UiO-66 coated mesh membrane with underwater ... - ACS Publications

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Functional Inorganic Materials and Devices

UiO-66 coated mesh membrane with underwater superoleophobicity for high-efficiency oil-water separation Xiaojing Zhang, Yuxin Zhao, Shanjun Mu, Chunming Jiang, Mingqiu Song, Qianrong Fang, Ming Xue, Shilun Qiu, and Banglin Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05137 • Publication Date (Web): 07 May 2018 Downloaded from http://pubs.acs.org on May 7, 2018

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ACS Applied Materials & Interfaces

UiO-66 coated mesh membrane with underwater superoleophobicity for high-efficiency oil-water separation Xiaojing Zhang,a† Yuxin Zhao,c† Shanjun Mu,c Chunming Jiang,cMingqiu Song,a Qianrong Fang,a Ming Xue,*aShilun Qiua and Banglin Chen*b Dr. X. Zhang, Dr. M. Song, Prof. Q. Fang, Prof. S. Qiu, Prof. M. Xue State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, China. E-mail: [email protected] Prof. B. Chen Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA. E-mail: [email protected] Dr. Y. Zhao, Prof. S. Mu, Prof. C. Jiang State Key Laboratory of Safety and Control for Chemicals, SINOPEC Research Institute of Safety Engineering, Shandong Qingdao, 266101, P. R. China †X. Zhang and Y. Zhao contributed equally to this work.

KEYWORDS: metal-organic frameworks, membrane, wettability, superoleophobicity, oil-water separation

ABSTRACT: A UiO-66 coated mesh membrane with micro-and nanostructures was designed and successfully fabricated on steel mesh through a simple solution immersion process, exhibiting hydrophilic and underwater superoleophobic properties. It displays an outstanding oilwater separation efficiency over 99.99% with a high water permeation flux of 12.7 ×104 L m-2 h-1, so high purity water (with the residual oil content less than 4 ppm) can be readily obtained from such a simple mesh membrane from various oil-water mixtures. Its large-scale membrane

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production will facilitate its practical usage for the industrial and environmental water purification. INTRODUCTION Oil-water separation is a very significant research topic for the basic scientific research as well as for addressing global environmental and economic challenges. Oil pollutions have been generated by the petroleum, steel and textile industries, and the frequent oil spills during oil transportation, and have been becoming critical environmental issues.1-3 Over the past two decades, there has been extensive research endeavours to pursue novel materials to address these environmental and economic challenges.4,5 Conventional techniques such as settling tanks, centrifugation, skimmers, air flotation and biological treatment for the oil-water separations with the drawbacks of high operation cost and low separation efficiency.6,7 Many adsorbent materials such as activated carbon, hydrophobic aerogels, crosslinked polymers have been implemented in practical applications;8-10 however, they also display poor separation efficiency because they typically absorb both oil and water simultaneously. Membrane separation is a very promising and economical approach to tackle energy and environmental challenges, and has rapidly developed in the past decades.11-16 Based on the capillarity for the oil-water separation, mesh membranes have been considered as an effective approach with high separation efficiency and flux, and low energy consumption.17-22 In this separation process, it is critical to maintain one phase on the surface preferentially, so it is important to develop the coated materials with extreme surface wettability.23 Until now, two kinds of surface materials have been applied in the oil-water membrane separation. One is the “oil-removing” material with both superhydrophobic and superoleophilic surface wettability,


