Abstract
Graphene oxide (GO)-based membranes provide an encouraging opportunity for oil-in-water emulsion separation with high separation efficiency. In this work, novel hierarchically structured membrane consisting of GO and halloysite nanotubes (HNTs) was successfully fabricated by vacuum-assisted filtration method. XRD and TEM measurements showed the successful intercalation of HNTs into the interlayers of GO nanosheets. With the incorporation of the one-dimensional hollow tubular structure halloysite nanotubes, GO-HNTs(GOH) membrane possessed combined advantages of high oil rejection rate and excellent fouling resistance properties. The permeate fluxes increased from 286.6 L/(m2·h) for GO membrane to 716 L/(m2·h) for GOH membrane. The results indicate that the GOH membranes have great potential applications in water purification and wastewater treatment.
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Baker, R. W. (2012). Membrane technology and applications (Vol. 6, pp. 3771–3777). Hoboken: Wiley.
Chen, S., Zhu, J., Wu, X., Han, Q., & Wang, X. (2010). Graphene oxide--MnO2 nanocomposites for supercapacitors. ACS Nano, 4, 2822–2830.
Chen, X., Qiu, M., Ding, H., Fu, K., & Fan, Y. (2016). A reduced graphene oxide nanofiltration membrane intercalated by well-dispersed carbon nanotubes for drinking water purification. Nanoscale, 8, 5696–5705.
Darvishzadeh, T., Tarabara, V. V., & Priezjev, N. V. (2013). Oil droplet behavior at a pore entrance in the presence of crossflow: Implications for microfiltration of oil–water dispersions. Journal of Membrane Science, 447, 442–451.
Dikin, D. A., Stankovich, S., Zimney, E. J., Piner, R. D., Dommett, G. H., Evmenenko, G., Nguyen, S. T., & Ruoff, R. S. (2007). Preparation and characterization of graphene oxide paper. Nature, 448, 457–460.
Fan, J., Duan, J., Yu, Z., Wu, D., & Zhu, H. (2016). Oleophobicity of chitosan/Micron-alumina-coated stainless steel mesh for oil/water separation. Water, Air, & Soil Pollution, 227, 163.
Gao, P., Liu, Z., Sun, D. D., & Ng, W. J. (2014). The efficient separation of surfactant-stabilized oil–water emulsions with a flexible and superhydrophilic graphene–TiO2 composite membrane. Journal of Materials Chemistry A, 2, 14082–14088.
Geim, A. K., & Novoselov, K. S. (2007). The rise of graphene. Nature Materials, 6, 183–191.
Gopal, A. (2015). A simple approach to stepwise synthesis of graphene oxide nanomaterial. Journal of Nanomedicine & Nanotechnology, 6, 369–375.
Han, Y., Jiang, Y., & Gao, C. (2015). High-flux graphene oxide nanofiltration membrane intercalated by carbon nanotubes. ACS Applied Materials & Interfaces, 7, 8147–8155.
Hemmati, M., Rekabdar, F., Gheshlaghi, A., Salahi, A., & Mohammadi, T. (2012). Effects of air sparging, cross flow velocity and pressure on permeation flux enhancement in industrial oily wastewater treatment using microfiltration. Desalination & Water Treatment, 39, 33–40.
Hu, X., Yu, Y., Zhou, J., Wang, Y., Liang, J., Zhang, X., Chang, Q., & Song, L. (2015). The improved oil/water separation performance of graphene oxide modified Al2O3 microfiltration membrane. Journal of Membrane Science, 476, 200–204.
Huang, Y., Li, H., Wang, L., Qiao, Y., Tang, C., Jung, C., Yoon, Y., Li, S., & Yu, M. (2015). Ultrafiltration membranes with structure-optimized Graphene-oxide coatings for antifouling oil/water separation. Advanced Materials Interfaces, 2, 1400133.
Hummers, W. S., & Offeman, R. E. (1958). Preparation of graphitic oxide. Journal of the American Chemical Society, 80, 1339–1339.
Jin, J., Gao, J. S., Qin, H., & Liu, P. (2015). SWCNT-intercalated GO ultrathin films for ultrafast separation of molecules. Journal of Materials Chemistry A, 3, 6649–6654.
Ju, H., Mccloskey, B. D., Sagle, A. C., Wu, Y. H., Kusuma, V. A., & Freeman, B. D. (2008). Crosslinked poly(ethylene oxide) fouling resistant coating materials for oil/water separation. Journal of Membrane Science, 307, 260–267.
Kim, J., Cote, L. J., Kim, F., Yuan, W., Shull, K. R., & Huang, J. (2010). Graphene oxide sheets at interfaces. Journal of the American Chemical Society, 132, 8180–8186.
Krishnamoorthy, K., Veerapandian, M., Yun, K., & Kim, S. J. (2013). The chemical and structural analysis of graphene oxide with different degrees of oxidation. Carbon, 53, 38–49.
Lee, C., Wei, X., Kysar, J. W., & Hone, J. (2008). Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 321, 385–388.
Levis, S. R., & Deasy, P. B. (2002). Characterisation of halloysite for use as a microtubular drug delivery system. International Journal of Pharmaceutics, 243, 125–134.
Li, H., Song, Z., Zhang, X., Huang, Y., Li, S., Mao, Y., Ploehn, H. J., Bao, Y., & Yu, M. (2013). Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation. Science, 342, 95–98.
Li, G., Wang, X., Tao, L., Li, Y., Quan, K., Wei, Y., Chi, L., & Yuan, Q. (2015). Cross-linked graphene membrane for high-performance organics separation of emulsions. Journal of Membrane Science, 495, 439–444.
