Journal of Porous Materials

, Volume 26, Issue 6, pp 1619–1629 | Cite as

Facile preparation of 3D graphene-based/polyvinylidene fluoride composite for organic solvents capture in spent fuel reprocessing

  • Yiyun Geng
  • Jihao Li
  • Zheng LiEmail author
  • Mumei Chen
  • Haogui Zhao
  • Lan ZhangEmail author


“Red oil” explosion is an important safety issue in spent fuel reprocessing and the most fundamental measure to prevent “red oil” explosion is the capture of organic solvents in water phase requiring further treatment. In this paper, superhydrophobic graphene/polyvinylidene fluoride composite aerogel (GA–PVDF) was synthesized by using HI as reductant under mild condition. The characterizations of SEM, FTIR, XRD, contact angle, mechanical property and oil/water absorption ability were performed to optimize the preparation conditions of GA–PVDF. It is found under optimal condition, the composite shows excellent water resistance, oil–water separation and mechanical properties. Furthermore, the recyclability and possible operation model of obtained GA–PVDF were also investigated. The result demonstrates that the composite material can be simply and efficiently used to capture the organic solvents without water uptake, which is attractive in the application of spent fuel reprocessing. Moreover, the recyclability of material also ensures the reduction of secondary waste. All of these indicate that GA–PVDF has great application potential for oil–water separation and “red oil” explosion prevention in spent fuel reprocessing.


Graphene/PVDF aerogels “Red oil” explosion Oil–water separation Recyclability 



This work was financially supported by National Natural Science Foundation of China (Nos. 11305244; 11505270) and “Strategic Priority Research Program” of the Chinese Academy of Sciences (Grant No. XDA02030000).

Compliance with ethical standards

Conflict of interest

There are no conflicts of interest to declare.

Supplementary material

10934_2019_760_MOESM1_ESM.mpg (11.3 mb)
Supplementary material 1 (MPG 11524 kb) Movie S1 Squeezing recovery process of GA-PVDF impregnated with 30% TBP-n-dodecane.
10934_2019_760_MOESM2_ESM.mpg (10.7 mb)
Supplementary material 2 (MPG 10924 kb) Movie S2 The static oil-water separation experiment for removing 30% TBP-n-dodecane from a system.
10934_2019_760_MOESM3_ESM.mpg (21.2 mb)
Supplementary material 3 (MPG 21744 kb) Movie S3 The continuous oil-water separation experiment for removing 30% TBP-n-dodecane from a system.
10934_2019_760_MOESM4_ESM.doc (1.1 mb)
Supplementary material 4 (DOC 1171 kb)


