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,介绍了代表性的研究工作,阐述了其制备过程、润湿特性以及对油水混合物或者油水乳液的分离效果,并讨论了利用超亲水/水下超疏油、超疏水/超亲油两种类型的材料分离不混溶的油水混合物、"水包油"型乳液和"油包水"型乳液等三类油水混合物的物理化学机理。最后,对该领域的挑战和未来的发展方向进行了展望。     

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。     

超疏水油水分离材料研究进展

近年来,石油泄漏和有机污染物排放对环境和生态系统造成了严重甚至不可挽回的损害,油水分离已成为一个全球性的挑战,如何处理油水混合物并将其有效分离已成为目前亟待解决的问题.许多仿生超疏水材料已被用于选择性油水分离研究,显示出诱人的应用前景.本文作者简要介绍了自然界超疏水现象以及固体表面浸润性理论,分析了材料的疏水亲油原理,重点介绍了近年来超疏水油水分离材料的研究应用进展,并对本领域的研究趋势进行了展望.     

超亲水疏油材料的制备及其油水分离性能

含油污水的随意排放对海洋、沿海周边环境以及人类健康造成了严重的影响。传统的油水分离方法易造成环境二次污染,同时也是对有限资源的一种损耗。因此,如何高效环保地解决含油污水问题具有重要意义。物理过滤/吸附法被认为是一种高效环保的分离方法,基于仿生学原理,许多可用于物理选择性分离的超亲油疏水和超亲水疏油材料被制备出来。超亲油疏水材料易被油污染,重复利用率低;相比之下,超亲水疏油材料具有自清洁性且重复利用率高,在油水分离方面具有广阔的应用前景。根据基底材料的选择不同,本文综述了金属基以及高分子基超亲水疏油材料的研究现状,总结了其优缺点,并对今后超亲水疏油材料的研究方向和重点进行了展望。     

超疏水-超亲油棉织物的制备及在油水分离中的应用

采用溶胶-凝胶法制得Zn O溶胶,以棉织物为基底,在其表面浸涂Zn O溶胶,再经辛基三甲氧基硅烷表面修饰后显示出超疏水性和超亲油性,水滴和油滴在其表面的接触角分别为152°和0°.利用棉织物表面的超疏水性和超亲油性,可以实现对油水混合物中油和水的有效分离.为防水服饰的设计、超疏水/超亲油材料的制备及在油水混合物的分离与应用提供借鉴.     

溶液浸泡结合表面涂层制备超疏水-超疏油表面

超疏水-超疏油材料在防污、防水、防油等领域有广泛的应用前景而引起人们极度关注。 本文用全氟辛酸溶液浸泡锌粉制得超疏水-超疏油锌粉,用聚乙烯醇胶将超疏水-超疏油锌粉粘合、固定到玻璃、木头、塑料、不锈钢、纸片、石头表面后可制得超疏水-超疏油表面,水滴、油滴在其表面的接触角均超过150°。 锌粉与全氟辛酸反应后生成Zn[CF₃(CF₂)₆COO]₂,氟代长链烷基的低表面能化学组成与微纳米粗糙结构的协调作用使其表现出超疏水、超疏油性能。 相关研究有望为超双疏材料的设计、制备及其在自清洁、防水防油及抗污等领域的应用提供借鉴。     

超疏水表面黏附性的研究进展

结合作者课题组的相关工作,简要地论述了超疏水表面固液黏附性的主要影响因素和评价标准,介绍了天然和人工仿生具有特殊黏附性超疏水表面的研究进展,包括超疏水高黏附表面、超疏水低黏附表面、可控黏附性超疏水表面、各向异性黏滞力超疏水表面、黏滞力响应性智能超疏水表面以及超亲/超疏水图案表面制备及运用.特别介绍了作者研究小组在仿生可控黏滞力超疏表面制备以及超亲/超疏水图案表面运用的研究.最后对具有特殊黏附性超疏表面的研究进行总结和展望.     

绿色环保特殊浸润性纺织品的前沿进展

介绍了仿生超疏表面的工作机制以及疏水整理液的发展, 系统综述了近10年来特殊浸润性在开拓多功能绿色纺织领域的研究进展, 讨论了双面超疏、 超疏/超亲、 图案化及可响应浸润性纺织品的制备技术及应用, 介绍近几年在纺织品疏水化功能改性方面取得的前瞻性工作, 包括自清洁防污、 油水分离、 机械耐久、 图案化、 自修复、 单向运输等, 特别是在智能响应、 电子可穿戴、 能源等新兴领域方面的应用. 最后, 对超疏水纺织功能材料目前所面临的挑战及未来发展的方向进行了展望.     

