Bioinspired Dynamic Antifouling of Oil-Water Separation Membrane by Bubble-Mediated Shape Morphing

Oil–water separation membranes easily fail to oil foulants with low surface energy and high viscosity, which severely limits these membranes’ applications in treating oily wastewater. Herein, an oil–water separation membrane by bioinspired bubble-mediated antifouling strategy is fabricated via growing hierarchical cobalt phosphide arrays on stainless steel mesh. The as-prepared membrane is superhydrophilic/superaerophobic and electrocatalytic for hydrogen evolution under water, which helps to rapidly generate and release abundant microbubbles surrounding the oil-fouled region on the membrane. These microbubbles can spontaneously coalesce with the oil foulants to increase their buoyancy and warp their interface tension by morphing the oil shape. And this spontaneous coalescence also increases the kinetic energy of oil foulants resulting from the decreased bubbles’ interface energy and potential energy. The synergy of the warped interface tension, increased buoyancy, and kinetic energy drives the efficiently dynamic antifouling of this membrane. This dynamic antifouling even can remove some solid sediment such as oily sand particles that causes more serious fouling of the membrane. Thus, this membrane maintains high flux (>11920 L m⁻² h⁻¹ bar⁻¹) in the long-term separation of oil–water and oil–sand–water emulsions by dynamically recovering the decayed flux on demand, which exhibits great potential in treating industrial oily wastewater.     

Paper‐Based Surfaces with Extreme Wettabilities for Novel,Open‐Channel Microfluidic Devices

In this work, a facile methodology is discussed, involving fluoro‐silanization followed by oxygen plasma etching, for the fabrication of surfaces with extreme wettabilities, i.e., surfaces that display all four possible combinations of wettabilities with water and different oils: hydrophobic–oleophilic, hydrophilic–oleophobic, omniphobic, and omniphilic. Open‐channel, paper‐based microfluidic devices fabricated using these surfaces with extreme wettabilities allow for the localization, manipulation, and transport of virtually all high‐ and low‐surface tension liquids. This in turn expands the utility of paper‐based microfluidic devices to a range of applications never before considered. These include, as demonstrated here, continuous oil–water separation, liquid–liquid extraction, open‐channel microfluidic emulsification, microparticle fabrication, and precise measurement of mixtures' composition. Finally, the biocompatibility of the developed microfluidic devices and their utility for cell patterning are demonstrated.     

A Simple Poly(Vinyl Sulfonate) Coating for All-Purpose,Self-Cleaning Applications: Molecular Packing Density–Defined Surface Superhydrophilicity

In this study, poly(vinyl sulfonate) (PVS)–capped surfaces are constructed on the polyelectrolyte multilayers (PEMs) of poly(diallyldimethylammonium chloride) and poly(styrene sulfonate) via electrostatic assembly. The water wetting behavior on the resulting PVS-capped PEMs is meticulously correlated with the number of surface sulfonate groups with the aid of sum frequency generation spectroscopy and quartz crystal microbalance. It is found that when the molecular packing density of surface sulfonate groups is adjusted to be comparable to the maximal packing density of spheres in two dimensions (≈0.9), the PVS capping is able to effectively adsorb water molecules from the surrounding to form hydrogen-bonded networks, which not only promote complete surface wetting by water in air but also diminish surface affinity to adhesion of ice, oil and wax deposited atop. As a result, the PVS-capped PEMs are able to fulfil all the self-cleaning functions proposed for superhydrophilic surfaces including anti-fogging, anti-icing, anti-grease, anti-smudge, anti-graffiti, and anti-wax. After being coated with the self-cleaning PVS-capped PEMs, conventional stainless steel meshes are able to perform oil-water separation without prior water wetting.     

