Preparation of superhydrophobic materials for oil/water separation and oil absorption using PMHS–TEOS-derived xerogel and polystyrene

Fabrication of suerhydrophobic materials towards oil/water separation and oil absorption has been receiving great attention nowadays, due to the significant increase of industrial oily wastewater and frequent accident of oil spill. In most previous studies, the usage of expensive precursors restricted the wide applications of prepared superhydrophobic materials. In this work, superhydrophobic filter paper, fabric and polyester sponges were fabricated by dip-coating the mixed solution of polystyrene and xerogels, which were prepared with tetraethoxysilane and polymethylhydrosiloxane, based on previous work. The as-fabricated fabric can effectively separate oil and water mixtures and possesses excellent reusability; more significantly, the materials maintained its good hydrophobic and excellent oil/water separation capacity even after ten cycles. Interestingly enough, the stability was provided, as a result, the fabric still exhibited superhydrophobic after 100 abrasion times and showed high repellency towards many liquids with different pH values. Additionally, the coated polyester sponges can quickly absorb various oil and organic liquid, which will offer a practical application for the treatment of seawater or oily wastewater. By contrast, this experiment process is simple and avoided using costly fluoro-chemicals or complicated fabrication process.     

Removal of Oil Spills through a Self‐Propelled Smart Device

Oil/water separation through superhydrophobic/superoleophilic materials has attracted considerable interest over the past decades; however, dealing with oil spills on broad waters through an active way remains a challenge. Herein, we report a self‐propelled smart device driven by the decomposition of hydrogen peroxide that can spontaneously move on the water surface and collect floating oil droplets inside with superhydrophobic and superoleophilic properties. Moreover, the self‐propelled smart device exhibits excellent stability and high efficiency for oil/water separation. We believe this study may provide a promising strategy for fabricating smart aquatic devices that have potential applications in water remediation.     

油水分离用天然材料表面化学研究进展

油水乳液和油水混合物的分离对解决工业含油废水以及原油泄漏造成的污染问题具有重要的意义.近年来应用于油水分离的超润湿材料引起了广泛的关注,并展现出良好的应用前景.本文综述了近年来利用超润湿性低成本、环保的天然材料通过过滤和吸附技术分离油水乳液和混合物的研究进展.对于每一种天然材料,如沙粒、木材、椰子壳等,介绍了代表性的研...     

Oil/Water Separation with Selective Superantiwetting/Superwetting Surface Materials

The separation of oil from oily water is an important pursuit because of increasing worldwide oil pollution. Separation by the use of materials with selective oil/water absorption is a relatively recent area of development, yet highly promising. Owing to their selective superantiwetting/superwetting properties towards water and oil, superhydrophobic/superoleophilic surfaces and underwater superoleophobic surfaces have been developed for the separation of oil/water‐free mixtures and emulsions. In this Review, after a short introduction to oil/water separation, we describe the principles of materials with selective oil/water absorption and outline recent advances in oil/water separation with superwetting/superantiwetting materials, including their design, their fabrication, and models of experimental setups. Finally, we discuss the current state of this new field and point out the remaining problems and future challenges.     

Superhydrophobic Micro/Nanostructured Copper Mesh with Self-Cleaning Property for E ective Oil/Water Separation

In this work, a simple method was carried out to successfully fabricate superoleophilic and superhydrophobic N-dodecyltrimethoxysilane@tungsten trioxide coated copper mesh. The as-fabricated copper mesh displayed prominent superoleophilicity and superhydrophobicity with a huge water contact angle about 154.39^° and oil contact angle near 0^°. Moreover, the coated copper mesh showed high separation efficiency approximately 99.3%, and huge water flux about 9962.3 L·h^-1·m^-2, which could be used to separate various organic solvents/water mixtures. Furthermore, the coated copper mesh showed favorable stability that the separation efficiency remained above 90% after 10 separation cycles. Benefiting from the excellent photocatalytic degradation ability of tungsten trioxide, the coated copper mesh possessed the self-cleaning capacity. Therefore, the mesh contaminated with lubricating oil could regain superhydrophobic property, and this property of self-cleaning permitted that the fabricated copper mesh could be repeatedly used for oil and water separation.     

