Engineering a Robust,Versatile Amphiphilic Membrane Surface Through Forced Surface Segregation for Ultralow Flux‐Decline

Unlike biofoulants/pollutants, oil foulants/pollutants are prone to coalesce, spread and migrate to form continuous fouling layer covering on the surfaces. Therefore, such kind of fouling can not be simply alleviated by hydrophilic modification with currently extensively used antifouling materials such as poly(ethylene glycol) (PEG)‐based or zwitterionic polymers etc. In the present study, an amphiphilic porous membrane surface, comprising hydrophilic fouling resistant domains and hydrophobic fouling release microdomains, is explored via a "forced surface segregation" approach. The resultant membranes exhibit both superior oil‐fouling and bio‐fouling resistant property: membrane fouling is exquisitely suppressed and the permeation flux‐decline is decreased to an ultralow level. It can be envisaged that the present study may open a novel avenue to the design and construction of robust, versatile antifouling surfaces.     

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.     

Visible‐Light‐Activated Photocatalytic Films toward Self‐Cleaning Membranes

Membranes are among the most promising means of delivering increased supplies of fit‐for‐purpose water, but membrane fouling remains a critical issue restricting their widespread application. Coupling photocatalysis with membrane separation has been proposed as a potentially effective approach to reduce membrane fouling. However, commonly used materials in photocatalysis limit use of low‐cost sources such as sunlight due to their large bandgaps. There are few examples of in situ photocatalytic self‐cleaning of membranes, with removal from the filtration system and ex situ illumination being more common. In this work, a visible‐light‐activated photocatalytic film prepared by nitrogen doping into the lattice of TiO₂ is deposited on commercial ceramic membranes via atomic layer deposition. The synergy between membrane separation and redox reactions between organic pollutants and reactive oxygen species produced by the visible‐light‐activated layer offers a possibility for stable and sustainable membrane operation under in situ solar irradiation.     

Polyphenol‐Sensitized Atomic Layer Deposition for Membrane Interface Hydrophilization

Improvements in energy–water systems will necessitate fabrication of high‐performance separation membranes. To this end, interface engineering is a powerful tool for tailoring properties, and atomic layer deposition (ALD) has recently emerged as a promising and versatile approach. However, most non‐polar polymeric membranes are not amenable to ALD processing due to the absence of nucleation sites. Here, a sensitization strategy for ALD‐coating is presented, illustrated by membrane interface hydrophilization. Facile dip‐coating with polyphenols effectively sensitizes hydrophobic polymer membranes to TiO₂ ALD coating. Tannic acid‐sensitized ALD‐coated membranes exhibit outstanding underwater crude oil repulsion and rigorous mechanical stability through bending and rinsing tests. As a result, these membranes demonstrate outstanding crude oil‐in‐water separation and reusability compared to untreated membranes or those treated with ALD without polyphenol pretreatment. A possible polyphenol‐sensitized ALD mechanism is proposed involving initial island nucleation followed by film intergrowth. This polyphenol sensitization strategy enriches the functionalization toolbox in material science, interface engineering, and environmental science.     

Biomimetic and Superwettable Nanofibrous Skins for Highly Efficient Separation of Oil‐in‐Water Emulsions

Developing a feasible and efficient separation membrane for the purification of highly emulsified oily wastewater is of significance but challenging due to the critical limitations of low flux and serious membrane fouling. Herein, a biomimetic and superwettable nanofibrous skin on an electrospun fibrous membrane via a facile strategy of synchronous electrospraying and electrospinning is created. The obtained nanofibrous skin possesses a lotus‐leaf‐like micro/nanostructured surface with intriguing superhydrophilicity and underwater superoleophobicity, which are due to the synergistic effect of the hierarchical roughness and hydrophilic polymeric matrix. The ultrathin, high porosity, sub‐micrometer porous skin layer results in the composite nanofibrous membranes exhibiting superior performances for separating both highly emulsified surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions. An ultrahigh permeation flux of up to 5152 L m^?2 h^?1 with a separation efficiency of >99.93% is obtained solely under the driving of gravity (≈1 kPa), which was one order of magnitude higher than that of conventional filtration membranes with similar separation properties, showing significant applicability for energy‐saving filtration. Moreover, with the advantage of an excellent antioil fouling property, the membrane exhibits robust reusability for long‐term separation, which is promising for large‐scale oily wastewater remediation.     

