A stable ZIF-8-coated mesh membrane with micro-/nano architectures produced by a facile fabrication method for high-efficiency oil-water separation

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  • ReceivedJun 27, 2018
  • AcceptedAug 27, 2018
  • PublishedSep 19, 2018


With the possibility of large-area processing, the ZIF-8-coated mesh membranes with rough micro-/nanostructures and underwater superoleophobic properties were successfully fabricated at ambient temperature and pressure. These membranes exhibited excellent separation efficiency over 99.99% for various oil-water mixtures with the residual oil content in the collected water less than 4 ppm, and high water flux of 10.2×104 L m−2 h−1. Furthermore, the ZIF-8-coated mesh membrane displayed outstanding stability towards high temperature and various organic solvents immersion. More importantly, based on its facile fabrication method, this kind of ZIF-8-coated mesh membrane can be easily enlarged, which is critical for the practical oil-water separation applications.

Funded by

the National Natural Science Foundation of China(21571076,21390394,21571079,61701543)

“111” project(B07016)

the Ministry of Science and Technology of SINOPEC(A381)

Open Projects of State Key Laboratory of Safety and Control for Chemicals(SKL-038)

Zhao Y

and Xue M are inventors on a Chinese patent(CN201810148543.6)


This work was financially supported by the National Natural Science Foundation of China (21571076, 21390394, 21571079 and 61701543), “111” project (B07016), the Ministry of Science and Technology of SINOPEC (A381) and Open Projects of State Key Laboratory of Safety and Control for Chemicals (SKL-038). Song M, Zhao Y, and Xue M are inventors of a Chinese patent (CN201810148543.6).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Xue M, Zhao Y, and Qiu S conceived and designed this work. Song M and Xue M conducted the synthesis and analyzed the data. Song M, Zhao Y, Mu S, Jiang C, Li Z, Yang P and Fang Q performed the characterization. Song M, Zhao Y, and Xue M wrote the paper. All authors contributed to the general discussion. Song M and Zhao Y contributed equally to this work.

Author information

Mingqiu Song is currently doing her research at the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, under the supervision of Prof. Shilun Qiu and Prof. Ming Xue. Her research interest mainly focuses on the synthesis and design of MOF membranes and their applications.

Yuxin Zhao obtained his BSc degree in chemistry of materials at China University of Petroleum (East) in 2009. He obtained his PhD degree in chemical engineering and technology at China University of Petroleum (East) (2009–2014) in Prof. Zifeng Yan’s group, with Best Undergraduate Thesis Award. In July 2015, Zhao joined SINOPEC Research Institute of Safety Engineering to start his independent academic career. His research interest is in the synthesis of new classes of materials and nanostructures, with an emphasis on their functionality.

Ming Xue received BSc (2003) and PhD (2008) degree from Jilin University (China) in Prof. Shilun Qiu’s group. He joined the University of Texas at San Antonio (USA) during 2007--2008 and 2014--2015 in Prof. Banglin Chen’s group. Currently, he works in the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University. His group focuses on the design and synthesis of multifunctional MOF materials and membranes for the applications in adsorption, separation and other advanced applications.


Supplementary information

Supplementary data are available in the online version of the paper.


[1] Schrope M. Oil spill: Deep wounds. Nature, 2011, 472: 152-154 CrossRef PubMed ADS Google Scholar

[2] Chan YJ, Chong MF, Law CL, et al. A review on anaerobic–aerobic treatment of industrial and municipal wastewater. Chem Eng J, 2009, 155: 1-18 CrossRef Google Scholar

[3] Ge J, Shi LA, Wang YC, et al. Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spill. Nat Nanotech, 2017, 12: 434-440 CrossRef PubMed ADS Google Scholar

[4] Ge J, Zhao HY, Zhu HW, et al. Advanced sorbents for oil-spill cleanup: recent advances and future perspectives. Adv Mater, 2016, 28: 10459-10490 CrossRef PubMed Google Scholar

[5] Gaaseidnes K, Turbeville J. Separation of oil and water in oil spill recovery operations. Pure Appl Chem, 1999, 71: 95-101 CrossRef Google Scholar

[6] Zhang Y, Wei S, Liu F, et al. Superhydrophobic nanoporous polymers as efficient adsorbents for organic compounds. Nano Today, 2009, 4: 135-142 CrossRef Google Scholar