基于特殊润湿性材料的油水分离

频繁发生的石油泄漏事故以及工业含油污水的违规排放不仅造成了巨大的经济损失,而且严重破坏了人类赖以生存的生态环境。为了净化被油污染的水域,研究者们近年来开始研究出了各种特殊润湿性(如超疏水或超疏油)的材料用于实现油水分离。超疏水和超疏油可以通过设计材料表面的微观几何形貌和化学分子组成来获得。通过各种微纳制备手段使材料表现出对油和水截然相反的极端润湿性,是这类材料实现油水分离的关键所在。本文首先阐述了实现油水分离的重要意义,并介绍了材料表面润湿性的相关理论基础。根据材料对水和油所表现出的不同超疏液性与超亲液性,对油水分离材料从以下三类分别介绍：(ⅰ)超疏水/超亲油材料,(ⅱ)超疏油/超亲水材料,(ⅲ)智能响应润湿性材料。对于每一类油水分离材料,本文概括了国际上近期相关的代表性研究工作,包括材料的制备方法和实现油水分离的原理和过程,以及这些材料的主要特点和应用。最后,针对基于特殊润湿性材料实现油水分离,探讨了该研究领域目前存在的主要问题和面临的挑战,并对该领域的应用前景进行了展望。     

A versatile coating approach to fabricate superwetting membranes for separation of water-in-oil emulsions

Separation of oil/water mixtures, especially for the emulsified oil/water mixtures, is important because of the frequent occurrence of oil spill accidents. Utilizing superwetting porous membrane has become a promising approach to separate either surfactant-free or surfactant-stabilized emulsions. Herein we report a facile and versatile strategy for preparing hydrophobic/under-oil superhydrophobic membranes by coating the skeletons of the membranes with the poly[(3,3,3-trifluoropropyl)methylsiloxane] (PTFPMS) nanoparticles. The obtained membranes could be used to separate various waterin- oil emulsions with high flux and separation efficiency. In addition, owning to the outstanding resistance of PTFPMS to the most organic solvents or oils, the modified membranes exhibited the excellent reusability and the antifouling properties that were critical in the practical applications. Many commercially available membranes can be modified by such a simple method.     

基于原位结晶苯膦酸锆膜的油水分离网的制备及应用

运用水热法在铜网表面原位结晶生长苯膦酸锆,获得微纳米级粗糙结构,且苯环排列在苯膦酸锆表面的最外层,使铜网具有超疏水和超亲油的性质,无需任何低表面能物质修饰,即可对油水混合物进行分离.苯膦酸锆层与基底存在一定的结合力,具有机械稳定性;同时又具有抗酸碱的化学稳定性.这种油水分离网不仅能够实现油水混合物的分离,还可以实现乳化油的油水分离,在实际生产运用过程中具有较好的应用前景.     

Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces

Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation.     

Superhydrophobic and superoleophilic polyethylene aerogel coated natural rubber latex foam for oil-water separation application

The oil-water separation has made an attention due to over-increased production of oily water from the industrial process and everyday routine of humans. The current work reports on preparation and characterization of High-Density Polyethylene (HDPE) aerogel coated Natural Rubber Latex foam (NRLF) with superhydrophobic and superoleophilic character, good sorption capacity for oil-water separation application and were investigated. The HDPE aerogel and the coated NRLF material was prepared by a cooling process from a solution of HDPE in xylene solvent (HDPE sole, which resulted into thermally induced phase separation of the Polyethylene molecular network). The HDPE aerogel coated NRLF displayed a porous surface morphology with particle-like structural features. The HDPE aerogel coated NRLF showed superhydrophobicity with static water contact angle >150°. The effect and recyclability of the HDPE aerogel coated NRLF for oil-water separation was investigated using different model oil solvents to explore their repeatable application in oil spill clean-up process. Modified NRLF shows an excellent mechanical property (compressibility). The average modulus and average stiffness of the modified NRLF increased with the increase of the concentration of HDPE sol. The modified superhydrophobic sponge has good durability under acid and base conditions.     

