Nanosecond Laser-Induced Underwater Superoleophobic and

Feb 3, 2018 - ... excellent separation efficiencies (>96%) and the superior water/oil breakthrough pressure coupled with the high water/oil flux are a...
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Nanosecond laser induced underwater superoleophobic and underoil superhydrophobic mesh for oil/water separation Zhongxu Lian, Jinkai Xu, Zuobin Wang, Zhanjiang Yu, Zhankun Weng, and Huadong Yu Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b03986 • Publication Date (Web): 03 Feb 2018 Downloaded from http://pubs.acs.org on February 7, 2018

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Nanosecond laser induced underwater superoleophobic and underoil superhydrophobic mesh for oil/water separation Zhongxu Lian ,† Jinkai Xu,† Zuobin Wang,‡ Zhanjiang Yu,† Zhankun Weng,‡ Huadong Yu*,† † National and Local Joint Engineering Laboratory for Precision Manufacturing and Detection Technology, Changchun University of Science and Technology, Changchun, 130022, China ‡ International Research Centre for Nano Handling and Manufacturing of China, Changchun University of Science and Technology, Changchun, 130022, China * Corresponding Author: [email protected]

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ABSTRACT

Materials with the special wettability have drawn considerable attention especially in the practical application for the separation and recovery of the oily wastewater, whereas there still remain challenges of the high cost materials, significant time and complicated production equipment. Here, a simple method to fabricate the underwater superoleophobic and underoil superhydrophobic brass mesh via the nanosecond laser ablation is reported for the first time, which provided the micro/nano-scale hierarchical structures. This mesh is superhydrophilic and superoleophilic in air but superoleophobic under water and superhydrophobic under oil. Based on the special wettability of the as-fabricated mesh, we demonstrate a proof of the light or heavy oil/water separation, and the excellent separation efficiencies (>96%), the superior water/oil breakthrough pressure coupled with the high water/oil flux are achieved. Moreover, the nanosecond laser technique is simple and economical, and it is advisable for the large-area and mass fabrication of the underwater superoleophobic and underoil superhydrophobic mesh in the large-scale oil/water separation.

KEYWORDS: Special wettability, brass mesh, light or heavy oil/water separation, nanosecond laser technique

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INTRODUCTION With the increasingly serious oily wastewater pollution levels that accompanied the development of the industry and society, the removal and collection of the organic pollutants from water has become a worldwide problem.1–3 The commercial oil and water separation devices typically consume a large amount of manpower, material and financial resources to realize the clean-up of oil/water mixtures. Thus, it is desirable to develop an effective and inexpensive approach for the separation and recovery of the oily wastewater. The use of the novel materials with the special wettability has recently drawn considerable attention, and has emerged as a popular topic in all round use of the oil/water separation.4–8 As the typical examples of the special wettability, superhydrophobicity/superoleophilicity, underoil

superhydrophobicity,

superhydrophilicity/underwater

superoleophobicity,

and

switchable oil/water wettability have been the topic of recent research on the separation and recovery of the oily wastewater, and diverse methods have been proposed, such as salt-induced phase inversion approach,9,10 sol–gel method,11–13 layer-by-layer assembly,14–18 coating method,19–21

chemical

etching,22–24

electrochemical

process,25–28

plasma

etching,29–31

hydrothermal method,32–36 and femtosecond laser irradiation.37–45 Particularly, the switchable oil/water wettability is particularly fascinating, which is a good choice to separate the light or heavy oil/water mixtures using the different circumstance stimulus, such as CO2/N2,46 pH,25,47–51 light,12,44,52–56 thermo,57,58 magnetic-field,59,60 and electricity.61–63 However, the previous methods used to switch oil/water wettability for the oil/water separation always involve the special equipment, significant time and complex process. Compared with the oil/water separation methods, the underwater superoleophobicity and underoil superhydrophobicity are expected to 3