2D Heterostructure Membranes with Sunlight‐Driven Self‐Cleaning Ability for Highly Efficient Oil–Water Separation

Introducing solar energy into membrane filtration to decrease energy and chemicals consumption represents a promising direction in membrane fields. In this study, a kind of 0D/2D heterojunction is fabricated by depositing biomineralized titanium dioxide (TiO₂) nanoparticles with delaminated graphitic carbon nitride (g‐C₃N₄) nanosheets, and subsequently a kind of 2D heterostructure membrane is fabricated via intercalating g‐C₃N₄@TiO₂ heterojunctions into adjacent graphene oxide (GO) nanosheets by a vacuum‐assisted self‐assembly process. Due to the enlarged interlayer spacing of GO nanosheets, the initial permeation flux of GO/g‐C₃N₄@TiO₂ membrane reaches to 4536 Lm^?2 h^?1 bar^?1, which is more than 40‐fold of GO membranes (101 Lm^?2 h^?1 bar^?1) when utilized for oil/water separation. To solve the sharp permeation flux decline, arising from the adsorption of oil droplets, the a sunlight‐driven self‐cleaning process is followed, maintaining a flux recovery ratio of more than 95% after ten cycles of filtration experiment. The high permeation flux and excellent sunlight‐driven flux recovery of these heterostructure membranes manifest their attractive potential application in water purification.     

Ultrathin 2D‐Layered Cyclodextrin Membranes for High‐ Performance Organic Solvent Nanofiltration

Synthetic membranes with a high selectivity for demanding molecular separations and high permeance have a large potential for the reduction of energy consumption in separation processes. Herein, for the first time, the fabrication of an ultrathin layered macrocycle membrane for molecular separation in organic solvent nanofiltration using per‐6‐amino‐β‐cyclodextrin as a monomer for membrane manufacturing by interfacial polymerization is reported. Compared to a regular nonfunctionalized cyclodextrin, a higher reactivity is observed, enabling a very fast membrane formation under mild conditions. The formed membrane is composed of a layered structure of polymerized cyclodextrin, which shows high stability in different organic solvents. The membrane exhibits excellent separation performance for organic solvent nanofiltration, both with nonpolar and polar solvents. Most importantly, this new membrane type can discriminate between molecules with nearly identical molecular weights but different shapes. The unmatched high permeance and shape selectivity of the membranes can be attributed to the ultralow thickness, controlled microporosity, as well as the layered macrocycle structure, which makes the membranes promising for high‐performance molecular separation in the chemical and biochemistry industry.     

Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction

A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.     

Novel Organic‐Dehydration Membranes Prepared from Zirconium Metal‐Organic Frameworks

Membranes with outstanding performance that are applicable in harsh environments are needed to broaden the current range of organic dehydration applications using pervaporation. Here, well‐intergrown UiO‐66 metal‐organic framework membranes fabricated on prestructured yttria‐stabilized zirconia hollow fibers are reported via controlled solvothermal synthesis. On the basis of the adsorption–diffusion mechanism, the membranes provide a very high flux of up to ca. 6.0 kg m^?2 h^?1 and excellent separation factor (>45 000) for separating water from i ‐butanol (next‐generation biofuel), furfural (promising biochemical), and tetrahydrofuran (typical organic). This performance, in terms of separation factor, is one to two orders of magnitude higher than that of commercially available polymeric and silica membranes with equivalent flux. It is comparable to the performance of commercial zeolite NaA membranes. Additionally, the membrane remains robust during a pervaporation stability test (≈300 h), including exposure to harsh environments (e.g., boiling benzene, boiling water, and sulfuric acid) where some commercial membranes (e.g., zeolite NaA membranes) cannot survive.     

High‐Efficiency Water‐Transport Channels using the Synergistic Effect of a Hydrophilic Polymer and Graphene Oxide Laminates

Graphene oxide (GO) laminates possess unprecedented fast water‐transport channels. However, how to fully utilize these unique channels in order to maximize the separation properties of GO laminates remains a challenge. Here, a bio‐inspired membrane that couples an ultrathin surface water‐capturing polymeric layer (<10 nm) and GO laminates is designed. The proposed synergistic effect of highly enhanced water sorption from the polymeric layer and molecular channels from the GO laminates realizes fast and selective water transport through the integrated membrane. The prepared membrane exhibits highly selective water permeation with an excellent water flux of over 10 000 g m^?2 h^?1, which exceeds the performance upper bound of state‐of‐the‐art membranes for butanol dehydration. This bio‐inspired strategy demonstrated here opens the door to explore fast and selective channels derived from 2D or 3D materials for highly efficient molecular separation.     