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another one is the “water-removing” material with superoleophobic surfaces.24 Several polymer based membranes with superhydrophobic and superoleophilic properties had been successfully fabricated by polytetrafluoroethylene (PTFE), polydimethylsiloxane (PDMS) and poly(stearyl methacrylate) (PStMA) etc.25-27 These “oil-removing” mesh membranes usually encounter two main disadvantages: Firstly, the membrane surface is easily fouled by the oils because of the intrinsic oleophilicity, which has a serious effect on the separation efficiency after a limited number of using times; Secondly, the separation process is rather complex, because water phase with higher density tends to generate a barrier layer between the membrane surface and the oil phase, thus preventing the permeation of oil. In general, the “oil-removing” mesh membranes are not applicable to separate the water-rich oil-water mixture.24 Enlightened by the antiwetting behaviour of the oil droplet on the lower side of lotus leaves or the fish scale in water, underwater superoleophobic materials have been rapidly developed in recent years.28-30 As we known, the contact angle based on Young’s equation is generally applied to evaluate the wettability of the solid surface.31 Young’s equation is suitable for a liquid droplet on the solid surface not only in air, but also under the second liquid.32 Through theoretical calculations and experimental results, it has been demonstrated the hydrophilic surfaces in air exhibit the oleophobic phenomenon underwater.33 Furthermore, it is well known that after the introduction of the rough structure on the solid surface, the Cassie state is achieved in the threephase system of oil/water/solid.34 Hydrophilic surface membranes with micro/nanohierarchical structures, prefer to attract the water phase, reducing the overall interfacial energy. Water molecules are tightly trapped in the rough solid surface, resulting in the composite water-solid interface, thus exhibiting the underwater superoleophobic performance.35


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The advancement in underwater superoleophobic materials presents a new promise and opportunity to address the efficient oil-water separation through the “water-removing” membranes. Although some hydrophilic polymer and all-inorganic materials have been fabricated onto mesh membranes, the “water-removing” membranes with high separation efficiency, large separation capacity, long-term durability and the scalability of the preparation process have still not realized.24 As novel multifunctional crystalline materials,36-41 metal-organic frameworks (MOFs)

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have recently attracted immense attentions for their surface wettability

as well.46-51 In fact, ZIF-8 (zeolite imidazole framework) nanoparticales have succesfully been incorporated into polymer coated “water-removing” membranes to improve the oil-water separation performance.52,53 To make use of the intrinsically hydrophilic carboxyl and hydroxyl functional groups, some MOFs materials have been recently developed for the water harvesting.54 In particular, the neutron powder diffraction study indicated that water molecules preferred to form hydrogen bonds with the hydroxyl groups of the Zr6(O)4(OH)4(-CO2)12 within the Zr-based MOFs.55,56 As well established, the Zr-based MOF UiO-66 has high mechanical, thermal and chemical stabilities due to its exceptional metal-ligand bond strength.57-59 Given the fact that MOF materials can be readily fabricated onto mesh membranes without any modifications, 60,61 as shown in our HKUST-1 coated mesh membrane,62 we are now developing the UiO-66 coated mesh membrane for the oil-water separation application. In this work, a facile strategy was successfully demonstrated to grow UiO-66 nanocrystals on stainless steel mesh at ambient room temperature and pressure. The UiO-66 coated mesh membrane combined a hydrophilic chemical composition with a micro/nanohierarchical rough structure to realise oil and water separation. The UiO-66 coated mesh membrane displayed hydrophilic and underwater superoleophobic properties. An outstanding separation efficiency


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over 99.99% was obtained, with the water permeation flux of 12.7 ×104 L m-2 h-1, and the residual oil content of less than 4 ppm for diverse oil-water mixtures, which are among the best values reported. More importantly, the UiO-66 coated mesh membrane can be readily scaled up for the practical applications. EXPERIMENTAL SECTION Materials. ZrCl4 (>99.5%), Zirconium(IV) propoxide solution (70 wt% in 1-propanol, Sigma Aldrich), 1,4-benzenedicarboxylic acid (H2BDC, Sigma Aldrich), benzoicacid (99.0%, TCI Chemical Industry Co., Ltd.), N, N’-dimethylformamide (DMF, West Long Chemical Co., Ltd), ethanol (99.85%, West Long Chemical Co., Ltd), stainless mesh (400 mesh/38µm, 500 mesh/28µm, 800 mesh/10µm, Local supermarkets, China) were used as supports. Synthesis of UiO-66 seeds. ZrCl4 (0.343 mmol, 0.080 g) were dissolved in 20 mL DMF using ultrasound about 1 min, then 1,4-benzenedicarboxylic acid (H2BDC) (0.343 mmol, 0.057 g) and benzoicacid (0.343 mmol, 0.048 g) were added to the solution. The mixture was sealed in a Teflon lined autoclave and placed in 120 oC oven for 24 hours. The precipitate with around 50 nm was isolated by the centrifugation and washed with DMF, ethanol repeatedly. Synthesis of UiO-66 coated mesh membrane. Firstly, the cleaned stainless steel mesh was previously modified by seeding with UiO-66 seed nanolcrystals (10 wt%) in deionized water suspension under ultrasonic. 142 µL zirconium propoxide solution (0.316 mmol, 0.1038 g) was add to 14 mL DMF under ultrasonic 10 min. Then the linker H2BDC was add and stirred 30 min. The seeded stainless steel mesh was placed in the solution for 12 h at room temperature. Then the UiO-66 coated mesh membrane was obtained.