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appear on the same surface without considering the shortcomings. To the best of our knowledge, studies on the underwater superoleophobicity and underoil superhydrophobicity used for removing and collecting of the oil from water are extremely limited.64–66 Indeed, designing functional interfacial materials to separate the light or heavy oil/water mixtures based on a simple and economical approach has always been the biggest dream of scientists and engineers, especially for the more complex oil/water mixtures. Up to now, fabrication of oil/water separation membrane by laser ablation has been reported.37,67,68 Nanosecond laser technique utilized here for fabricating the micro/nano-scale hierarchical structures is economical, high-efficient, and maskless and single-step that can also be utilized for the large-area fabrication. In addition, the nanosecond laser system has the advantages such as low cost, simple operation and high efficiency, and does not require the special environment, compared with the femtosecond and picosecond lasers. Consequently, the fabrication potential is high demand for the practical industrial applications. Although the nanosecond laser technique has been utilized to fabricate the superhydrophobic surfaces,69–71 the development of the underwater superoleophobic and underoil superhydrophobic surfaces for separating oil/water mixtures has not been reported yet. In this paper, we report for the first time a sample strategy for fabricating the micro/nano-scale hierarchical structures on brass mesh though the nanosecond laser technique, which is superhydrophilic and superoleophilic in air but underwater superoleophobic and underoil superhydrophobic. Based on the special ability of the as-fabricated mesh, we demonstrate a proof of the light or heavy oil/water separation. MATERIALS AND METHODS

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Materials. The brass meshes were purchased from Hebei Lijie Metal Wire Mesh Manufacturing Co. Ltd.. The dodecane, 1,2-dichloroethane, and chloroform were obtained from Sigma-Aldrich. Sodium chloride (NaCl), hydrochloric acid (HCl), sodium hydroxide (NaOH), absolute ethanol, acetone and silicone oil were purchased from Jilin Hao Di Chemical Reagent Co., Ltd.. All reagents mentioned above were of analytical grade and could be used without further purification. The kerosene and soybean oil were obtained from China Petroleum & Chemical Co., Ltd. and Kerry Oil Co., Ltd., respectively. The resistivity of the distilled water was larger than 1 MΩ cm. Sample Fabrication. The basic concept of laser technique is schematically shown in Figure S1 (Supporting Information), the laser penetrated the transparent confining layer and focused on the brass mesh. The silica glass with the size of 100 × 100 × 2 mm3 was selected as the confining layer to ensure the laser focus point at the brass mesh. The sample of the brass mesh with the same area of 60 × 60 mm2 installed in the work platform was selected. The micro/nano-scale hierarchical morphologies were formed using a Q-switched nanosecond laser marking system with a wavelength of 1064 nm and a pulse width of 100 ns using the line-by-line scanning process. The parameters namely Q frequency, scanning speed, power and interval of adjacent laser scanning lines were 20 kHz, 500 mm/s, 10 W and 10 µm, respectively. Preparation of Oil/Water Separation. The gravity-driven method for the light or heavy oil/water separation of the brass meshes with the underwater superoleophobicity and underoil superhydrophobicity was used, and the original and as-fabricated brass meshes were prewetted by the water or oil in the oil/water separation process. Then the 200 mL mixtures of oil and water in volunetric ratio 1:1 were poured onto the original and as-fabricated brass meshes.

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Material Characterization. Surface morphologies of original and as-fabricated brass meshes were examined by a scanning electron microscope (SEM, FEI Quanta 250). The droplet images on the meshes under air, water and oil environments were captured by a digital camera (EOS M3). The chemical composition of the original and as-fabricated brass meshes was characterized by energy dispersive spectroscopy (EDS, X-Max). The contact angle and hysteresis of water or oil droplet with the volume kept at ~5 µL were obtained using a contact angle meter (OCA 20 data physics) under air, water and oil environments, and all the contact angle values were performed by measuring three different positions on the meshes.

Figure 1. (a,b) SEM images of the brass mesh obtained by the nanosecond laser. (c,d) SEM images of the original brass mesh.