Micro–nano structural engineering of filter paper surface for high selective oil–water separation

Cellulose-based lotus-leaf-like filter paper for selective separation of oil/water was prepared. Experimentally, cellulose nanofibril aerogel microspheres prepared by ultrasonic atomization method were coated on commercial filter papers to form unique “micro–nano” structured surface. By controlling both the morphology and chemistry of the surface, the papers could be either under-water superoleophobic or under-oil superhydrophobic. It was found that the filter papers could be engineered to effectively filter only oil or only water from their mixtures.     

Fabrication of Superhydrophobic and Superoleophilic Polystyrene Surfaces by a Facile One‐Step Method

A facile one‐step method has been developed to prepare both superhydrophobic and superoleophilic surfaces of polystyrene (PS) without any chemical modification. A rough film consisting of micro‐bead and nano‐fiber mixed structures is formed by spraying a PS solution onto a large area and any type of substrate. The mixed structures with such unique wettability properties can be used in oil/water separation and as oil sorbents.

     

Solvothermal synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces

Reported here is a facile synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces. Taking this nanoporous polymer as a media, superhydrophobicity is rapidly imparted onto three typical kinds of substrates, including paper, transparent polydimethylsiloxane (PDMS), and finger skin. Quantitative characterization showed that the adhesion between the water droplet and polymer-coated substrates decreased significantly compared to that on the original surface, further indicating the effective wetting mode transformation. The nanoporous polymer coating would open a new door for facile, rapid, safe, and larger scale fabrication of superhydrophobic surfaces on general substrates.     

Activation of Cellulose Assisted by CO2 for the Preparation of a Superhydrophobic Nanocoating

There is increasing demand for superhydrophobic materials, which can be used for separating oil and water efficiently. To avoid secondary pollution, it is desirable to prepare such materials with green technology. Here, we present an environmentally benign method for fabricating superhydrophobic materials by using organic base based solvents in which cellulose can be dissolved and activated. The dissolved cellulose could be chemically modified with a silanization reagent, and the solvent could be recycled after CO₂ was removed. The obtained cellulose nanocoating exhibited excellent hydrophobic effects. By spraying it on filter paper (water contact angle (WCA)=165°) for oil and water separation, the separation efficiency of more than 95 % was achieved; ultrasonication of an ordinary sponge in its dispersion (WCA=163°), meant it could be used as an oil absorber. It can also absorb a certain amount of bisphenol A (BPA), with the concentration decreasing by 66 % from the original concentration (0.1 mm ). Besides the high separation efficiency, it is resistant to a wide range of pH solutions, which means that it could be used in harsh environments. More importantly, the process is cost‐effective, the solvent can be recycled, and the whole process is green. Thus, the activation method provides a green route for the preparation of other cellulose‐based materials.     

超疏水超亲油玉米秸秆粉油污吸附剂的制备及其在油水分离中的应用

超疏水超亲油材料因其在油水分离等领域有广泛的应用前景而引起人们极大关注。 目前,有很多方法可以用来制备超疏水超亲油材料,但因其过程复杂、成本高、环境适应性差限制了其在实际生产、生活中应用。 本文以玉米秸秆为原料,经TiO₂ 溶胶浸涂并经辛基三甲氧基硅烷修饰后显示出超疏水和超亲油,水滴、油滴在其表面的接触角分别为160°和0°。 研究结果显示,玉米秸秆粉表面的超疏水性源于其表面微纳米复合阶层结构及低表面能化学组成的协同作用。 利用玉米秸秆粉表面的憎水性和亲油性,能将其用于水面油污的吸附和分离,具有分离效率高、稳定性好、可循环利用的优点。 相比于其它材料,以玉米秸秆为原料制备超疏水超亲油的油污吸附剂,原料丰富、成本低、过程简单、易降解、可循环利用,有望在生产、生活中得到应用。     

Green Approach to the Fabrication of Superhydrophobic Mesh Surface for Oil/Water Separation

We report a simple and environment friendly method to fabricate superhydrophobic metallic mesh surfaces for oil/water separation. The obtained mesh surface exhibits superhydrophobicity and superoleophilicity after it was dried in an oven at 200 °C for 10 min. A rough silver layer is formed on the mesh surface after immersion, and the spontaneous adsorption of airborne carbon contaminants on the silver surface lower the surface free energy of the mesh. No low‐surface‐energy reagents and/or volatile organic solvents are used. In addition, we demonstrate that by using the mesh box, oils can be separated and collected from the surface of water repeatedly, and that high separation efficiencies of larger than 92 % are retained for various oils. Moreover, the superhydrophobic mesh also possesses excellent corrosion resistance and thermal stability. Hence, these superhydrophobic meshes might be good candidates for the practical separation of oil from the surface of water.     

