Oil/water separation is an important field, not only for scientific research but also for practical applications aiming to resolve industrial oily wastewater and oil-spill pollution, as well as environmental protection.Recently, research into the role of special wettability for oil/water separation has attracted much attention. In this review we summarize the design, fabrication, applications and recent developments of special wettable materials for oil/water separation. Based on the different types of separation, we organize this review into three parts: "oil-removing" type materials with superhydrophobicity and superoleophilicity (that selectively filter or absorb oil from oil/water mixtures), "water-removing" type materials with superhydrophilicity and superoleophobicity (that selectively separate water from oil/water mixtures), and smart controllable separation materials. In each section, we present in detail the representative work, introduce the design idea, outline their fabrication methods, and discuss the role of special wettability on the separation. Finally, the challenges and outlook for the future of this subject are discussed.

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An oil/water separation mesh with high separation efficiency and intrusion pressure of water has been successfully developed by combining mussel-inspired chemistry and Michael addition reaction. The substrate of the stainless steel mesh was first coated with the adhesive polydopamine (PDA) film by simple immersion in an aqueous solution of dopamine at pH of 8.5. Then n-dodecyl mercaptan (NDM) was conjugated with PDA film through Michael addition reaction at ambient temperature. The as-prepared mesh showed highly hydrophobicity with the water contact angle of 144° and superoleophilicity with the oil contact angle of 0°. It can be used to separate a series of oil/water mixtures like gasoline, diesel, etc. The separation efficiency remains high after 30 times use (99.95% for hexane/water mixture). More importantly, the relatively high intrusion pressure (2.2 kPa) gives the opportunity to separation of large amount of oil and water mixtures. This study provides a new prospect to simply introduce multiple molecules on the adhesive PDA-based mesh to achieve various functional oil/water separation materials.

Thermo and pH dual-controllable oil/water separation materials are successfully fabricated by photo initiated free radical polymerization of dimethylamino ethyl methacrylate (DMAEMA). The PDMAEMA hydrogel coated mesh shows superhydrophilicity and underwater superoleophobicity at certain temperature and pH. Due to the double responsiveness of PDMAEMA hydrogel, the as-prepared mesh can selectively separate water from oil/water mixtures and make water and oil permeate through the mesh orderly and be collected separately by adjusting the temperature or pH. Water can pass through the as-prepared mesh under 55 °C (pH 7) and pH less than 13 (T = 25 °C) while oil is kept on the mesh. When the temperature is above 55 °C or pH is larger than 13, the water retention capacity of PDMAEMA hydrogel is significantly reduced and the swelling volume is decreased. Therefore, oil can permeate through the mesh and be collected in situ. Additionally, this material has excellent potential to be used in practical applications and has created a new field for water/oil separation in which the process can be diversified and more intelligent.

Recently, large quantities of oily wastewater discharged from our daily life and industries have caused serious environmental problems. In addition, frequent oil spill accidents occurred all over the world have also lead to a waste of precious resources. Oil/water separation has become a worldwide challenge for us to overcome. Nowadays, superwetting materials have attracted considerable attention. Among them, porous materials with special wettability are more popular since this kind of materials is easy to fabricate, cost saving and time saving. Moreover, by combining the design of special wettability with the proper pore size, the porous materials could achieve the separation of sundry oil/water mixtures including immiscible oil/water mixtures and stabilized emulsions. In this review, we summarized two types of superwetting porous materials for immiscible oil/water mixtures separation and emulsion separation: water blocking porous materials with superhydrophobic/superoleophilic wettability and oil blocking porous materials with superhydrophilic/underwater superoleophobic wettability. In each type, we introduce the mechanism, fabricating process, effects of oily wastewater treatment and the representative works in detail. Moreover, the smart controllable superwetting porous materials and the wastewater treatment of other pollutants are also introduced briefly.

Reversible addition−fragmentation chain transfer (RAFT) polymerization was used to prepare a series of homo- and copolymers of N-alkyl-substituted acrylamides. The acrylamide monomers have similar chemical structures, but they all exhibit difference in reactivities, especially between N-monosubstituted and N,N-disubstituted acrylamides during the RAFT process. Results from size exclusion chromatography and matrix-assisted laser desorption ionization time-of-flight mass spectrometry indicate chain transfers to monomers are easier to occur for N-monosubstituted polyacrylamides, with negative deviations of the molecular weights from the theoretical values. The high transfer activity makes them good macro-chain transfer agents (CTAs). The stronger electron-donating conjugative effect renders the disubstituted acrylamides more reactive, meaning that they can react more readily with monosubstituted polyacrylamide−CTAs to form a sequent block. Tri- and tetrablock copolymers with multiple thermosensitivity have been successfully prepared and tested following these guiding principles.

A facile solvothermal route is developed to fabricate polydivinylbenzene (PDVB) and decorate the polymer onto porous substrates. "Controllable" separation can be realized by selecting substrates with different pore sizes. The PDVB-modified mesh shows superhydrophobicity/superoleophilicity, and can be used for oil/seawater mixture separation, while the PDVB-modified membrane exhibits high hydrophobicity/superoleophilicity, and is able to separate surfactant stabilized nanoscale water-in-oil emulsions.

Schematic diagram of pore formation mechanism of β-PP during stretching at 25 °C and 90 °C.