Ultrafast,Reversible Transition of Superwettability of Graphene Network and Controllable Underwater Oil Adhesion for Oil Microdroplet Transportation

Recently, reversible surface superwettability has attracted enormous interest, and methods to shorten the cycle time of transition have also garnered the attention of researchers. Herein, a superhydrophobic, open‐cell graphene network (OCGN) is fabricated via self‐assembly of graphene oxide and vapor ejection. Owing to the special open‐cell microstructure, the OCGNs can be transformed to be superhydrophilic rapidly within only 1 s by air plasma treatment. Moreover, the OCGNs with pure graphene composition have a high conductivity and show an ultrafast Joule heating rate of up to 20 °C s^?1 at a voltage of 20 V. By means of this property, for the first time an ultrafast recovery of the superhydrophobicity for OCGNs by self‐induced Joule heating with the shortest time of 1 min is reported. The mechanism of ultrafast, reversible transition is also explored specifically in this study. In addition, the superhydrophilic OCGNs show superoleophobicity in water and their underwater adhesion for oil droplets can be controlled by plasma treatment. Finally, the OCGNs with different oil adhesion properties are fabricated and the underwater oil microdroplet transportation is realized using OCGNs. Therefore, the OCGNs with smart surface can be an excellent candidate for achieving multifunctional superwettability of surfaces.     

Particle‐Stabilized Materials: Dry Oils and (Polymerized) Non‐Aqueous Foams

Oil (liquids with low surface tension and practically immiscible with water) drops can be dispersed in air if relatively oleophobic particles are available. However, such particles with oil‐repellent surfaces cannot simply be prepared by controlling the particle surface chemistry alone. Herein the preparation of oil‐in‐air materials (oil marbles, dry oils) by changing the wetting behavior of particles by tuning the oil properties, which allows the formation of the metastable Cassie–Baxter wetting state of particle assemblies on oil drop surfaces, is presented. The oil‐in‐air materials can be converted to air‐in‐oil materials (non‐aqueous foams) by tailoring the oil properties, as the robustness of the metastable Cassie–Baxter state of the particle assemblies critically depends on the particle wettability. This conversion implies the phase inversion of dispersed systems consisting of air and oils. It is also shown that particle‐stabilized non‐aqueous foams can be utilized as template to produce macroporous polymers.     

Bioinspired,Stimuli‐Responsive,Multifunctional Superhydrophobic Surface with Directional Wetting,Adhesion, and Transport of Water

A novel smart stimuli responsive surface can be fabricated by the subsequent self‐assembly of the graphene monolayer and the TiO₂ nanofilm on various substrates, that is, fabrics, Si wafers, and polymer thin films. Multiscale application property can be achieved from the interfacial interaction between the hierarchical graphene/TiO₂ surface structure and the underlying substrate. The smart surface possesses superhydrophobic property as a result of its hierarchical micro‐ to nanoscale structural roughness. Upon manipulating the UV induced hydrophilic conversion of TiO₂ on graphene/TiO₂ surface, smart surface features, such as tunable adhesiveness, wettability, and directional water transport, can be easily obtained. The existence of graphene indeed enhances the electron–hole pair separation efficiency of the photo‐active TiO₂, as the time required for the TiO₂ superhydrophilic conversion is largely reduced. Multifunctional characteristics, such as gas sensing, droplet manipulation, and self‐cleaning, are achieved on the smart surface as a result of its robust superhydrophobicity, tunable wettability, and high photo‐catalytic activity. It is also revealed that the superhydrophilic conversion of TiO₂ is possibly caused by the atomic rearrangement of TiO₂ under UV radiation, as a structural transformation from {101} to {001} is observed after the UV treatment.     

Zwitterionic Nanohydrogel Grafted PVDF Membranes with Comprehensive Antifouling Property and Superior Cycle Stability for Oil‐in‐Water Emulsion Separation