RESULTS AND DISCUSSIONS Morphology and Chemistry. Our approach is based on the underwater superoleophobic and underoil superhydrophobic brass meshes fabricated by the construction of micro/nano-scale hierarchical structures fabricated by a Q-switched nanosecond laser marking system. The surface morphologies of the original and as-fabricated brass meshes were studied using the SEM, and the

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results are displayed in Figure 1. After treated with a nanosecond laser, it can be seen that the pore diameter of the mesh became small with the pore size of about 65 µm (Figure 1a), and the high magnification shows that the mesh had the micro/nano-scale hierarchical structures (Figure 1b). As shown in Figure 1c, the original mesh had an average pore diameter of about 75 µm (200 mesh size), and Figure 1d reveals that the original mesh was smooth. The chemical composition of the original and as-fabricated brass meshes were investigated using the EDS (Figure S2, Supporting Information), and O element was clearly observed on the fabricated mesh, which may be due to the oxidation of metal happened in the laser process, resulting in the formation of the oxide coating with the micro/nano-scale hierarchical structures on the original mesh. The underwater superoleophobicity and underoil superhydrophobicity of the treated mesh depended critically on both geometrical structure and chemical composition, which could be used for the separation and recovery of the oily wastewater.

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Figure 2. (a,b) Photographs of water droplet and water contact angle or oil droplet and oil contact angle on the treated mesh in air. (c,d) Underwater−oil droplet and oil contact angle or underoil−water droplet and water contact angle on the treated mesh. (e) Underwater oil contact angles of different oil droplets and water contact angles under different oily liquids on the treated mesh. (f.g) Photographs of underwater−oil droplet and oil contact angle or underoil−water droplet and water contact angle on the untreated mesh. The light oil and heavy oil were employed using kerosene and 1,2-dichloroethane, respectively.

Wetting Properties. The wettability of water and oil on the treated and untreated brass meshes was primary evaluated in the contact angle measuring under air, water and oil environments. After the laser treatment, when the water and oil droplets came in contact with the brass mesh, the droplets were rapidly spread in air, with the water contact angle below 10° and oil (kerosene) contact angle approximately equal to 0° (Figures 2a,b), exhibiting superhydrophilicity and superoleophilicity simultaneously. Conversely, the treated mesh was extremely non-wetting when immersed under water or oil. As observed in Figure 2c, the oil droplet (1,2-dichloroethane) on the treated mesh under water was of spherical shape with a contact angle of 157.5°, exhibiting the underwater superoleophobicity on the treated mesh at this moment. The reason for this disparity may be that the water trapped in the superhydrophilic hierarchical structures minimized the contact between the oil droplet and the mesh submerged in oil. Analogously, when submerged in oil (kerosene), the treated mesh had the underoil superhydrophobicity with a water contact angle of 156.3° (Figure 2d). This result is because the oil can be infiltrated and trapped in the micro/nano-scale hierarchical structures due to the superoleophilicity of the mesh, leading to a great decrease in contact between the water droplet and the mesh submerged in oil. According to the recent theoretical model of Cassie state,72 when a rough surface contacts with water, air can occupy all interspaces between the microstructures on the surface, and be trapped among the microstructures, resulting in the formation of the

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water/air/solid interface. This model will help study the underoil superhydrophobicity and underwater superoleophobicity of treated mesh. When the treated mesh contacts with the water/oil droplets, oil/water can easily enter into the microstructures and be trapped in them due to the superhydrophilicity and superoleophilicity of the mesh, forming the oil/water/solid interface (Figure S3 (Supplementary information)). The treated mesh also exhibited the underwater superoleophobicity and underoil superhydrophobicity toward a wide range of oil liquids including kerosene, soybean oil, dodecane, 1,2-dichloroethane, and chloroform (Figure 2e). As shown in Figure S4 (Supporting Information), the water and oil contact angles of the untreated mesh were 121.7° and 21.2° in air, respectively. The untreated mesh had the underwater oleophobicity (θ ≈ 134.3°) and underoil superhydrophobicity (θ ≈ 154.1°) when submerged in water and oil (Figures 2f,g). Furthermore, the adhesion of the treated and untreated meshes under water and oil was further investigated. The surface of the treated mesh presented not only the underwater superoleophobicity and underoil superhydrophobicity but also oil and water nonadhesion (Figures 3a,c), indicating that the treated mesh has the oil-repellent and water-repellent properties. On the contrary, for the untreated mesh, although it shows underoil superhydrophobicity, the oil and water droplets were adhering onto the surface of the mesh (Figures 3b,d).