Li, F., Yu, Z., Shi, H., Yang, Q., Chen, Q., Pan, Y., Zeng, G., & Yan, L. (2017). A mussel-inspired method to fabricate reduced graphene oxide/g-C3N4 composites membranes for catalytic decomposition and oil-in-water emulsion separation. Chemical Engineering Journal, 322, 33–45.
Liu, R., Zhang, B., Mei, D., Zhang, H., & Liu, J. (2011). Adsorption of methyl violet from aqueous solution by halloysite nanotubes. Desalination, 268, 111–116.
Marcano, D. C., Kosynkin, D. V., Berlin, J. M., Sinitskii, A., Sun, Z., Slesarev, A., Alemany, L. B., Lu, W., & Tour, J. M. (2010). Improved synthesis of graphene oxide. ACS Nano, 4, 4806–4814.
Mi, B. (2014). Graphene oxide membranes for ionic and molecular sieving. Science, 343, 740–742.
Motta, A., Borges, C., Esquerre, K., & Kiperstok, A. (2014). Oil produced water treatment for oil removal by an integration of coalescer bed and microfiltration membrane processes. Journal of Membrane Science, 469, 371–378.
O'Hern, S. C., Boutilier, M. S., Idrobo, J. C., Song, Y., Kong, J., Laoui, T., Atieh, M., & Karnik, R. (2014). Selective ionic transport through tunable subnanometer pores in single-layer graphene membranes. Nano Letters, 14, 1234–1241.
Padaki, M., Murali, R. S., Abdullah, M. S., Misdan, N., Moslehyani, A., Kassim, M. A., Hilal, N., & Ismail, A. F. (2015). Membrane technology enhancement in oil–water separation. A review. Desalination, 357, 197–207.
Rein, D. M., Khalfin, R., & Cohen, Y. (2012). Cellulose as a novel amphiphilic coating for oil-in-water and water-in-oil dispersions. Journal of Colloid & Interface Science, 386, 456–463.
Safarpour, M., Khataee, A., & Vatanpour, V. (2015). Effect of reduced graphene oxide/TiO2 nanocomposite with different molar ratios on the performance of PVDF ultrafiltration membranes. Separation & Purification Technology, 140, 32–42.
Tummons, E. N., Tarabara, V. V., Chew, J. W., & Fane, A. G. (2016). Behavior of oil droplets at the membrane surface during crossflow microfiltration of oil–water emulsions. Journal of Membrane Science, 500, 211–224.
Wang, K., Lin, X., Jiang, G., Liu, J. Z., Jiang, L., Doherty, C. M., Hill, A. J., Xu, T., & Wang, H. (2014). Slow hydrophobic hydration induced polymer ultrafiltration membranes with high water flux. Journal of Membrane Science, 471, 27–34.
Yang, L., Wang, Z., Li, X., Yang, L., Lu, C., & Zhao, S. (2016). Hydrophobic modification of Platanus fruit fibers as natural hollow fibrous sorbents for oil spill cleanup. Water Air & Soil Pollution, 227, 346.
Yuan, P., Southon, P. D., Liu, Z., Green, M. E. R., Hook, J. M., Antill, S. J., & Kepert, C. J. (2008). Functionalization of Halloysite clay nanotubes by grafting with γ-Aminopropyltriethoxysilane. Journal of Physical Chemistry C, 112, 15742–15751.
Zhang, W., Shi, Z., Zhang, F., Liu, X., Jin, J., & Jiang, L. (2013). Superhydrophobic and superoleophilic PVDF membranes for effective separation of water-in-oil emulsions with high flux. Advanced Materials, 25, 2071–2076.
Zhang, W., Zhu, Y., Liu, X., Wang, D., Li, J., Jiang, L., & Jin, J. (2014). Salt-induced fabrication of Superhydrophilic and underwater Superoleophobic PAA-g-PVDF membranes for effective separation of oil-in-water emulsions. Angewandte Chemie, 53, 856–860.
Zhang, J., Xue, Q., Pan, X., Jin, Y., Lu, W., Ding, D., & Guo, Q. (2017). Graphene oxide/polyacrylonitrile fiber hierarchical-structured membrane for ultra-fast microfiltration of oil-water emulsion. Chemical Engineering Journal, 307, 643–649.
Zhao, X., Su, Y., Liu, Y., Li, Y., & Jiang, Z. (2016a). Free-standing Graphene oxide-Palygorskite Nanohybrid membrane for oil/water separation. ACS Applied Materials & Interfaces, 8, 8247–8256.
Zhao, Y., Li, C., Fan, X., Wang, J., Yuan, G., Song, X., Chen, J., & Li, Z. (2016b). Study on the separation performance of the multi-channel reduced graphene oxide membranes. Applied Surface Science, 384, 279–286.
Zhu, Z., Zhang, B., Chen, B., Cai, Q., & Lin, W. (2016). Biosurfactant production by marine-originated bacteria bacillus Subtilis and its application for crude oil removal. Water Air & Soil Pollution, 227, 328–328.
Acknowledgements
This work was financed by National Natural Science Foundation of China (Grant No. 5140003), Anhui Provincial Natural Science Foundation (1508085QE105), Scientific Research Fund of Anhui Provincial Education Department (KJ2016A791, KJ2017A030), Anhui Province Institute of High Performance Rubber Materials and Products, and The 211 Project of Anhui University.
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Zhu, Y., Chen, P., Nie, W. et al. Greatly Improved Oil-in-Water Emulsion Separation Properties of Graphene Oxide Membrane upon Compositing with Halloysite Nanotubes. Water Air Soil Pollut 229, 94 (2018). https://doi.org/10.1007/s11270-018-3757-6
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DOI: https://doi.org/10.1007/s11270-018-3757-6