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Synthesis of Large UiO-66 Coated Mesh Membrane. The cleaned 10 x 10 cm2 stainless steel mesh sheet previously was modified by seeding with UiO-66 seed nanolcrystals (10 wt%) in deionized water suspension under ultrasonic. A seed layer was formed on the surface of the stainless mesh sheet. 568 µL zirconium propoxide solution (1.264 mmol, 0.4152 g) was add to 64 mL DMF under ultrasonic 10 min. Then the linker H2BDC was add and stirred 30 min. The seeded stainless mesh was placed in the solution for 12 h at room temperature. Then the large UiO-66 coated mesh membrane was obtained. Preparation of The Mixture of Oil and Water. The water and oil (e.g. pump oil, diesel, cyclohexane and soybean oil, respectively) were mixed in a ratio of 50%, and oils were dyed with Sudan III for clear observation. Oil-water separation Experiment. The UiO-66 coated mesh membranes were used to separate the oil-water mixture in a homemade set-up. One piece of the prewetted UiO-66 coated membrane was horizontally placed between the ends of two identical glass tubes, which were then fixed by the rubber gasket and clamp. The mixture of oil (diesel, vegetable oil, pump oil, cyclohexane, respectively) and water was pured onto the membrane through the glass tube, and the filtrate was collected in the jar. In this separation process, the driving force is its own gravity. The oil content in the filtrate was characterized by the infrared spectrometer (IR) oil content instrument. Characterization: The crystalline structures of the UiO-66 seed and membranes were analysised by PXRD data collected on a PANalytical B.V. Empyrean using a Cu Kα source (λ = 1.5418 Å) in the range of 2θ = 4.0-40.0. The scanning electron microscopy (SEM, EDXS) studies of these UiO-66 seed and UiO-66 coated mesh membranes were performed on a JEOS


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JSM-6510. Contact angles were analysised on the OCA20 instrument (DataPhysics, Germany). The oil concentration of the filtrate was characterized by the infrared spectrometer (IR) oil content instrument (OIL-460, China). RESULTS AND DISCUSION These UiO-66 coated mesh membranes were fabricated by a simple solution immersion process on the stainless steel mesh substrate at ambient temperature and pressure. After the seeding process, the layer of seed crystals was formed on the mesh. TEM and SEM images indicated UiO-66 seeds were uniform with around 50 nm in size (Figure S1). And the inset in Figure 1a showed UiO-66 seeds dispersed on the stainless steel mesh uniformly. SEM images of the UiO66 coated mesh membrane (500 mesh/28 µm) demonstrated the rough UiO-66 coatings covered the mesh surface completely after the secondary growth (Figures 1b and c), which was different from the smooth bare stainless steel mesh obviously (Figure S2). An SEM image at higher magnification showed that the UiO-66 coated mesh membrane comprised continuous intergrown octahedral nanocrystals that were homogeneous and dense in size, around 200 nm, with a corrugated geometrical structure (Figure 1d). Viewed from the cross section, it was obvious that the UiO-66 nanocrystals compactly connected with the threads of stainless steel mesh (Figure S3). The growth of nanostructured UiO-66 crystals resulted in the preparation of a rich micro/nano hierarchical surface, greatly promoting the formation of surface roughness. Similarly, SEM images of hierarchical UiO-66 coatings on with 400 mesh/38 µm and 800 mesh/10 µm showed that a rough surface texture was constructed (Figure S4). PXRD pattern of the UiO-66 seeds matched very well with the simulated pattern. The major crystallographic planes of the UiO-66 coated mesh membrane were in accordance with the simulation because of the relatively thin crystal layer (Figure S5). In addition, the hydrothermal stability was analysed by suspending