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Figure 3. Comparisons of the (a,b) underwater oil droplet (7 µL) and (c,d) underoil water droplet (7 µL) on different surfaces: (a,c) the treated mesh (T. Mesh), (b,d) the untreated mesh (Unt. Mesh).

Oil/Water Separation. Since the mesh exhibited the underwater superoleophobicity and underoil superhydrophobicity, we can separate the light or heavy oil/water mixtures (the light and heavy oils were dyed red) by utilizing the special wettability of the treated mesh. When a light oil(kerosene)/water mixture was poured onto the mesh prewetted by the water, the water would penetrate through the prewetted mesh and get collected in the container, and no oil was visible in the collected water (Figure 4a and Movie S1 (Supporting Information)). After cleaning the mesh with ethanol, the treated mesh could switch from underwater superoleophobic to underoil superhydrophobic. In this case, when a mixture of heavy oil (1,2-dichloroethane) and water was processed in the same way on the mesh with the underoil superhydrophobicity, the oil would penetrate through the mesh and get collected in the container (Figure 4b and Movie S2 (Supporting Information)). Also, after cleaning the mesh with ethanol, the mesh could switch from underoil superhydrophobic to underwater superoleophobic. More importantly, the switch is

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repeatable for at least five cycles (Figure S5, Supporting Information). The oil/water separation processes of the untreated mesh prewetted by the water/oil are shown in Figures 4c,d (Movies S3 and S4, Supporting Information) along with comparisons to the treated mesh.

Figure 4. Separation of the (a,c) light or (b,d) heavy oil/water mixture using the (a,b) treated and (c,d) untreated mesh. The light oil of kerosene and the heavy oil of 1,2-dichloroethane (DCE) were selected as the detecting probe.

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Figure 5. (a) Separation efficiencies of the treated mesh for separating different oil/water mixtures. (b) Separating efficiencies of the treated mesh for the separation of kerosene/water and 1,2-dichloroethane/water mixtures with the conversion times (the conversion condition: cleaning the mesh with ethanol).

The brass mesh obtained by the nanosecond laser was tested for all the separated light or heavy oil(i.e., kerosene, soybean oil, dodecane, 1,2-dichloroethane, and chloroform)/water mixtures with the same process. The separation efficiencies (separation efficiency = liquid collection (g)/liquid (g) × 100%, where the liquid is water or oil) was found to be more than 96.4% (water-removing) for the light oil(i.e., kerosene, soybean oil, dodecane)/water mixtures, and 96.3% (oil-removing) for the heavy oil(i.e., 1,2-dichloroethane and chloroform)/water mixtures (Figure 5a). To investigate the separation efficiency versus the conversion times (between underwater superoleophobicity and underoil superoleophilicity), we carried out the separation experiment using the kerosene/water and 1,2-dichloroethane/water mixtures as an example. This process could be converted multiple times with the unaffected separation efficiency (Figure 5b). Besides, the separation efficiency of the mesh was found to stay at above 97.3% (Figure S6) after the 20 repeat separation tests, indicating an excellent recyclability of the treated mesh.

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Figure 6. Separation of the kerosene/water mixtures employed with the solutions of (a) NaCl, (b) HCl, (c) NaOH and (d) hot water.