[7] Cheryan M, Rajagopalan N. Membrane processing of oily streams. Wastewater treatment and waste reduction. J Membrane Sci, 1998, 151: 13-28 CrossRef Google Scholar

[8] Kintisch E. An audacious decision in crisis gets cautious praise. Science, 2010, 329: 735-736 CrossRef PubMed ADS Google Scholar

[9] Peng Y, Li Y, Ban Y, et al. Metal-organic framework nanosheets as building blocks for molecular sieving membranes. Science, 2014, 346: 1356-1359 CrossRef PubMed ADS Google Scholar

[10] Ge Q, Wang Z, Yan Y. High-performance zeolite NAA membranes on polymer−zeolite composite hollow fiber supports. J Am Chem Soc, 2009, 131: 17056-17057 CrossRef PubMed Google Scholar

[11] Chen L, Shi G, Shen J, et al. Ion sieving in graphene oxide membranes via cationic control of interlayer spacing. Nature, 2017, 550: 380-383 CrossRef PubMed ADS Google Scholar

[12] Yu Y, Chen H, Liu Y, et al. Selective separation of oil and water with mesh membranes by capillarity. Adv Colloid Interface Sci, 2016, 235: 46-55 CrossRef PubMed Google Scholar

[13] Yu Z, Yun FF, Gong Z, et al. A novel reusable superhydrophilic NiO/Ni mesh produced by a facile fabrication method for superior oil/water separation. J Mater Chem A, 2017, 5: 10821-10826 CrossRef Google Scholar

[14] Dong Y, Li J, Shi L, et al. Underwater superoleophobic graphene oxide coated meshes for the separation of oil and water. Chem Commun, 2014, 50: 5586-5589 CrossRef PubMed Google Scholar

[15] Wen Q, Di J, Jiang L, et al. Zeolite-coated mesh film for efficient oil–water separation. Chem Sci, 2013, 4: 591-595 CrossRef Google Scholar

[16] Zhang F, Zhang WB, Shi Z, et al. Nanowire-haired inorganic membranes with superhydrophilicity and underwater ultralow adhesive superoleophobicity for high-efficiency oil/water separation. Adv Mater, 2013, 25: 4192-4198 CrossRef PubMed Google Scholar

[17] Crick CR, Gibbins JA, Parkin IP. Superhydrophobic polymer-coated copper-mesh; membranes for highly efficient oil–water separation. J Mater Chem A, 2013, 1: 5943-5948 CrossRef Google Scholar

[18] Dunderdale GJ, Urata C, Sato T, et al. Continuous, high-speed, and efficient oil/water separation using meshes with antagonistic wetting properties. ACS Appl Mater Interfaces, 2015, 7: 18915-18919 CrossRef Google Scholar

[19] Chu Z, Feng Y, Seeger S. Oil/water separation with selective superantiwetting/superwetting surface materials. Angew Chem Int Ed, 2015, 54: 2328-2338 CrossRef PubMed Google Scholar

[20] Feng L, Li S, Li Y, et al. Super-hydrophobic surfaces: from natural to artificial. Adv Mater, 2002, 14: 1857-1860 CrossRef Google Scholar

[21] Lu Z, Li Y, Lei X, et al. Nanoarray based “superaerophobic” surfaces for gas evolution reaction electrodes. Mater Horiz, 2015, 2: 294-298 CrossRef Google Scholar

[22] Nakajima A, Hashimoto K, Watanabe T. Recent studies on super-hydrophobic films. Monatshefte für Chem, 2001, 132: 31-41 CrossRef Google Scholar

[23] Järn M, Granqvist B, Lindfors J, et al. A critical evaluation of the binary and ternary solid–oil–water and solid–water–oil interaction. Adv Colloid Interface Sci, 2006, 123-126: 137-149 CrossRef PubMed Google Scholar

[24] Cassie ABD, Baxter S. Wettability of porous surfaces. Trans Faraday Soc, 1944, 40: 546-551 CrossRef Google Scholar

[25] Yong J, Chen F, Yang Q, et al. Superoleophobic surfaces. Chem Soc Rev, 2017, 46: 4168-4217 CrossRef PubMed Google Scholar

[26] Liu M, Wang S, Wei Z, et al. Bioinspired design of a superoleophobic and low adhesive water/solid interface. Adv Mater, 2009, 21: 665-669 CrossRef Google Scholar

[27] Liu K, Yao X, Jiang L. Recent developments in bio-inspired special wettability. Chem Soc Rev, 2010, 39: 3240 CrossRef PubMed Google Scholar