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the UiO-66 sample in water at 100 °C for 7 days. After such extensive treatment, the UiO-66 keeped the fully crystalline integrity, which was confirmed by the unshifted and sharp diffraction lines in the PXRD pattern, exhibiting the exceptional stability. Furthermore, the elemental mapping analysis indicated the Zr and O elements were distributed on the UiO-66 coated mesh membrane uniformly (Figure S6), showing the formation of a rough micro- and nanostructure, and carboxylate oxygens and hydroxyl groups of UiO-66 were introduced on the stainless steel mesh.

Figure 1. SEM images of the UiO-66 coated mesh membrane fabricated by seeding and secondary growth process on stainless steel mesh (500 mesh/28 µm). (a) The mesh surface after the seeding process; and a enlarged view of the UiO-66 nanocrystal uniformly distributed on the mesh in the inset. (b) The UiO-66 coated mesh membrane and (c) a single UiO-66 coated wire after secondary growth. (d) The higher magnification image of UiO-66 coated membrane surface, in which the homogeneous intergrown octahedral nanocrystals can be clearly observed.


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In general, the hydrophilic surface has a water contact angle (CA) of < 90°; on the contrary, the hydrophobic surface has a water CA of > 90°. And the surface with a water or oil CA of > 150° is usually considered superhydrophobic or superoleophobic, respectively. The wettability and properties of the pristine stainless steel mesh and UiO-66 coated mesh membrane (500 mesh/28 µm) as representative were analyzed by the CA measurements. The water CA of the bare stainless steel mesh was around 120° in air (Figure 2a), but the UiO-66 coated mesh membrane exhibited an excellent hydrophilic properties with the water CA of 25° (Figure 2c), which indicated that the water wetting behaviour was greatly enhanced, because the hydrophilic carboxylate and hydroxyl groups, and rough micro- and nanostructure of UiO-66 were introduced on the mesh. In addition, the hydrophilicity of UiO-66 nanocrystals coated mesh was better than the bulk UiO-66 powder sample with a water CA of 37°, which revealed that the hierarchically rough structures on the membrane surface raised the hydrophilicity (Figure S7). When the bare mesh was immersed in water, because of the inherent hydrophobicity, the oil contact angle (OCA) was about 80° (Figure 2b). Remarkably, the UiO-66 coated mesh membranes showed outstanding superoleophobic behaviours underwater, with a high OCA of 150° (Figure 2d). And as shown in Figure 3a, a UiO-66 coated mesh membrane was soaked into the water, exhibiting obviously underwater superolephobic properties. As we known, the Cassie model has been applied in the oil/water/solid three phase system with the rough surface, which is shown in Equation:24,35

(1)


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where θ and θ′ is the OCA on the smooth or rough surface underwater, respectively, and f refers to the area fraction of the solid. The smaller f results in the lower probability of the oil droplets touching the solid surface, and the larger OCA θ′ underwater. Our UiO-66 coated membranes have the highly rough surface due to the sharp polyhedral nanocrystals, so the quite small area fraction of the solid leads to the large OCA underwater, which was schematically illustrated in Figure 2e.

Figure 2. Special wettability behaviours. Photographs of (a) a water droplet and (b) an underwater oil droplet (dichloroethane) on a pristine stainless steel mesh; (c) a water droplet and (d) an underwater oil droplet (dichloroethane) on the UiO-66 mesh membrane; e) a schematic illustration of a oil droplet on the UiO-66 coated membrane with a rather rough micro/nanostructure underwater.


