liquids that differ in surface tension. ACS Appl Mater Interfaces 2(3):677–683CrossRefGoogle Scholar
  12. 12.
    Arbatan T, Fang X, Wei S (2011) Superhydrophobic and oleophilic calcium carbonate powder as a selective oil sorbent with potential use in oil spill clean-ups. Chem Eng J 166(2):787–791CrossRefGoogle Scholar
  13. 13.
    Nguyen D-D, Tai N-H, Lee S-B, Kuo W-S (2012) Superhydrophobic and superoleophilic properties of graphene-based sponges fabricated using a facile dip coating method. Energy Environ Sci 5(7):7908–7912CrossRefGoogle Scholar
  14. 14.
    Adebajo M-O, Frost R-L, Kloprogge J-T, Carmody O (2003) Porous materials for oil spill cleanup: a review of synthesis and absorbing properties. J Porous Mater 10(3):159–170CrossRefGoogle Scholar
  15. 15.
    Bi H, Yin Z, Cao X, Xie X, Tan C, Huang X, Chen B, Chen F, Yang Q, Bu X, Lu X, Sun L, Zhang H (2013) Carbon fiber aerogel made from raw cotton: a novel, efficient and recyclable sorbent for oils and organic solvents. Adv Mater 25(41):5916–5921CrossRefGoogle Scholar
  16. 16.
    Choi H-M, Cloud R-M (1992) Natural sorbents in oil spill cleanup. Environ Sci Technol 26(4):772–776CrossRefGoogle Scholar
  17. 17.
    Zhang X, Li Z, Liu K, Jiang L (2013) Bioinspired multifunctional foam with self-cleaning and oil/water separation. Adv Funct Mater 23(22):2881–2886CrossRefGoogle Scholar
  18. 18.
    Zhu Q, Pan Q, Liu F (2011) Facile removal and collection of oils from water surfaces through superhydrophobic and superoleophilic sponges. J Phys Chem C 115(35):17464–17470CrossRefGoogle Scholar
  19. 19.
    Pham V-H, Dickerson J-H (2014) Superhydrophobic silanized melamine sponges as high efficiency oil absorbent materials. ACS Appl Mater Interfaces 6(16):14181–14188CrossRefGoogle Scholar
  20. 20.
    Ke Q, Jin Y, Jiang P, Yu J (2014) Oil/water separation performances of superhydrophobic and superoleophilic sponges. Langmuir 30(44):13137–13142CrossRefGoogle Scholar
  21. 21.
    Wu L, Li L, Li B, Zhang J, Wang A (2015) Magnetic, durable and superhydrophobic polyurethane@Fe3O4@SiO2 @fluoropolymer sponges for selective oil absorption and oil/water separation. ACS Appl Mater Interfaces 7(8):4936–4946CrossRefGoogle Scholar
  22. 22.
    Zhou X, Zhang Z, Xu X, Men X, Zhu X (2013) Facile fabrication of superhydrophobic sponge with selective absorption and collection of oil from water. Ind Eng Chem Res 52(27):9411–9416CrossRefGoogle Scholar
  23. 23.
    Shinde S-L, Nanda K-K (2012) Facile synthesis of large area porous Cu2O as super hydrophobic yellow-red phosphors. RSC Adv 2(9):3647–3650CrossRefGoogle Scholar
  24. 24.
    Wang F, Lei S, Xue M, Ou J, Li W (2014) In situ separation and collection of oil from water surface via a novel superoleophilic and superhydrophobic oil containment boom. Langmuir 30(5):1281–1289CrossRefGoogle Scholar
  25. 25.
    Kong L, Chen X, Yu L, Wu Z, Zhang P (2015) Superhydrophobic cuprous oxide nanostructures on phosphor-copper meshes and their oil-water separation and oil spill cleanup. ACS Appl Mater Interfaces 7(4):2616–2625CrossRefGoogle Scholar
  26. 26.
    Zheng Z, Huang B, Wang Z, Guo M, Qin X, Zhang X, Wang P, Dai Y (2009) Crystal faces of Cu2O and their stabilities in photocatalytic reactions. J Phys Chem C 113(32):14448–14453CrossRefGoogle Scholar
  27. 27.
    Duan B, Gao H, He M, Zhang L (2014) Hydrophobic modification on surface of chitin sponges for highly effective separation of oil. ACS Appl Mater Interfaces 6(22):19933–19942CrossRefGoogle Scholar
  28. 28.
    Lee S, Liang C-W, Martin L-W (2011) Synthesis, control, and characterization of surface properties of Cu2O nanostructures. ACS Nano 5(5):3736–3743CrossRefGoogle Scholar
  29. 29.
    Gao Y, Zhou Y-S, Xiong W, Wang M, Fan L, Rabiee-Golgir H, Jiang L, Hou W, Huang X, Jiang L, Silvain J, Lu Y-F (2014) Highly efficient and recyclable carbon soot sponge for oil cleanup. ACS Appl Mater Interfaces 6(8):5924–5929CrossRefGoogle Scholar
  30. 30.
    Kresse G, Furthmüller J (1996) Efficiency of ab initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6(1):15–50CrossRefGoogle Scholar
  31. 31.
    Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54(16):11169–11186CrossRefGoogle Scholar
  32. 32.
    Kresse G, Hafner J (1994) Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys Rev B 49(20):14251–14269CrossRefGoogle Scholar
  33. 33.
    Perdew J-P, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77(18):3865–3868CrossRefGoogle Scholar
  34. 34.
    Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59(3):1758–1775CrossRefGoogle Scholar
  35. 35.
    Monkhorst H-J, Pack J-D (1976) Special points for brillouin-zone integrations. Phys Rev B 16(4):5188–5192CrossRefGoogle Scholar
  36. 36.
    Werner A, Hochheimer H-D (1982) High-pressure X-ray study of Cu2O and Ag2O. Phys Rev B 25(9):5929–5934CrossRefGoogle Scholar
  37. 37.
    Soldemo M, Stenlid J-H, Besharat Z, Yazdi M-G, Önsten A, Leygraf C, Göthelid M, Brinck T, Weissenrieder J (2016) The surface structure of Cu2O(100). J Phys Chem C 120(8):4373–4381CrossRefGoogle Scholar
  38. 38.
    Islam M-M, Diawara B, Maurice V, Marcus P (2009) Bulk and surface properties of Cu2O: a first-principles investigation. J Mol Struct 903(1):41–48CrossRefGoogle Scholar
  39. 39.
    Islam M-M, Diawara B, Maurice V, Marcus P (2010) Surface reconstruction modes of Cu2O(001) surface: a first principles study. Surf Sci 604(17):1516–1523CrossRefGoogle Scholar
  40. 40.
    Bonn D, Eggers J, Indekeu J, Meunier J, Rolley E (2009) Wetting and spreading. Rev Mod Phys 81(2):739–805CrossRefGoogle Scholar
  41. 41.
    Stenlid J-H, Soldemo M, Johansson A-J, Leygraf C, Göthelid M, Weissenrieder J, Brinck T (2016) Reactivity at the Cu2O(100): Cu-H2O interface: a combined DFT and PES study. PCCP 18(44):30570–30584CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical Engineering, School of Chemical Engineering and TechnologyXi’an Jiaotong UniversityXi’anPeople’s Republic of China
  2. 2.State Key Laboratory of Safety and Control for ChemicalsSINOPEC Safety Engineering InstituteQingdaoPeople’s Republic of China

Personalised recommendations