[28] Darmanin T, Guittard F. Superhydrophobic and superoleophobic properties in nature. Mater Today, 2015, 18: 273-285 CrossRef Google Scholar

[29] Ma Q, Cheng H, Yu Y, et al. Preparation of superhydrophilic and underwater superoleophobic nanofiber-based meshes from waste glass for multifunctional oil/water separation. Small, 2017, 13: 1700391 CrossRef PubMed Google Scholar

[30] Gao X, Xu LP, Xue Z, et al. Dual-scaled porous nitrocellulose membranes with underwater superoleophobicity for highly efficient oil/water separation. Adv Mater, 2014, 26: 1771-1775 CrossRef PubMed Google Scholar

[31] Zhang JP, Chen XM. Exceptional framework flexibility and sorption behavior of a multifunctional porous cuprous triazolate framework. J Am Chem Soc, 2008, 130: 6010-6017 CrossRef PubMed Google Scholar

[32] Yuan D, Zhao D, Sun D, et al. An isoreticular series of metal-organic frameworks with dendritic hexacarboxylate ligands and exceptionally high gas-uptake capacity. Angew Chem Int Ed, 2010, 49: 5357-5361 CrossRef PubMed Google Scholar

[33] Li JR, Sculley J, Zhou HC. Metal–organic frameworks for separations. Chem Rev, 2012, 112: 869-932 CrossRef PubMed Google Scholar

[34] Shen K, Zhang L, Chen X, et al. Ordered macro-microporous metal-organic framework single crystals. Science, 2018, 359: 206-210 CrossRef PubMed ADS Google Scholar

[35] Ye Y, Zhang L, Peng Q, et al. High anhydrous proton conductivity of imidazole-loaded mesoporous polyimides over a wide range from subzero to moderate temperature. J Am Chem Soc, 2015, 137: 913-918 CrossRef PubMed Google Scholar

[36] Sun Q, He H, Gao WY, et al. Imparting amphiphobicity on single-crystalline porous materials. Nat Commun, 2016, 7: 13300 CrossRef PubMed ADS Google Scholar

[37] Huang G, Yang Q, Xu Q, et al. Polydimethylsiloxane coating for a palladium/MOF composite: highly improved catalytic performance by surface hydrophobization. Angew Chem Int Ed, 2016, 55: 7379-7383 CrossRef PubMed Google Scholar

[38] Kim H, Yang S, Rao SR, et al. Water harvesting from air with metal-organic frameworks powered by natural sunlight. Science, 2017, 356: 430-434 CrossRef PubMed ADS Google Scholar

[39] Zhao C, Dai X, Yao T, et al. Ionic exchange of metal–organic frameworks to access single nickel sites for efficient electroreduction of CO2. J Am Chem Soc, 2017, 139: 8078-8081 CrossRef PubMed Google Scholar

[40] Huang XC, Lin YY, Zhang JP, et al. Ligand-directed strategy for zeolite-type metal–organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. Angew Chem Int Ed, 2006, 45: 1557-1559 CrossRef PubMed Google Scholar

[41] Park KS, Ni Z, Côté AP, et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc Natl Acad Sci USA, 2006, 103: 10186-10191 CrossRef PubMed ADS Google Scholar

[42] Qiu S, Xue M, Zhu G. Metal–organic framework membranes: from synthesis to separation application. Chem Soc Rev, 2014, 43: 6116-6140 CrossRef PubMed Google Scholar

[43] Yao J, Wang H. Zeolitic imidazolate framework composite membranes and thin films: synthesis and applications. Chem Soc Rev, 2014, 43: 4470-4493 CrossRef PubMed Google Scholar

[44] Kang Z, Xue M, Fan L, et al. “Single nickel source” in situ fabrication of a stable homochiral MOF membrane with chiral resolution properties. Chem Commun, 2013, 49: 10569-10571 CrossRef PubMed Google Scholar

[45] Liu X, Demir NK, Wu Z, et al. Highly water-stable zirconium metal–organic framework UiO-66 membranes supported on alumina hollow fibers for desalination. J Am Chem Soc, 2015, 137: 6999-7002 CrossRef PubMed Google Scholar

[46] Chen Y, Zhang S, Cao S, et al. Roll-to-roll production of metal-organic framework coatings for particulate matter removal. Adv Mater, 2017, 29: 1606221 CrossRef PubMed Google Scholar