Graphene‐Directed Supramolecular Assembly of Multifunctional Polymer Hydrogel Membranes

Polymer‐based nanoporous hydrogel membranes hold great potential for a range of applications including molecular filtration/separation, controlled drug release, and as sensors and actuators. However, to be of practical utility, polymer membranes generally need to be fabricated as ultrathin yet mechanically robust, have a large‐area yet be defect‐free and in some cases, their structure needs the capability to adapt to certain stimuli. These stringent and sometimes self‐conflicting requirements make it very challenging to manufacture such bulk nanostructures in a controllable, scalable and cost‐effective manner. Here, a versatile approach to the fabrication of multifunctional polymer‐based hydrogel membranes is demonstrated by a single step involving filtration of an aqueous dispersion containing chemically converted graphene (CCG) and a polymer. With CCG uniquely serving as a membrane‐ and pore‐forming directing agent and as a physical cross‐linker, a range of water soluble polymers can be readily processed into nanoporous hydrogel membranes through supramolecular interactions. With the interconnected CCG network as a robust and porous scaffold, the membrane nanostructure can easily be fine‐tuned to suit different applications simply by controlling the chemistry and concentration of the incorporated polymer. This work provides a simple and versatile platform for the design and fabrication of new adaptive supramolecular membranes for a variety of applications.     

Phototunable Underwater Oil Adhesion of Micro/Nanoscale Hierarchical‐Structured ZnO Mesh Films with Switchable Contact Mode

Controllable surface adhesion of solid substrates has aroused great interest both in air and underwater in solving many challenging interfacial science problems such as robust antifouling, oil‐repellent, and highly efficient oil/water separation materials. Recently, responsive surface adhesion, especially switchable adhesion, under external stimulus in air has been paid more and more attention in fundamental research and industrial applications. However, phototunable underwater oil adhesion is still a challenge. Here, an approach to realize phototunable underwater oil adhesion on aligned ZnO nanorod array‐coated films is reported, via a special switchable contact mode between an unstable liquid/gas/solid tri‐phase contact mode and stable liquid/liquid/solid tri‐phase contact mode. The photo‐induced wettability transition to water and air exists (or does not) in the micro/nanoscale hierarchical structure of the mesh films, playing important role in controlling the underwater oil adhesion behavior. This work is promising in the design of novel interfacial materials and functional devices for practical applications such as photo‐induced underwater oil manipulation and release, with loss‐free oil droplet transportation.     

Surfactant‐Assisted Emulsion Self‐Assembly of Nanoparticles into Hollow Vesicle‐Like Structures and 2D Plates

The emulsion‐based self‐assembly of nanoparticles into low‐dimensional superparticles of hollow vesicle‐like assemblies is reported. Evaporation of the oil phase at relatively low temperatures from nanoparticle‐containing oil‐in‐water emulsion droplets leads to the formation of stable and uniform sub‐micrometer vesicle‐like assembly structures in water. This result is in contrast with those from many previously reported emulsion‐based self‐assembly methods, which produce solid spherical assemblies. It is found that extra surfactants in both the oil and water phases play a key role in stabilizing nanoscale emulsion droplets and capturing hollow assembly structures. Systematic investigation into what controls the morphology in emulsion self‐assembly is carried out, and the approach is extended to fabricate more complex rattle‐like structures and 2D plates. These results demonstrate that the emulsion‐based assembly is not limited to typical thermodynamic spherical assembly structures and can be used to fabricate various types of interesting low‐dimensional assembly structures.     

Gold Nanoparticles and g‐C3N4‐Intercalated Graphene Oxide Membrane for Recyclable Surface Enhanced Raman Scattering

Toxic organic pollutants in the aquatic environment cause severe threats to both humans and the global environment. Thus, the development of robust strategies for detection and removal of these organic pollutants is essential. For this purpose, a multifunctional and recyclable membrane by intercalating gold nanoparticles and graphitic carbon nitride into graphene oxide (GNPs/g‐C₃N₄/GO) is fabricated. The membranes exhibit not only superior surface enhanced Raman scattering (SERS) activity attributed to high preconcentration ability to analytes through π–π and electrostatic interactions, but also excellent catalytic activity due to the enhanced electron–hole separation efficiency. These outstanding properties allow the membrane to be used for highly sensitive detection of rhodamine 6G with a limit of detection of 5.0 × 10^?14m and self‐cleaning by photocatalytic degradation of the adsorbed analytes into inorganic small molecules, thus achieving recyclable SERS application. Furthermore, the excellent SERS activity of the membrane is demonstrated by detection of 4‐chlorophenol at less than nanomolar level and no significant SERS or catalytic activity loss was observed when reusability is tested. These results suggest that the GNPs/g‐C₃N₄/GO membrane provides a new strategy for eliminating traditional, single‐use SERS substrates, and expands practical SERS application to simultaneous detection and removal of environmental pollutants.     

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%).     