Fabrication,chemical modification,and topographical patterning of reactive gels assembled from azlactone‐functionalized polymers and a diamine

The work reported here demonstrates an approach to the fabrication of chemically reactive and topographically patterned hydrogels using the azlactone‐functionalized polymer poly(2‐vinyl‐4,4'‐dimethylazlactone) (PVDMA) and the hydrophilic diamine Jeffamine®. Gels were initially assembled in DMSO but can be subsequently transferred into aqueous media to form hydrogels. Spectroscopic characterization of assembled gels demonstrated that variation in the stoichiometric ratio of azlactones to amines during gel synthesis permits control over the extent of crosslinking in the gels. Residual azlactones not consumed during crosslinking can be exploited to further functionalize these gels with hydrophobic, hydrophilic, and macromolecular amines that influence the physicochemical properties of these materials in aqueous solvents. The surface and bulk of these gels can be differentially functionalized (i.e., different functional groups on the gel surface relative to the bulk) by taking advantage of different rates of diffusion of macromolecular amines versus small molecule amines into assembled gels. Finally, these azlactone‐functionalized gels can be topographically patterned with microwell arrays using a replica molding technique and chemically modified postfabrication with amine nucleophiles. This reactive approach to the fabrication of topographically patterned and chemically functionalized hydrogels offers a straightforward method for the rapid synthesis of micropatterned scaffolds of interest in a broad range of applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3185–3194     

用于油/水分离的环保无氟超疏水织物的制备与性能

针对目前用于油/水分离的超疏水材料普遍存在的原料不环保、不可降解、涂层耐久性差等缺点,采用简便的浸渍法,制备了一种环保、工艺简单且性能优良的超疏水材料。首先,使用水性聚氨酯（WPU）将聚甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯P（MMA-r-GMA）微球固定在棉织物表面,构造微纳米级粗糙结构。其次,通过水解-缩合反应,将无毒的十六烷基三甲氧基硅烷（HDTMS）与甲基三乙氧基硅烷（MTES）锚定在棉织物表面,制备得到超疏水棉织物。结果表明,改性棉织物接触角最高可达157.3（°）,滚动角为5（°）。同时具有很好的耐溶剂性,在酸碱溶液中浸泡30 min后,接触角几乎无变化。油水分离效率最高可达97.8%,即使在经过10次循环分离之后,油水分离效率仍然在95%以上。该超疏水织物具有出色的油水分离效率和优良的稳定性,可用于可持续且环保的油水分离领域。     

Rapid and Efficient Separation of Oil from Oil‐in‐Water Emulsions Using a Janus Cotton Fabric

A novel bi‐functional Janus cotton fabric is used to separate oil from oil‐in‐water emulsions. This fabric is superhydrophobic on one surface and polyamine‐bearing on the other. When used as a filter, the polyamine‐bearing side causes the micrometer‐sized oil droplets to coalesce. The coalesced oil then fills fabric pores on the superhydrophobic side and selectively permeates it. Oil separation using this method is rapid and the separated oil is pure. Furthermore, the content of the model oil hexadecane (HD) in water after a separation can be reduced to less than 0.03±0.03 vol %. These features demonstrate the practical potential of this technology.     

Ultraviolet-durable superhydrophobic zinc oxide-coated mesh films for surface and underwater-oil capture and transportation

In this paper, we report a simple and an inexpensive method for fabricating superhydrophobic/superoleophilic mesh films from microstructured ZnO coatings. The microstructured ZnO coatings, which do not contain any fluorinated compounds, maintain their superhydrophobicity and superoleophilicity after ultraviolet irradiation and display environmental stability. Furthermore, those microstructured ZnO-coated mesh films exhibit good selectivity (even underwater) and excellent recyclability, making them promising candidates for many potential applications, including liquid-liquid separation, water treatment, and liquid transportation.