[47] Zhang G, Zhang J, Su P, et al. Non-activation MOF arrays as a coating layer to fabricate a stable superhydrophobic micro/nano flower-like architecture. Chem Commun, 2017, 53: 8340-8343 CrossRef PubMed Google Scholar

[48] Jayaramulu K, Datta KKR, Rösler C, et al. Biomimetic superhydrophobic/superoleophilic highly fluorinated graphene oxide and ZIF-8 composites for oil-water separation. Angew Chem Int Ed, 2016, 55: 1178-1182 CrossRef PubMed Google Scholar

[49] Kang Z, Wang S, Fan L, et al. Surface wettability switching of metal-organic framework mesh for oil-water separation. Mater Lett, 2017, 189: 82-85 CrossRef Google Scholar

[50] Ma Q, Li G, Liu X, et al. Zeolitic imidazolate framework-8 film coated stainless steel meshes for highly efficient oil/water separation. Chem Commun, 2018, 54: 5530-5533 CrossRef PubMed Google Scholar

[51] Zhang X, Zhao Y, Mu S, et al. UiO-66-coated mesh membrane with underwater superoleophobicity for high-efficiency oil–water separation. ACS Appl Mater Interfaces, 2018, 10: 17301-17308 CrossRef Google Scholar

[52] Cai Y, Chen D, Li N, et al. Nanofibrous metal–organic framework composite membrane for selective efficient oil/water emulsion separation. J Membrane Sci, 2017, 543: 10-17 CrossRef Google Scholar

[53] Guo H, Zhu G, Hewitt IJ, et al. “Twin copper source” growth of metal−organic framework membrane: Cu3(BTC)2 with high permeability and selectivity for recycling H2. J Am Chem Soc, 2009, 131: 1646-1647 CrossRef PubMed Google Scholar

[54] Kang Z, Xue M, Fan L, et al. Highly selective sieving of small gas molecules by using an ultra-microporous metal–organic framework membrane. Energy Environ Sci, 2014, 7: 4053-4060 CrossRef Google Scholar

  • Scheme 1

    Schematic diagram of the preparation route of ZIF-8-coated mesh membrane with underwater superoleophobicity.

  • Figure 1

    SEM images of ZIF-8-coated mesh membrane prepared on stainless steel mesh (500 mesh) by seeding and secondary growth process. (a) The bare stainless steel mesh and (b) the seeded stainless steel mesh with uniform ZIF-8 seeds. (c) The ZIF-8-coated mesh membrane and (d) a single ZIF-8-coated wire after secondary growth. (e) The magnified image of ZIF-8-coated membrane surface, in which the homogeneous intergrown polyhedral nanocrystals can be clearly observed. (f) The cross-sectional view of ZIF-8-coated mesh membrane.

  • Figure 2

    3D and 2D AFM images of the bare thread of stainless steel mesh (a1, a2) and after coated with ZIF-8 (b1, b2).

  • Figure 3

    Special wettability of ZIF-8-coated mesh membrane underwater. (a) The photograph of several oil droplets on the ZIF-8-coated mesh membrane; (b) a contact angle image of an oil droplet on the ZIF-8-coated mesh membrane underwater; (c, d) schematic illustrations of an oil droplet on a rough micro and nano architecture surface of ZIF-8-coated mesh membrane (dichloroethane dyed with Sudan III).

  • Figure 4

    Photographs of the oil-water separation process using (a, b) the ZIF-8-coated mesh membrane, (c, d) the large-area ZIF-8-coated mesh membrane and (e, f) the ZIF-8-coated “boat” (cyclohexane was dyed with Sudan III).

  • Figure 5

    Oil-water separation performances of the ZIF-8-coated mesh membrane. (a) The separation efficiency and residual oil contents in the collected water for various oils. (b) The influence of different mesh number on water flux and intrusion pressure of oil (calculated by cyclohexane).

  • Figure 6

    Stability and recyclability of ZIF-8-coated mesh membrane (500 mesh). (a, b) Underwater oil contact angles (UWOCAs) of the ZIF-8-coated mesh membrane after heating treatment under different temperatures and immersing in various organic solvents for 20 h. The inset: photos of underwater oil droplets (dichloroethane) standing on ZIF-8-coated mesh membranes after heating and immersing treatment. (c, d) Water flux and separation efficiency for oil-water mixtures of ZIF-8-coated mesh membrane during the 10 cycles.

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