High‐Performance CO2 Capture through Polymer‐Based Ultrathin Membranes

Thin film composite (TFC) membranes have attracted great research interest for a wide range of separation processes owing to their potential to achieve excellent permeance. However, it still remains challenging to fully exploit the superiority of thin selective layers when mitigating the pore intrusion phenomenon. Herein, a facile and generic interface‐decoration‐layer strategy collaborating with molecular‐scale organic–inorganic hybridization in the selective layer to obtain a high‐performance ultrathin film composite (UTFC) membrane for CO₂ capture is reported. The interface‐decoration layer of copper hydroxide nanofibers (CHNs) enables the formation of an ultrathin selective layer (≈100 nm), achieving a 2.5‐fold increase in gas permeance. The organic part in the molecular‐scale hybrid material contributes to facilitating CO₂‐selective adsorption while the inorganic part assists in maintaining robust membrane structure, thus remarkably improving the selectivity toward CO₂. As a result, the as‐prepared membrane shows a high CO₂ permeance of 2860 GPU, superior to state‐of‐the‐art polymer membranes, with a CO₂/N₂ selectivity of 28.2. The synergistic strategy proposed here can be extended to a wide range of polymers, holding great potential to produce high‐efficiency ultrathin membranes for molecular separation.     

Atom‐Thick Membranes for Water Purification and Blue Energy Harvesting

Membrane‐based processes, namely, water purification and harvesting of osmotic power deriving from the difference in salinity between seawater and freshwater are two strategic research fields holding great promise for overcoming critical global issues such as the world growing energy demand, climate change, and access to clean water. Ultrathin membranes based on 2D materials (2DMs) are particularly suitable for highly selective separation of ions and effective generation of blue energy because of their unique physicochemical properties and novel transport mechanisms occurring at the nano‐ and sub‐nanometer length scale. However, due to the relatively high costs of fabrication compared to traditional porous membrane materials, their technological transfer toward large‐scale applications still remains a great challenge. Herein, the authors present an overview of the current state‐of‐the‐art in the development of ultrathin membranes based on 2DMs for osmotic power generation and water purification. The authors discuss several synthetic routes to produce atomically thin membranes with controlled porosity and describe in detail their performance, with a particular emphasis on pressure‐retarded osmosis and reversed electrodialysis methods. In the last section, an outlook and current limitations as well as viable future developments in the field of 2DM membranes are provided.     

Engineering Carbon Nanotube Forest Superstructure for Robust Thermal Desalination Membranes

Desalination by membrane distillation (MD) using low‐grade or waste heat provides a potential route for sustainable water supply. Nonwetting, porous membranes that provide a selective pathway for water vapor over nonvolatile salt are at the core of MD desalination. Conventional water‐repelling MD membranes (i.e., hydrophobic and superhydrophobic membranes) fail to ensure long‐term desalination performance due to pore wetting and surface fouling. To address these challenges, a defect‐free carbon nanotube forest (CNTF) is engineered in situ on a porous electrospun silica fiber substrate. The engineered CNTF forms an ultrarough and porous interface structure, allowing outstanding wetting resistance against water in air and oil underwater. As a result of this antiwetting property, the composite CNTF membrane displays a stable water vapor flux and a near complete salt rejection (>99.9%) in the desalination of highly saline water containing low surface tension contaminants. The antimicrobial property of the composite CNTF membrane imparted by the unique forest‐like architecture and the oxidative effect of carbon nanotubes (CNTs) are further demonstrated. The results exemplify an effective strategy for engineering CNT architecture to elucidate the structure–property–performance relationship of the nanocomposite membranes and to guide the design of robust thermal desalination membranes.     

Self‐Supporting,Double Stimuli‐Responsive Porous Membranes From Polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) Diblock Copolymers

Asymmetric membranes are prepared via the non‐solvent‐induced phase separation (NIPS) process from a polystyrene‐block‐poly(N,N‐dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) block copolymer. The polymer is prepared via sequential living anionic polymerization. Membrane surface and volume structures are characterized by scanning electron microscopy. Due to their asymmetric character, resulting in a thin separation layer with pores below 100 nm on top and a macroporous volume structure, the membranes are self‐supporting. Furthermore, they exhibit a defect‐free surface over several 100 µm². Polystyrene serves as the membrane matrix, whereas the pH‐ and temperature‐sensitive minority block, PDMAEMA, renders the material double stimuli‐responsive. Therefore, in terms of water flux, the membranes are able to react on two independently applicable stimuli, pH and temperature. Compared to the conditions where the lowest water flux is obtained, low temperature and pH, activation of both triggers results in a seven‐fold permeability increase. The pore size distribution and the separation properties of the obtained membranes were tested through the pH‐dependent filtration of silica particles with sizes of 12–100 nm.     

Inside Front Cover: Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction (Adv. Funct. Mater. 8/2006)

The inside cover shows a hierarchical, mesoporous, multilayer TiO2 photocatalytic membrane synthesized via a novel sol–gel dip‐coating process employing surfactant templates reported by Dionysiou and co‐workers on p. 1067. The resulting asymmetric mesoporous TiO2 membrane supported onto a porous Al2O3 substrate exhibited hierarchical changes in pore diameter and materials porosity from the top to the bottom layer. The TiO2 membrane has multiple simultaneous functions, including photocatalysis, disinfection, separation, and anti‐biofouling. A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.