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Encouraged by excellent hydrophilic and underwater superoleophobic properties of the UiO-66 coated membranes, a series of oil-water separation experiments were performed by using the setup as shown in Figures 3b-c. A oil-water mixture was poured onto the pre-wetted stainless steel membranes, which had been fixed between two glass tubes. The bare mesh exhibited both oil and water permeating through the mesh completely in the oil-water separation process (Figure 3b), which indicated that the bare mesh was unable to separate the oil and water (Video S1). However, compared to the bare mesh, only water could permeate through the UiO-66 coated membrane with high flux, and no obvious oil remained in the collected water (Figure 3c). Oil was maintained above the UiO-66 coated membrane due to the superoleophobic properties (Video S2). Similarly, the separation process using 400 mesh and 800 mesh as the supports of the UiO-66 coated mesh membranes are shown in Videos S3 and S4, respectively. Water passed through quickly and the oil was left above the UiO-66 membrane. The separation mechanism is the hydrophilic surface of UiO-66 coated mesh membrane preferentially attracts water phase in the three-phase system of oil/water/solid, and the highly rough surface results in a quite small area fraction of the solid. Water molecules are tightly trapped in the rough UiO-66 micro/nanostructures, forming a barrier layer, which allows the water phase to pass through the membrane by its gravity quickly, and rejects the oil phase.


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Figure 3. Photographs of (a) oil droplets (dichloromethane) on the UiO-66 caoted membrane in water, the oil-water separation process using (b) a bare stainless steel mesh and (c) a UiO-66 coated mesh membrane, (d) oil column (cyclohexane) above a UiO-66 coated mesh membrane after stirring in water for 10 days, (e, f) the oil-water separation process using a large-area UiO66 coated “boat”. (oils dyed with Sudan III). The UiO-66 coated mesh membranes exhibited superior oil-water separation performance for various oils, such as cyclohexane, vegetable oil, pump oil and diesel. To test the separation properties of these meshes, the residual oil content in the filtrate was characterized by the infrared spectrometer oil content analyser. There was only a very small amount of oil in the collected water (< 4 ppm) after the separation, which revealed that the different immiscible oil-


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water mixtures can be separated by the UiO-66 coated mesh membrane effectively (Figure 4a). Furthermore, to evaluate the separation efficiency of various oil-water mixtures, the separation efficiency is calculated by the equation: （2）

where R (%) is the oil rejection coefficient, Co is the oil concentration of the oil-water mixture and Cp is the oil concentration of the filtrate after separation. For the UiO-66 coated mesh membrane, the separation efficiency is over 99.99%. To further study the separation performance of these UiO-66 coated mesh membranes with different mesh numbers (400 mesh/38 µm, 500 mesh/28 µm, 800 mesh/10 µm), the water permeation flux and intrusion pressures were measured. The permeate Flux (F) is calculated by this equation: (3) where V is the volume of water which permeates through the membrane, S is the area of the membrane, and t is the permeation time. The intrusion pressure (P) value is calculated by: (4) where P is the pressure, ρ is the density of oil, g is the gravitational acceleration and hmax is the maximum height of oil, which was held by the UiO-66 coated membrane. It was obvious the flux increased with decreasing mesh number because of an increase of the pore size, but the opposite trend was seen with the intrusion pressure of oil (Figure 4b). These results revealed that the larger effective pore size of the UiO-66 coated mesh membrane was


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more beneficial to the permeation of water, whereas the smaller pore size increased the thickness of the trapped water layer, and thus the membrane had sufficient surface tension to hold on more oil. The water permeation flux was as high as 12.7×104 L m-2 h-1, and a high intrusion pressure of 6600 Pa was achieved. To compare with others reported literatures, the performance of the UiO66 membrane were among the best values reported (Table S1). Because of the excellent separation properties, the UiO-66 coated mesh membrane was able to separate different oil-water mixtures and thus has potential industrial application. The stability and cycling tests of the UiO-66 coated mesh membrane were evaluated by characteriszing its intrusion pressures and water permeation flux during 10 days of stirring at 400 rpm in water. Here, the stainless steel mesh with 500 mesh/28 µm was taken as an example and discussed in detail. As shown in Figures 4c-d, the permeation flux of the UiO-66 coated mesh membrane remained 10.7×104 L m-2 h-1 after 10 days (Figure 4c). Most notably, the intrusion pressures retained a high value compared with the new mesh (0 day). The maximum height of cyclohexane was over 40 cm after stirring in water for 10 days (Figure 3d). These intrusion pressures and permeation flux results indicated that the UiO-66 coated mesh membrane displayed excellent recycled and stable properties. In addition, the morphology of the used UiO66 coated membrane had been characterized in detail by SEM, which revealed that UiO-66 nanocrystals still coated the mesh compactly and there were no obvious cracks on the surface (Figure S8).