Fouling caused by oil and other pollutants is one of the most serious challenges for membranes used for oil/water separation. Aiming at improving the comprehensive antifouling property of membranes and thus achieving long‐term cyclic stability, it is reported in this work the design of a kind of zwitterionic nanosized hydrogels grafted poly(vinylidene fluoride) (PVDF) microfiltration membrane (ZNG‐g‐PVDF) with superior fouling‐tolerant property for oil‐in‐water emulsion separation. Sulfobetaine zwitterionic nanohydrogels with the diameter of ≈ 50 nm are synthesized by an inverse microemulsion polymerization process. They are then grafted onto the surface of PVDF microfiltration membrane, endowing the membrane a superhydrophilic and nearly zero oil adhesion property. This ZNG‐g‐PVDF membrane exhibits great tolerance and resistance to salts pH, especially an excellent antifouling property to oil‐in‐water emulsions containing various pollutants such as surfactants, proteins, and natural organic materials (e.g., humic acid). The comprehensive antifouling property of the membrane gives rise to the cyclic stability of the membrane greatly improved. A nearly 100% recovery ratio of permeating flux is achieved during several cycles of oil‐in‐water emulsion filtration. The ZNG‐g‐PVDF membrane shows great potential in treating practical oily wastewater containing complicated components in the effluent.     

Improved Interfacial Floatability of Superhydrophobic/Superhydrophilic Janus Sheet Inspired by Lotus Leaf

Interfacial materials exhibiting superwettability have emerged as important tools for solving the real‐world issues, such as oil‐spill cleanup, fog harvesting, etc. The Janus superwettability of lotus leaf inspires the design of asymmetric interface materials using the superhydrophobic/superhydrophilic binary cooperative strategy. Here, the presented Janus copper sheet, composed of a superhydrophobic upper surface and a superhydrophilic lower surface, is able to be steadily fixed at the air/water interfaces, showing improved interfacial floatability. Compared with the floatable superhydrophobic substrate, the Janus sheet not only floats on but also attaches to the air–water interface. Similar results on Janus sheet are discovered at other multiphase interfaces such as hexane/water and water/CCl₄ interfaces. In accordance with the improved stability and antirotation property, the microboat constructed by a Janus sheet shows the reliable navigating ability even under turbulent water flow. This contribution should unlock more functions of Janus interface materials, and extend the application scope of the binary cooperative materials system with superwettability.     

Multiple Superwettable Nanofiber Arrays Prepared by a Facile Dewetting Strategy via Controllably Localizing a Low‐Energy Compound

Superwettable solid surfaces have attracted substantial research interest due to their outstanding performance. Various approaches have been developed for preparing superwettable surfaces via constructing a highly textured surface roughness and/or altering the surface free energy. Here, a facile dewetting strategy is proposed to produce multiple superwettabilities on copper hydroxide nanofiber arrays (Cu(OH)₂‐NFAs) by controlling the localized state of low‐energy silicone oil. It is proposed that both the capillary forces along each nanofiber and the evaporation of the octane solvent contribute to the localization of the silicone oil in the NFAs. By varying the concentration of the silicone oil, its localized state changes from a scattered discontinuous distribution to a continuous thin/thick film, which leads to variations in the surface energy and surface roughness. Consequently, Cu(OH)₂‐NFAs with superhydrophilicity, superhydrophobicity with both high and low adhesion, and super slippery properties are prepared. Notably, a very small amount of silicone oil can alter the surface wettability of the Cu(OH)₂‐NFAs from superhydrophilic to superhydrophobic, which is attributable to the migration of silicone oil to the top of the nanofibers during the dewetting process. These results will provide new insights on the facile fabrication of functional surfaces with multiple superwettabilities.     

Polyester Materials with Superwetting Silicone Nanofilaments for Oil/Water Separation and Selective Oil Absorption

Superhydrophobic and superoleophilic polyester materials are successfully prepared by one‐step growth of silicone nanofilaments onto the textile via chemical vapor deposition of trichloromethylsilane. The successful growth of silicone nanofilaments is confirmed with scanning electron microscopy, energy‐dispersive X‐ray analysis, and investigation of the wetting behavior of water on the textile. Even microfibers deeply imbedded inside a woven material could be coated very well with the nanofilaments. The coated textile is water repellant and could only be wetted by liquids of low surface tension. The applications of the coated textile as a membrane for oil/water separation and as a bag for selective oil absorption from water are studied in detail. Owing to the superwetting properties and flexibility of the coated textile, excellent reusability, oil/water separation efficiency, and selective oil absorption capacity are observed, which make it very promising material, e.g., for practical oil absorption.     

