Polydopamine and Its Derivative Materials: Synthesis and Promising Applications in Energy, Environmental, and Biomedical Fields

Oil spills and industrial organic pollutants have induced severe water pollution and threatened every species in the ecological system. To deal with oily water, special wettability stimulated materials have been developed over the past decade to separate oil-and-water mixtures. Basically, synergy between the surface chemical composition and surface topography are commonly known as the key factors to realize the opposite wettability to oils and water and dominate the selective wetting or absorption of oils/water. In this review, we mainly focus on the development of materials with either super-lyophobicity or super-lyophilicity properties in oil/water separation applications where they can be classified into four kinds as follows (in terms of the surface wettability of water and oils): (i) superhydrophobic and superoleophilic materials, (ii) superhydrophilic and under water superoleophobic materials, (iii) superhydrophilic and superoleophobic materials, and (iv) smart oil/water separation materials with switchable wettability. These materials have already been applied to the separation of oil-and-water mixtures: from simple oil/water layered mixtures to oil/water emulsions (including oil-in-water emulsions and water-in-oil emulsions), and from non-intelligent materials to intelligent materials. Moreover, they also exhibit high absorption capacity or separation efficiency and selectivity, simple and fast separation/absorption ability, excellent recyclability, economical efficiency and outstanding durability under harsh conditions. Then, related theories are proposed to understand the physical mechanisms that occur during the oil/water separation process. Finally, some challenges and promising breakthroughs in this field are also discussed. It is expected that special wettability stimulated oil/water separation materials can achieve industrial scale production and be put into use for oil spills and industrial oily wastewater treatment in the near future.

Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: a new strategy beyond nature

Studying nature to reveal the mechanisms of special wetting phenomena in biological systems can effectively inspire the design and fabrication of functional interfacial materials with superwettability. In this Review, the historical development, new phenomena and emerging applications of superwettability systems are discussed.

Nature-inspired superwettability systems

Polydopamine is one of the simplest and most versatile approaches to functionalizing material surfaces, having been inspired by the adhesive nature of catechols and amines in mussel adhesive proteins. Since its first report in 2007, a decade of studies on polydopamine molecular structure, deposition conditions, and physicochemical properties have ensued. During this time, potential uses of polydopamine coatings have expanded in many unforeseen directions, seemingly only limited by the creativity of researchers seeking simple solutions to manipulating surface chemistry. In this review, we describe the current state of the art in polydopamine coating methods, describe efforts underway to uncover and tailor the complex structure and chemical properties of polydopamine, and identify emerging trends and needs in polydopamine research, including the use of dopamine analogs, nitrogen-free polyphenolic precursors, and improvement of coating mechanical properties.

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Polydopamine Surface Chemistry: A Decade of Discovery.

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.

Oil/Water Separation with Selective Superantiwetting/Superwetting Surface Materials

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.

Special wettable materials for oil/water separation

We report a simple and inexpensive method for fabricating double-layer TiO2-based mesh. The upper layer is a TiO2 coated mesh film with micro- and nano-structures, while the lower is the same TiO2 mesh film but modified with ODP (octadecyl phosphonic acid) to impart its superhydrophobic and superoleophilic properties. Such a mesh can be successfully used for the separation of insoluble oil from water due to its special wettability, as well as the degradation of soluble pollutants in water under UV light because of the photocatalytic abilities of TiO2, making it a promising candidate for water purification.

Integrated oil separation and water purification by a double-layer TiO2-based mesh

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 mole...

Mussel-Inspired Chemistry and Michael Addition Reaction for Efficient Oil/Water Separation

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.

Thermo and pH dual-responsive materials for controllable oil/water separation.

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.

Yingze Cao

Papers

Special wettable materials for oil/water separation

Integrated oil separation and water purification by a double-layer TiO2-based mesh

Mussel-Inspired Chemistry and Michael Addition Reaction for Efficient Oil/Water Separation

Thermo and pH dual-responsive materials for controllable oil/water separation.

Superwetting Porous Materials for Wastewater Treatment: from Immiscible Oil/Water Mixture to Emulsion Separation