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Figure 4. Oil-water separation results of these UiO-66 coated membranes. (a) Residual oil content in the collected water and separation efficiency for a series of oil-water mixtures. (b) The effect of different UiO-66 coated mesh membranes on intrusion pressure and water flux of oil (cyclohexane). (c, d) The flux and Intrusion pressures of UiO-66 coated mesh membrane during 10 days of agitation in water. Compared with most of inorganic coated membranes, which usually have been fabricated by the annealing method, chemical vapor deposition or hydrothermal synthesis,17 the UiO-66 coated mesh membrane could be easily scaled up through the simple solution immersion fabrication process at room temperature. A 10 x 10 cm2 stainless steel mesh sheet was used to prepare the UiO-66 coated mesh membrane. As shown in Figure 3e, a boat-like UiO-66 coated mesh membrane was put on the beaker to evaluate the separation property. The oil-water mixture was then dumped onto the membrane. It was obvious that the clean water penetrated through the


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membrane quickly, but the dyed red oil was successfully keeped in the “boat” (Figure 3f). Continuous separation of several oil-water mixtures had been carried out by using this UiO-66 coated “boat” was shown in Video S5. In the whole testing process, the oil content of the collected water remained less than 4 ppm, and no obvious flux decrease emerged, which revealed that the UiO-66 coated mesh membrane had the capability to treat a large amount of oil-water mixture. CONCLUSIONS We realized a very simple strategy to fabricate an underwater superoleophobic UiO-66 coated mesh membrane at ambient room temperature and pressure. The resulting UiO-66 membranes exhibited high-efficiency oil-water separation properties, with the remarkable separation efficiency over 99.99%, and the water permeate flux from 3.8 × 104 L m-2 h-1 to 12.7 × 104 L m-2 h-1. The separation efficiency and intrusion pressure of the UiO-66 coated mesh membrane shows no obvious change after stirring in water for 10 days, indicating high stability and durability properties. Given the fact that the functional sites and surfaces of MOF materials could be readily tuned, while a number of water stable MOF materials had been discovered, this work will facilitate the extensive research on MOF mesh membranes which will eventually lead to some useful membranes for the oil spill cleanup and industrial waste water treatment.

Supporting Information Supporting Information is available from the is available free of charge on the ACS Publications website or from the author.


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ACKNOWLEDGEMENTS This work is financially supported by NSFC (21571076, 21390394, 21571079, 61701543), the Ministry of Science and Technology of SINOPEC (no. A381), Open Projects of State Key Laboratory of Safety and Control for Chemicals (no. SKL-038), “111” project (B07016) and partly supported by Welch Foundation (AX-1730). REFERENCES (1) Shannon, M. A.; Bohn, P. W.; Elimelech, M.; Georgiadis, J. G.; Marinas, B. J.; Mayes, A. M. Science and technology for water purification In the coming decades. Nature 2008, 452, 301310. (2) Schrope, M. Oil spill: Deep wounds. Nature News 2011, 472, 152-154. (3) Chan,Y. J.; Chong, M. F.; Law, C. L.; Hassell, D. G. A review on anaerobic–aerobic treatment of industrial and municipal wastewater. Chem. Eng. J. 2009, 155, 1-18. (4) Ma, Q. L.; Cheng, H. F.; Yu, Y. F.; Huang,Y.; Lu, Q. P; Han, S. K.; Chen, J. Z.; Wang, R.; Fane, A. G.; Zhang, H. Preparation of Superhydrophilic and Underwater Superoleophobic Nanofiber-Based Meshes from Waste Glass for Multifunctional Oil/Water Separation. Small 2017, 13, 1700391. (5) 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. Nat. Nanotechnol. 2017, 12, 434-440.


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Table of Content Figure


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UiO-66 coated mesh membrane with underwater ... - ACS Publications

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