Enhanced Liquid Transport on a Highly Scalable,Cost-Effective,and Flexible 3D Topological Liquid Capillary Diode

Directional liquid-transport surfaces have various applications, such as, open microfluidic devices, fog collection, oil–water separation, and surface lubrication. However, current liquid-transport surfaces are expensive, complicated to manufacture, and lack scalability. Moreover, they exhibit low transport speeds and distances. In this study, a laser cutter is used to fabricate scalable, low-cost unidirectional liquid-transporting surfaces with enhanced transport speed and distance using polymeric materials. Cutting and engraving methods are used to create a liquid capillary diode comprising 3D wedge shapes, thereby obtaining an appropriate pressure gradient and liquid pinning. The developed liquid capillary diode exhibits the fastest transport speed (3–17.7 mm s⁻¹) reported so far, and a large normalized distance (L/R: transport distance/radius of dispensed droplet). The transport distance increases with the square root of time under various contact angles and liquid viscosities, which agree well with the theoretical scaling results obtained using the modified Washburn model. Additionally, the flexible liquid capillary diode operates adequately even when bent with the maximum curvature of 0.1 mm⁻¹. The results provide better design guidelines for 3D topological liquid-transport surfaces for various applications.     

Collective Wetting of a Natural Fibrous System and Its Application in Pump‐Free Droplet Transfer

Novel wetting strategies in plants have inspired numerous notable biomimetic surfaces over the past decade, such as self‐cleaning surfaces mimicking the water repellency of lotus leaves and directional water transport surfaces imitating the slippery surface on carnivorous plants. Here, a new wetting behavior in dandelion seed (genus Taraxacum) is found, characterized by capturing a droplet inside it. The critical conditions required for wetting of the fiber assay in terms of the fibrous geometry and liquid surface tension are identified, and how these factors quantitatively affect the volume of the captured droplet is shown further. More importantly, the reverse process can be triggered by introducing a competitive liquid phase with smaller surface tension to the wetted fiber assay, as it is demonstrated by the release of the captured water droplet in oil. These results enhance the understanding on wetting of fibrous structures and would benefit the design of novel intelligent and responsive devices. This newly identified wetting behavior holds great potential for fine control and micromanipulation of liquid. As a demonstration, it is illustrated that the natural fibrous structure is capable of manipulating a small volume of liquid for droplet‐based multiplexed chemical reaction.     

Spontaneous Directional Self-Cleaning on the Feathers of the Aquatic Bird Anser cygnoides domesticus Induced by a Transient Superhydrophilicity

In nature, the feathers of the goose Anser cygnoides domesticus stay superhydrophobic over a long term, thought as the main reason for keeping the surface clean. However, contaminants, especially those that are oleophilic or trapped within textures, cannot be removed off the superhydrophobic feathers spontaneously. Here, a different self-cleaning strategy based on superhydrophilic feathers is revealed that is imparted by self-coating of the amphiphilic saliva, which enables removing away low-surface-tension and/or small-size contaminants by forming directional water sheeting depending on their unique anisotropic microstructures. Particularly, the surface superhydrophilicity is switchable to superhydrophobicity upon exposure to air for maintaining a clean surface for a long time, which is further enhanced by coating with self-secreted preening oil. By alternate switching between a transient superhydrophilicity and a long-term stable superhydrophobicity, the goose feathers exhibit an integrated smart self-cleaning strategy, which is also shared by other aquatic birds. An attractive point is the re-entrant structure of the feathers, which facilitates not only liquid spreading on superhydrophilic feathers, but also long-term stability of the cleaned surface by shedding water droplets off the superhydrophobicity feathers. Thus, artificial self-cleaning microtextures are developed. The result renews the common knowledge on the self-cleaning of aquatic bird feathers, offering inspiration for developing bioinspired self-cleaning microtextures and coatings.     