In addition, the separation process could be repeated when the more complex kerosene/water mixtures employed with the solutions of NaCl (3.5 wt%), HCl (pH = 1), NaOH (pH = 13) and hot water (80°C) were used (Figure 6 and Movies S5–S8 (Supporting Information)). The oil/water mixtures were successfully separated with the high efficiency of above 96% (Figure S7, Supporting Information). The treated mesh submerged in the corresponding solutions showed the robust superoleophobicity. As shown in Figure S8 (Supporting Information), the kerosene droplet remained a spherical shape on the surfaces of the treated mesh with the oil contact angle of above 150° in the solutions of NaCl, HCl, NaOH and hot water, indicating the stable superoleophobicity of the treated mesh under these conditions. The treated mesh with the oil/water-repellent property can be obtained under the condition of water/oil wetting in advance for the separation and recovery of the oily wastewater. We mainly focus on the oil/water-repellent property of the water/oil layer. The theoretical liquid breakthrough pressure (∆Pthe ) of the water/oil layer is expressed using eqns (1) and (2):73

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∆Pthe = 2γ L1L 2 / R = 4γ L1L 2 sin(θ − π / 2 − α ) / D

D = 2r (1 − cos α ) + d

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(1)

(2)

where γL1L2 is surface tension of liquid(L1)/liquid(L2) interface (Supporting Information),74 R is curvature of oil or water surface, θ is oil or water contact angle, α is the angle between the line connecting the wire centers and the radius to the air/water/solid or oil/water/solid boundary, D is the distance between the two oil/water/solid boundary, r is radius of wire, and d is pore size. It is clear from the eqn (1), because of the superhydrophilicity and superoleophilicity (θ < 90°) of the treated mesh in air, the ∆Pthe of water/oil layer is less than zero, so the treated mesh cannot support any pressure (Figures S9a,b (Supporting Information)). In this case, the liquid would penetrate through the prewetted mesh and get collected in the container. As observed in Figure S10 (Supporting Information), due to the underwater superoleophobicity and underoil superhydrophobicity (θ < 150°) of the treated brass mesh, the ∆Pthe of water/oil layer is greated than zero which means the mesh could withstand pressure in some extent and the droplets stayed on the mesh. During the oil/water separation process, as mentioned above, the liquids accumulated on the prewetted mesh due to the oil/water-repellent property, thus the mesh could also withstand pressure in some extent, and the liquids cannot pass through the mesh (Figures S9c,d (Supporting Information)). When the pressure reaches the limit, it results in the α~0°, and the liquid of the wetting phase will penetrate through the mesh, as shown in Figures S9e,f (Supporting Information). The theoretical liquid breakthrough pressure is expressed as using eqn (3):

∆Pthe = 4γ L1L 2 sin(θ − π / 2) / d

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(3)

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The theoretical liquid breakthrough pressures on the treated mesh are shown in Figure 7 along with comparisons to the measured experimental pressures. The experimental liquid breakthrough pressure (∆Pexp) of the water/oil layer, indicating the hmax of liquid that the treated mesh can support, is expressed using eqn (4):

∆Pexp = ρghmax

(4)

where ρ is the density of the liquid, g is the acceleration of gravity. The experimental pressures for various oils were achieved by pouring oil onto the treated mesh prewetted with water to obtain the hmax (the left inset in Figure 7). Similarly, the breakthrough pressure of water was measured by pouring water onto the treated mesh prewetted with different oils to achieved the hmax (the right inset in Figure 7). Here, the experimental data show good agreement with the theoretical data, suggesting that the high oil/water-permeation resistance was obtained on the treated mesh.

Figure 7. The theoretical and experimental values of the oil/water breakthrough pressures for a series of oils and water. The kerosene breakthrough pressure on the prewetted mesh by water (left), and the water breakthrough pressure on the prewetted mesh by kerosene (right).