仿生超疏水性表面的最新应用研究

近年来,除了荷叶表面,更多具有特殊润湿性的动植物表面同样受到关注。通过研究这些表面微观结构,人们成功地仿生制备出各种功能化超疏水表面,从而更好地满足工业中实际应用的需要。该综述简单地介绍了表面润湿的基本模型和最新的几种特殊表面结构,重点介绍近几年仿生超疏水表面应用的最新研究进展,主要包括超疏水表面在超疏油、表面润湿转换、外界刺激下的润湿行为调控、微流体、抗结冰等方面的应用。最后,对超疏水表面研究的未来发展进行了展望。     

超疏水超亲油铜网的制备及其在油水分离中的应用

以铜网为基底,通过浸涂法在其表面制得超疏水超亲油有机-无机复合薄膜,水滴、油滴在其表面的接触角分别为152°和10°。 线性低密度聚乙烯-SiO₂纳米球构成的复合阶层结构及低表面能线性低密度聚乙烯涂层的协同作用使铜网产生独特的润湿性。 该铜网具有很好的自清洁性和抗腐蚀性,可用于油水混合物的有效分离。 与传统方法相比,该方法制备超疏水-超亲油薄膜方法简单、成本低、无氟,有望在实践中得到应用。     

具有水下超疏油性能的MXene高效油水分离膜

基于二维材料MXene(Ti₃C₂T_x)的化学组成和纳米片状结构, 在不锈钢网上制备了具有MXene微纳结构表面的新型亲水和水下超疏油分离膜. 对于不同类型的油-水混合物, 该膜材料可实现重力驱动的高效油水分离, 收集的水中残油量小于4 mg/L, 具有高分离效率(>99.99%), 水通量高达57.52 L·m^-2·s^-1. 此外, 经高温处理和多种有机溶剂浸泡后MXene膜仍具有高效的油水分离性能, 并表现出优异的稳定性和循环性.     

仿生水下超疏油表面

水下超疏油表面是指在油/水/固三相体系中,对油的接触角大于150°的固体表面.从鱼体表面和荷叶下表面2种具有水下超疏油性质的生物体系出发,讨论了影响水下超疏油性质的因素,并据此提出了仿生水下超疏油表面的设计方法.通过介绍目前典型的人造水下超疏油表面的制备手段和研究进展,概括了水下超疏油体系的发展现状.对浸润性和黏附性响应性可控的智能水下超疏油体系以及水下超疏油体系在液滴操控、抗生物黏附和油水分离等领域的应用进行了简要介绍.最后对仿生水下超疏油体系目前研究存在的问题及挑战进行了总结,在此基础上展望了该领域未来的发展方向.     

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.     

Facile preparation of superhydrophilic and underwater superoleophobic mesh for oil/water separation in harsh environments

An effective solution to separate oil and water is urgently needed owing to the increasingly serious problem of oil pollution. Numerous studies have been done to endow ordinary materials with extreme wettability for oil/water separation. Unfortunately, most of these materials cannot work in harsh environments, resulting in the low stability and practicability in practice. Herein, a facile method was proposed to fabricate superhydrophilic and underwater superoleophobic mesh by immersing ordinary mesh in a mixture of sulfuric acid (H₂SO₄) and chromium trioxide (CrO₃). After immersing for just 1?min, the mesh was endowed with superhydrophilicity (CA?=?0°) and underwater superoleophobicity (hexane CA?=?151°, SA?=?14°). Increasing the immersion time to 3?min, the prepared mesh exhibited better superoleophobicity. A separation device was developed based on the prepared mesh and the separation efficiencies for diverse oil/water mixtures containing acid, alkaline, salt and hot water were above 95%. The device retained a high efficiency after being reused for 20 times and the prepared mesh maintained superoleophobicity after immersing underwater for 72?h and abrasion test of 100 cycles. This oil/water separation method is easy-to-use, inexpensive, power-free and it can be used to separate caustic oil/water mixtures.     