Directly Coating Hydrogel on Filter Paper for Effective Oil–Water Separation in Highly Acidic,Alkaline, and Salty Environment

The separation of oil–water mixtures in highly acidic, alkaline, and salty environment remains a great challenge. Simple, low‐cost, efficient, eco‐friendly, and easily scale‐up processes for the fabrication of novel materials to effective oil–water separation in highly acidic, alkaline, and salty environment, are urgently desired. Here, a facile approach is reported for the fabrication of stable hydrogel‐coated filter paper which not only can separate oil–water mixture in highly acidic, alkaline, and salty environment, but also separate surfactant‐stabilized emulsion. The hydrogel‐coated filter paper is fabricated by smartly crosslinking filter paper with hydrophilic polyvinyl alcohol through a simple aldol condensation reaction with glutaraldehyde as a crosslinker. The resultant multiple crosslinked networks enable the hydrogel‐coated filter paper to tolerate high acid, alkali, and salt up to 8 m H₂SO₄, 10 m NaOH, and saturated NaCl. It is shown that the hydrogel‐coated filter paper can separate oil–water mixtures in highly acidic, alkaline, and salty environment and oil‐in‐water emulsion environment, with high separation efficiency (>99%).     

Lossless,Passive Transportation of Low Surface Tension Liquids Induced by Patterned Omniphobic Liquidlike Polymer Brushes

Surfaces enabling directional liquid transportation are of great interest for a wide range of applications such as water collection, microfluidics, and heat transfer systems. Surfaces capable of lossless, long-range passive transportation of low surface tension (LST) liquids using wettability patterned, liquidlike coatings with minimal contact angle hysteresis are reported. Lossless LST droplet travel distances over 150 mm are achieved, enabled by a two-phase transportation mechanism: morphological transformation from a bulge to a channel shape, followed by directional transportation along the asymmetrical wedge-shaped channel. The developed surfaces can split, merge, and precisely transport various low-surface tension liquids, including alcohols, alkanes, and solvents. The developed transportation strategy can also enhance LST liquid dropwise condensation through continuous removal of the condensate, even on horizontally positioned surfaces without the assistance of gravity.     

Hydrophilic/Oleophilic Magnetic Janus Particles for the Rapid and Efficient Oil–Water Separation

The separation of microsized oil droplets from water is strongly required by the environmental protection and petroleum industry. However, the separation of microsized oil droplets from water is often ignored. Herein, magnetic Janus particles are reported with a convex hydrophilic surface/concave oleophilic surface by emulsion interfacial polymerization and selective surface assembly, realizing the rapid and efficient separation of microscaled tiny oil droplets from water. These magnetic Janus particles exhibit significant abilities to separate microscaled oil droplets from water, which usually occurs within 120 s with a separation efficiency >99%. Theoretical and experimental results demonstrate that these magnetic Janus particles can capture tiny oil droplets to make them coalesce into larger ones during the process of separation. Further studies reveal that these Janus particles can self‐assemble and closely pack onto the interface of larger oil droplets, acting as surfactants to stabilize them. Moreover, the shape effect of the Janus particle is demonstrated on the coalescence of the oil droplets.     

Graphene Foam with Switchable Oil Wettability for Oil and Organic Solvents Recovery

One of the most pervasive environmental issues is water contaminated with oil or organic solvents; this global challenge calls for emerging materials that could effectively separate oil or organic solvents from water. Here, such a material is presented by integrating 3D porous graphene foam (GF) with a smart pH‐responsive surface, showing switchable superoleophilic and superoleophobic properties in response to the medium pH. The key chemistry applied in this study is to modify the 3D porous GF with an amphiphilic copolymer containing a block of poly(2‐vinylpyridine) and polyhexadecyl acrylate (P2VP‐b‐PHA), resulting in a smart GF (ss‐GF) with an either superoleophilic or superoleophobic surface at different medium pH. The as‐designed ss‐GF can effectively absorb oil or organic solvents from the aqueous media by using its superoleophilic surface at pH of 7.0, and it can also completely release the adsorbates when the pH is switched to 3.0 (and the surface of ss‐GF is therefore shifted to superoleophobic); with a continuous operation of many cycles (e.g., >10). Furthermore, the as‐designed ss‐GF shows superior absorption capacity for oil and organic solvent, with a high capacity of ≈196 times of the weight relative to that of the pristine ss‐GF. The present work suggests encouraging applications of the ss‐GF to water–oil and water–organic solvent separation.     