  1. 1.
    Y.A. El-Nadi, Solvent extraction and its applications on ore processing and recovery of metals: classical approach. Sep. Purif. Rev. 46(3), 195–215 (2016). CrossRefGoogle Scholar
  2. 2.
    K. Chandran, B. Sreenivasulu, N. Ramanathan, P.C. Clinsha, A. Suresh, N. Sivaraman, Thermal decomposition behaviour of irradiated tri n-butyl phosphate and mixture of di and mono n-butyl phosphate-nitric acid systems. Thermochim. Acta 657, 1–11 (2017). CrossRefGoogle Scholar
  3. 3.
    R. Li, C. Liu, H. Zhao, S. He, Z. Li, Q. Li, L. Zhang, Di-1-methyl heptyl methylphosphonate (DMHMP): a promising extractant in Th-based fuel reprocessing. Sep. Purif. Technol. 173, 105–112 (2017)CrossRefGoogle Scholar
  4. 4.
    T.G. Srinivasan, P.R. Vasudeva Rao, Red oil excursions: a review. Sep. Sci. Technol. 49(15), 2315–2329 (2014). CrossRefGoogle Scholar
  5. 5.
    S. Manohar, K. Narayan Kutty, B.V. Shah, P.K. Wattal, S.L. Bajoria, N.S. Kolhe, V.K. Rathod, Removal of dissolved Trin-butyl phosphate from aqueous streams of reprocessing origin: engineering scale studies. Desalin Water Treat 38(1–3), 146–150 (2012). CrossRefGoogle Scholar
  6. 6.
    V.G. Lade, P.C. Wankhede, V.K. Rathod, Removal of tributyl phosphate from aqueous stream in a pilot scale combined air-lift mixer-settler unit: process intensification studies. Chem. Eng. Process. 95, 72–79 (2015). CrossRefGoogle Scholar
  7. 7.
    R. Natarajan, Reprocessing of spent nuclear fuel in India: present challenges and future programme. Prog. Nucl. Energy 101, 118–132 (2017). CrossRefGoogle Scholar
  8. 8.
    T. Liu, G. Zhao, W. Zhang, H. Chi, C. Hou, Y. Sun, The preparation of superhydrophobic graphene/melamine composite sponge applied in treatment of oil pollution. J. Porous Mater. 22(6), 1573–1580 (2015). CrossRefGoogle Scholar
  9. 9.
    M.H. Sorour, H.A. Hani, G.A. Al-Bazedi, A.M. El-Rafei, Hydrophobic silica aerogels for oil spills clean-up, synthesis, characterization and preliminary performance evaluation. J. Porous Mater. 23(5), 1401–1409 (2016). CrossRefGoogle Scholar
  10. 10.
    B. Doshi, M. Sillanpaa, S. Kalliola, A review of bio-based materials for oil spill treatment. Water Res. 135, 262–277 (2018). CrossRefPubMedGoogle Scholar
  11. 11.
    X. Yue, J. Li, T. Zhang, F. Qiu, D. Yang, M. Xue, In situ one-step fabrication of durable superhydrophobic-superoleophilic cellulose/LDH membrane with hierarchical structure for efficiency oil/water separation. Chem. Eng. J. 328, 117–123 (2017). CrossRefGoogle Scholar
  12. 12.
    F. Guo, Q. Wen, Z. Guo, Low cost and non-fluoride flowerlike superhydrophobic particles fabricated for both emulsions separation and dyes adsorption. J. Colloid Interface Sci. 507, 421–428 (2017). CrossRefPubMedGoogle Scholar
  13. 13.
    N. Cao, Q. Lyu, J. Li, Y. Wang, B. Yang, S. Szunerits, R. Boukherroub, Facile synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide composite aerogel for efficient oil/water separation. Chem. Eng. J. 326, 17–28 (2017). CrossRefGoogle Scholar
  14. 14.
    P. Saha, L. Dashairya, Reduced graphene oxide modified melamine formaldehyde (rGO@MF) superhydrophobic sponge for efficient oil–water separation. J. Porous Mater. 25(5), 1475–1488 (2018). CrossRefGoogle Scholar
  15. 15.
    S. Song, H. Yang, C. Su, Z. Jiang, Z. Lu, Ultrasonic-microwave assisted synthesis of stable reduced graphene oxide modified melamine foam with superhydrophobicity and high oil adsorption capacities. Chem. Eng. J. 306, 504–511 (2016). CrossRefGoogle Scholar
  16. 16.
    S. Yang, L. Chen, C. Wang, M. Rana, P.C. Ma, Surface roughness induced superhydrophobicity of graphene foam for oil-water separation. J. Colloid Interface Sci. 508, 254–262 (2017). CrossRefPubMedGoogle Scholar
  17. 17.
    C. Li, D. Jiang, H. Liang, B. Huo, C. Liu, W. Yang, J. Liu, Superelastic and arbitrary-shaped graphene aerogels with sacrificial skeleton of melamine foam for varied applications. Adv. Funct. Mater. 28(8), 1704674 (2018). CrossRefGoogle Scholar
  18. 18.
    S. Moradi, P. Englezos, S.G. Hatzikiriakos, Contact angle hysteresis: surface morphology effects. Colloid Polym. Sci. 291(2), 317–328 (2012). CrossRefGoogle Scholar
  19. 19.
    M.A. Riaz, P. Hadi, I.H. Abidi, A. Tyagi, X. Ou, Z. Luo, Recyclable 3D graphene aerogel with bimodal pore structure for ultrafast and selective oil sorption from water. RSC Adv. 7(47), 29722–29731 (2017). CrossRefGoogle Scholar
  20. 20.
    J. Li, J. Li, H. Meng, S. Xie, B. Zhang, L. Li, H. Ma, J. Zhang, M. Yu, Ultra-light, compressible and fire-resistant graphene aerogel as a highly efficient and recyclable absorbent for organic liquids. J. Mater. Chem. A 2(9), 2934 (2014). CrossRefGoogle Scholar
  21. 21.
    Y. Lin, G.J. Ehlert, C. Bukowsky, H.A. Sodano, Superhydrophobic functionalized graphene aerogels. ACS Appl. Mater. Interfaces. 3(7), 2200–2203 (2011). CrossRefPubMedGoogle Scholar