具有抗生物污染活性的分子筛膜用于高效油水分离

The development of the global economy has been accompanied by frequent oil spills caused by accidental leaks and industrial manufacturing, which have seriously threatened the aquatic environment and human health. Traditional methods for the treatment of oily wastewater include centrifugation, skimming, flotation, oil-absorbing technology, etc., which are limited by low separation efficiency as well as secondary pollution during the post-processing of oil absorption materials. Recently, separation technologies utilizing the special wettabilities of filtration membranes have been developed to enrich and recycle oils from wastewater. Among these, the fabrication of superhydrophilic/underwater superhydrophobic membranes have attracted intensive research interest, which can selectively allow the passage of water through the membrane while blocking the oils. However, microorganisms are more likely to breed on these hydrophilic surfaces, eventually leading to the blockage of the membranes. In this study, ZSM-5 zeolite crystals (MFI topological structure) were coated onto the stainless-steel meshes by means of seeding and secondary hydrothermal growth. Then, 70% of the total Na⁺ ions in the zeolite channels were substituted by Ag⁺ ions via an ion exchange process. The resultant membranes (Ag@ZCMFs) were superamphiphilic in air, with both water contact angle and oil contact angle of approximately 0°. However, they became superoleophobic when immersed in water, and the underwater oil contact angle reached 151.27° ± 4.34°. In terms of special wettability, Ag@ZCMF achieved efficient separation for various oil-water mixtures with separation efficiencies above 99%. The water flux and intrusion pressure of Ag@ZCMF depended on the diameter of pinholes in the membrane, which could be modulated by altering the time of secondary hydrothermal growth. For instance, the average diameter of pinholes in Ag@ZCMF with optimum secondary growth time of 14 h (Ag@ZCMF-14) reached approximately 21 μm, giving rise to the water flux and intrusion pressure of 54720 L·m^-2·h^-1 and 4357 Pa, respectively. The anti-corrosion test and rubbing test confirmed the high chemical and mechanical stability of Ag@ZCMF-14, respectively. The separation efficiency of Ag@ZCMF-14 remained stable during ten purification-regeneration cycles, and no obvious attenuation was observed, proving the high separation stability of Ag@ZCMF-14. Furthermore, the loaded Ag⁺ ions afforded the membrane excellent anti-biofouling activity, which could effectively inhibit the growth of both alga and bacteria in the operating environment, thus preventing membrane blockage during the oil-water separation process. In particular, the bacteriostatic rate of Ag@ZCMF-14 to Escherichia coli reached to 99.6%. These results demonstrate that Ag@ZCMFs with anti-biofouling activity has promising potential future applications in the removal of oil slicks from oily wastewater.     

Controllable wettability of laser treated aluminum mesh for on-demand oil/water separation

Oil/water separation has attracted more attention with the dramatic increasing of oil spill accidents and arbitrarily discharged oily industrial water. However, many reported materials with controllable wettability for on-demand oil/water separation of both heavy and light oil/water mixtures involve complicated devices and dangerous fabrication processes. Herein, we propose a simple, environmentally friendly and high-efficient method to fabricate Al mesh with controllable wettability. Heavy oil can be separated with a high efficiency of 99% in oil-removing mode. For light oil, the separation efficiency can also reach up to 99% in water-removing mode. Additionally, surface wettability of the mesh can be conversed from superhydrophobicity to superhydrophilicity by atmospheric pressure plasma jet (APPJ) and heating, thereby realizing continuous bidirectional separation. Therefore, this work provides a facile, green, and efficient way for on-demand oil/water separation and finds a promising solution for oil pollution problems.     

Electrospun N‐Substituted Polyurethane Membranes with Self‐Healing Ability for Self‐Cleaning and Oil/Water Separation

Membranes with special functionalities, such as self‐cleaning, especially those for oil/water separation, have attracted much attention due to their wide applications. However, they are difficult to recycle and reuse after being damaged. Herein, we put forward a new N‐substituted polyurethane membrane concept with self‐healing ability to address this challenge. The membrane obtained by electrospinning has a self‐cleaning surface with an excellent self‐healing ability. Importantly, by tuning the membrane composition, the membrane exhibits different wettability for effective separation of oil/water mixtures and water‐in‐oil emulsions, whilst still displaying a self‐healing ability and durability against damage. To the best of our knowledge, this is the first report to demonstrate a self‐healing membrane for oil/water separation, which provides the fundamental research for the development of advanced oil/water separation materials.     

Superhydrophilic and superoleophobic chitosan-based nanocomposite coatings for oil/water separation

To overcome easy oil fouling and poor efficiency of traditional oil/water separation materials, superhydrophilic and superoleophobic coatings were fabricated by spray casting chitosan (CTS)-based nanocomposites. The molecular rearrangement of hydrophilic and oleophobic constituents, combined with the hierarchical rough surface structures, enabled a coating with a water contact angle of 0° and a hexadecane contact angle of 157° ± 1°. Hexadecane droplets can easily slide off the dried and water-wetted coating without leaving any obvious oily trailing stains. When the superhydrophilic and superoleophobic CTS-based nanocomposite coatings were applied to oil/water separation, they exhibited excellent anti-fouling capacity, high separation efficiency and easy recyclability. The superhydrophilic and superoleophobic CTS-based coating would be a good candidate for the treatment of industrial oil-polluted water and the cleanup of oil spills.     

CO2‐Responsive Nanofibrous Membranes with Switchable Oil/Water Wettability

Responsive polymer interfacial materials are ideal candidates for controlling surface wetting behavior. Here we developed smart nanostructured electrospun polymer membranes which are capable of switching oil/water wettability using CO₂ as the trigger. In particular, the combination of CO₂‐responsiveness and porous nanostructure enables the as‐prepared membranes to be used as a novel oil/water on–off switch. We anticipate that the promising versatility and simplicity of this system would not only open up a new way of surface wettability change regulation by gas, but also have obvious advantages in terms of highly controlled oil/water separation and CO₂ applications.