Filefish‐Inspired Surface Design for Anisotropic Underwater Oleophobicity

Surfaces with anisotropic wettability, widely found in nature, have inspired the development of one‐dimensional water control on surfaces relying on the well‐arranged surface features. Controlling the wetting behavior of organic liquids, especially the motion of oil fluid on surfaces, is of great importance for a broad range of applications including oil transportation, oil‐repellent coatings, and water/oil separation. However, anisotropic oil‐wetting surfaces remain unexplored. Here, the unique skin of a filefish Navodon septentrionalis shows anisotropic oleophobicity under water. On the rough skin of N. septentrionalis, oil droplets tend to roll off in a head‐to‐tail direction, but pin in the opposite direction. This pronounced wetting anisotropy results from the oriented hook‐like spines arrayed on the fish skin. It inspires further exploration of the artificial anisotropic underwater oleophobic surfaces: By mimicking the oriented hook‐like microstructure on a polydimethylsiloxane layer via soft lithography and subsequent oxygen‐plasma treatment to make the PDMS hydrophilic, artificial fish skin is fabricated which has similar anisotropic underwater oleophobicity. Drawn from the processing of artificial fish skin, a simple principle is proposed to achieve anisotropic underwater oleophobicity by adjusting the hydrophilicity of surface composition and the anisotropic microtextures. This principle can guide the simple mass manufacturing of various inexpensive high surface‐energy materials, and the principle is demonstrated on commercial cloth corduroy. This study will profit broad applications involving low‐energy, low‐expense oil transportation, underwater oil collection, and oil‐repellant coatings on ship hulls and oil pipelines.     

Magnetocontrollable Droplet and Bubble Manipulation on a Stable Amphibious Slippery Gel Surface

Smart manipulation of liquid/bubble transport has garnered widespread attention due to its potential applications in many fields. Designing a responsive surface has emerged as an effective strategy for achieving controllable transport of liquids/bubbles. However, it is still challenging to fabricate stable amphibious responsive surfaces that can be used for the smart manipulation of liquid in air and bubbles underwater. Here, amphibious slippery surfaces are fabricated using magnetically responsive soft poly(dimethylsiloxane) doped with iron powder and silicone oil. The slippery gel surface retains its magnetic responsiveness and demonstrates strong affinity for bubbles underwater but shows small and switching resistance forces with the water droplets in air and bubbles underwater, which is the key factor for achieving the controllable transport of liquids/bubbles. On the slippery gel surface, the sliding behaviors of water droplets and bubbles can be reversibly controlled by alternately applying/removing an external magnetic field. Notably, compared with slippery liquid‐infused porous surfaces, the slippery gel surface demonstrates outstanding stability, whether in air or underwater, even after 100 cycles of alternately applying/removing the magnetic field. This surface shows potential applications in gas/liquid microreactors, gas–liquid mixed fluid transportation, bubble/droplet manipulation, etc.     

Droplets Crawling on Peristome‐Mimetic Surfaces

Controlling the mobility of liquids along surfaces is widely exploited in various technologies to achieve self‐lubrication, phase‐change heat transfer, and microfluidics. Despite commendable progress in directional liquid transport on peristome‐mimetic surfaces, liquid merely spreads directionally with a wetted trail remaining. It is a challenge to achieve directional contracting of spreading liquid at the rear side and ultimately unidirectional motion in bulk from one site to another. Here it is shown that liquids resting on the peristome‐mimetic surfaces can crawl directionally and rapidly in an inchworms‐like way under the action of sudden spontaneous bubbles levitation. Vacuuming or chemical reaction induces sudden nucleation, growth, coalescence (Ostwald ripening process), and rupture of bubbles in the asymmetric microcavities of the peristome‐mimetic surface with directional overpressure beneath the liquid, resulting in the guided contracting and spreading of the liquid. Bubbles regulate this new mode of liquid directional motion. The strategy offers opportunities for liquids directional motion for various applications, such as in microfluidic devices, oil–water separation, and water collection systems.