  22. 22.
    H. Chang, J. Qin, P. Xiao, Y. Yang, T. Zhang, Y. Ma, Y. Huang, Y. Chen, Highly reversible and recyclable absorption under both hydrophobic and hydrophilic conditions using a reduced bulk graphene oxide material. Adv. Mater. 28(18), 3504–3509 (2016). CrossRefPubMedGoogle Scholar
  23. 23.
    S. Pei, J. Zhao, J. Du, W. Ren, H.-M. Cheng, Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids. Carbon 48(15), 4466–4474 (2010). CrossRefGoogle Scholar
  24. 24.
    W. Chen, L. Yan, In situ self-assembly of mild chemical reduction graphene for three-dimensional architectures. Nanoscale 3(8), 3132–3137 (2011). CrossRefPubMedGoogle Scholar
  25. 25.
    W. Li, A. Amirfazli, A thermodynamic approach for determining the contact angle hysteresis for superhydrophobic surfaces. J. Colloid Interface Sci. 292(1), 195–201 (2005). CrossRefPubMedGoogle Scholar
  26. 26.
    R. Rioboo, B. Delattre, D. Duvivier, A. Vaillant, J. De Coninck, Superhydrophobicity and liquid repellency of solutions on polypropylene. Adv. Colloid Interface Sci. 175, 1–10 (2012). CrossRefPubMedGoogle Scholar
  27. 27.
    A. Marmur, Solid-surface characterization by wetting. Annu. Rev. Mater. Res. 39(1), 473–489 (2009). CrossRefGoogle Scholar
  28. 28.
    L. Peng, W. Lei, P. Yu, Y. Luo, Polyvinylidene fluoride (PVDF)/hydrophobic nano-silica (H-SiO2) coated superhydrophobic porous materials for water/oil separation. RSC Adv. 6(13), 10365–10371 (2016). CrossRefGoogle Scholar
  29. 29.
    W. Wu, R. Huang, W. Qi, R. Su, Z. He, Bioinspired peptide-coated superhydrophilic poly(vinylidene fluoride) membrane for oil/water emulsion separation. Langmuir 34(22), 6621–6627 (2018). CrossRefPubMedGoogle Scholar
  30. 30.
    C. Wei, F. Dai, L. Lin, Z. An, Y. He, X. Chen, L. Chen, Y. Zhao, Simplified and robust adhesive-free superhydrophobic SiO2-decorated PVDF membranes for efficient oil/water separation. J. Membr. Sci. 555, 220–228 (2018). CrossRefGoogle Scholar
  31. 31.
    G.J. Ross, J.F. Watts, M.P. Hill, P. Morrissey, Surface modification of poly(vinylidene fluoride) by alkaline treatment 1. The degradation mechanism. Polymer 41(5), 1685–1696 (2000). CrossRefGoogle Scholar
  32. 32.
    B. Zhao, C. Zhao, C. Wang, C.B. Park, Poly(vinylidene fluoride) foams: a promising low-k dielectric and heat-insulating material. J. Mater. Chem. C 6(12), 3065–3073 (2018). CrossRefGoogle Scholar
  33. 33.
    A. Lund, C. Gustafsson, H. Bertilsson, R.W. Rychwalski, Enhancement of β phase crystals formation with the use of nanofillers in PVDF films and fibres. Compos. Sci. Technol. 71(2), 222–229 (2011). CrossRefGoogle Scholar
  34. 34.
    Z. Peng, C. Xiong, W. Wang, F. Tan, X. Wang, X. Qiao, P.K. Wong, Hydrophobic modification of nanoscale zero-valent iron with excellent stability and floatability for efficient removal of floating oil on water. Chemosphere 201, 110–118 (2018). CrossRefPubMedGoogle Scholar
  35. 35.
    H. Sun, Z. Xu, C. Gao, Multifunctional, ultra-flyweight, synergistically assembled carbon aerogels. Adv. Mater. 25(18), 2554–2560 (2013). CrossRefPubMedGoogle Scholar
  36. 36.
    Y. Wu, N. Yi, L. Huang, T. Zhang, S. Fang, H. Chang, N. Li, J. Oh, J.A. Lee, M. Kozlov, A.C. Chipara, H. Terrones, P. Xiao, G. Long, Y. Huang, F. Zhang, L. Zhang, X. Lepro, C. Haines, M.D. Lima, N.P. Lopez, L.P. Rajukumar, A.L. Elias, S. Feng, S.J. Kim, N.T. Narayanan, P.M. Ajayan, M. Terrones, A. Aliev, P. Chu, Z. Zhang, R.H. Baughman, Y. Chen, Three-dimensionally bonded spongy graphene material with super compressive elasticity and near-zero Poisson’s ratio. Nat. Commun. 6, 6141 (2015). CrossRefPubMedGoogle Scholar
  37. 37.
    A.B.D. Cassie, S. Baxter, Wettability of porous surfaces. Trans. Faraday Soc. 40(4), 546–551 (1944). CrossRefGoogle Scholar
  38. 38.
    M. Chen, Z. Li, Y. Geng, H. Zhao, S. He, A. Chen, Q. Li, L. Zhang, A modular process for the treatment of high level liquid waste (HLLW) using solvent-impregnated graphene aerogel. Hydrometallurgy 179, 167–174 (2018). CrossRefGoogle Scholar
  39. 39.
    W. Wan, Y. Lin, A. Prakash, Y. Zhou, Three-dimensional carbon-based architectures for oil remediation: from synthesis and modification to functionalization. J. Mater. Chem. A 4(48), 18687–18705 (2016). CrossRefGoogle Scholar
  40. 40.
    F. Chen, Y. Lu, X. Liu, J. Song, G. He, M.K. Tiwari, C.J. Carmalt, I.P. Parkin, Table salt as a template to prepare reusable porous PVDF-MWCNT foam for separation of immiscible oils/organic solvents and corrosive aqueous solutions. Adv. Funct. Mater. 27(41), 1702926 (2017). CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Shanghai Institute of Applied PhysicsChinese Academy of SciencesShanghaiChina
  2. 2.University of Chinese Academy of SciencesBeijingChina

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