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With the separation process, the water/oil flux is another significant factor determining the performance of oil/water separation. Further measurements of the water/oil flux (F) are shown in Figure S11 (Supporting Information). The values are expressed be expressed as:

F = V St

(5)

where V is the volume of the water or oil that permeating through the treated mesh, S is the cross-sectional area of the mesh that water or oil contact with, and t is the time for the permeating 0.5 L of the water or oil through the treated mesh. The estimated water flux was 37.3 L m−2 s−1, and the estimated fluxes of the different oils were above 21.3 L m−2 s−1, exhibiting a very high separation rate for the treated mesh. CONCLUSION In summary, the superhydrophilic and superoleophilic brass mesh with the micro/nano-scale hierarchical structures has been fabricated successfully by the nanosecond laser technique in onestep manner. Due to the superamphiphilic nature of the surface, the treated mesh showed the underwater superoleophobic and underoil superhydrophobic properties. Based on this unique wettability of the mesh, we demonstrate that the treated mesh had the excellent efficiencies from various kinds of light or heavy oil/water, and the calculated separation efficiencies were above 96.3%. The separation efficiency of the mesh was found to stay at above 97.3% after the 20 repeat separation tests, showing that the mesh had high degree of reusability up to 20 cycles. In addition, the separation process could be repeated when the more complex oil/water mixtures employed with the solutions of NaCl, HCl, NaOH and hot water were used, and the separation efficiencies were as high as 98.2 ± 0.4%, 97.8 ± 0.4%, 96.8 ± 0.7% and 98.3 ± 0.3%, respectively. The superior water/oil breakthrough pressure coupled with the high water/oil flux 16

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of the treated mesh can satisfy the requirements for the oil/water separation process. Our work provides a solid basis for developing novel underwater superoleophobic and underoil superhydrophobic brass mesh in reduction of operational cost for oil/water separation, which is expected to be useful in some other fields, such as, microfluidic devices and marine antifouling. ASSOCIATED CONTENT Supporting Information. Additional results Figures S1–S11 and Movies S1–S8 are included. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail (Huadong Yu): [email protected] Present Addresses National and Local Joint Engineering Laboratory for Precision Manufacturing and Detection Technology, College of Mechanical and Electric Engineering, Changchun University of Science and Technology, Changchun, 130022, China Author Contributions The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources European Commission (EC, grant 644971), and the Ministry of Science and Technology of China (MOST, grant 2016YFE0112100).

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Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors are grateful for financial support from the China-EU H2020 International Science and Technology Cooperation Programme (FabSurfWAR Nos.2016YFE0112100 and 644971). 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, 301–310. [2] Feng, L.; Zhang, Z. Y.; Mai, Z. H.; Ma, Y. M.; Liu, B. Q.; Jiang L.; Zhu, D. B. A Super-hydrophobic and Super-oleophilic Coating Mesh Film for the Separation of Oil and Water. Angew. Chem., Int. Ed. 2004, 43, 2046–2048. [3] Chaudhary, J. P.; Nataraj, S. K.; Gogda, A.; Meena, R. Bio-based Superhydrophilic Foam Membranes for Sustainable Oil–Water Separation. Green Chem. 2014, 16, 4552–4558. [4] Wang, B.; Liang, W. X.; Guo Z. G.; Liu, W. M. Biomimetic Super-lyophobic and Super-lyophilic Materials Applied for Oil/Water Separation: a New Strategy beyond Nature. Chem. Soc. Rev. 2015, 44, 336–361. [5] Xue, Z. X.; Cao, Y. Z.; Liu, N.; Feng L.; Jiang, L. Special Wettable Materials for Oil/Water Separation. J. Mater. Chem. A 2014, 2, 2445–2460. [6] Chu, Z. L.; Feng, Y. J.; Seeger, S. Oil/Water Separation with Selective Superantiwetting/ Superwetting Surface Materials. Angew. Chem., Int. Ed. 2015, 54, 2328–2338. [7] Yong, J. L.; Chen, F.; Yang, Q.; Huo, J.; Hou, X. Superoleophobic Surface. Chem. Soc. Rev. 2017, DOI: 10.1039/c6cs00751a

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