Perfluoroalkyl Functionalized Superhydrophobic Covalent Organic Frameworks for Excellent Oil-Water Membrane Separation and Anhydrous Proton Conduction.

Rapid economic development has led to oil pollution and energy shortage. Membrane separation has attracted much attention due to its simplicity and efficiency in oil-water-separation. The development of membrane materials with enhanced separation properties is essential to improve the separation-efficiency. Proton exchange membrane fuel cells (PEMFCs) are expected to replace conventional engines due to their high-power-conversion rates and other favorable properties. Anhydrous-proton-conducting materials are vital components of PEMFCs. However, developing stable proton-conducting materials that exhibit high conductivity at varying temperatures remains challenging. Herein, two covalent organic frameworks (COFs) with long-side-chains are synthesized, and their corresponding COF@SSN membranes. Both membranes can effectively separate oil-water mixtures and water-in-oil emulsions. The TFPT-AF membrane achieves a maximum oil-flux of 6.05 × 105 g h-1 m-2 with an oil-water separation efficiency of above 99%, which is almost unchanged after 20 consecutive uses. COF@H3PO4 doped with different ratios of H3PO4 is prepared, the results show that the perfluorocarbon-chain system has  excellent anhydrous proton conductivity , achieving an ultra-high proton-conductivity of 3.98 × 10-1 S cm-1 at 125 °C. This study lays the foundation for tailor-made-functionalization of COF through pre-engineering and surface-modification, highlighting the great potential of COFs for oil-water separation and anhydrous-proton-conductivity.

Durable Nano-Flower Structured Foam Coupled with Electrically-Driven in Situ Aeration Enable High-Flux Oil/Water Emulsion Separation with Dynamic Antifouling Ability.

The conventional membranes used for separating oil/water emulsions are typically limited by the properties of the membrane materials and the impact of membrane fouling, making continuous long-term usage unachievable. In this study, a filtering electrode with synchronous self-cleaning functionality is devised, exhibiting notable antifouling ability and an extended operational lifespan, suitable for the continuous separation of oil/water emulsions. Compared with the original Ti foam, the in situ growth of NiTi-LDH (Layered double hydroxide) nano-flowers endows the modified Ti foam (NiTi-LDH/TF) with exceptional superhydrophilicity and underwater superoleophobicity. Driven by gravity, a rejection rate of over 99% is achieved for various emulsions containing oil content ranging from 1% to 50%, as well as oil/seawater emulsions. The flux recovery rate exceeds 90% after one hundred cycles and a 4-h filtration period. The enhanced separation performance is realized through the "gas bridge" effect during in situ aeration and electrochemical anodic oxidation. The internal aeration within the membrane pores contributes to the removal of oil foulants. This study underscores the potential of coupling foam metal filtration materials with electrochemical technology, providing a paradigm for the exploration of novel oil/water separation membranes.

Stable and Durable Superhydrophobic Cotton Fabrics Prepared via a Simple 1,4-Conjugate Addition Reaction for Ultrahigh Efficient Oil-Water Separation.

Superhydrophobic materials used for oil-water separation have received wide attention. However, the simple and low-cost strategy for making durable superhydrophobic materials remains a major challenge. Here, this work reports that stable and durable superhydrophobic cotton fabrics can be prepared using a simple two-step impregnation process. Silica nanoparticles are surface modified by hydrolysis condensation of 3-aminopropyltrimethoxysilane (APTMS). 1,4-conjugate addition reaction between the acrylic group of cross-linking agent pentaerythritol triacrylate (PETA) and the amino group of octadecylamine (ODA) forms a covalent cross-linked rough network structure. The long hydrophobic chain of ODA makes the cotton fabric exhibit excellent superhydrophobic properties, and the water contact angle (WCA) of the fabric surface reaches 158°. The modified cotton fabric has good physical and chemical stability, self-cleaning, and anti-fouling. At the same time, the modified fabric shows excellent oil/water separation efficiency (98.16% after 20 cycles) and ultrahigh separation flux (15413.63 L m-2 h-1) due to its superhydrophobicity, superoleophilicity, and inherent porous structure. The method provides a broad prospect in the future diversification applications of oil/water separation and oil spill cleaning.

Amphiphilic Superspreading Polymer Membranes Prepared by Capillary Force-Driven Self-Assembly.

To overcome the two main obstacles of large-scale application of superspreading material, self assembly is used to prepare superspreading polymer membrane (SPPM) in this work. An amphiphilic SPPM is prepared by capillary force-driven self assembly using PP melt-blown nonwovens and polyvinyl alcohol (PVA). The prepared SPPM has low preparation cost and stable performance since self assembly needs low energy consumption, and the production is thermodynamically stable. By using cryo-electron microscopy, transmission electron microscopy, X-ray photoelectron spectrum and scanning electron microscope with energy dispersive X-ray spectroscopy. It is proved that PVA is successfully assembled on the fiber surface of PP melt-blown nonwovens. The prepared SPPM has excellent spreading performance, the "spreading times" of both water and oil are less than 0.5 s. They showed much superior performance compared to traditional materials when applied in oil-water separation, seawater desalination, and ion separation. This work will definitely promote the development of self assembly, superspreading materials, and related sciences.

Review on demulsification techniques for oil/water emulsion: Comparison of recyclable and irretrievable approaches.

Since the establishment of the first global refinery in 1856, crude oil has remained one of the most lucrative natural resources worldwide. However, during the extraction process from reservoirs, crude oil gets contaminated with sediments, water, and other impurities. The presence of pressure, shear forces, and surface-active compounds in crude oil leads to the formation of unwanted oil/water emulsions. These emulsions can take the form of water-in-oil (W/O) emulsions, where water droplets disperse continuously in crude oil, or oil-in-water (O/W) emulsions, where crude oil droplets are suspended in water. To prevent the spread of water and inorganic salts, these emulsions need to be treated and eliminated. In existing literature, different demulsification procedures have shown varying outcomes in effectively treating oil/water emulsions. The observed discrepancies have been attributed to various factors such as temperature, salinity, pH, droplet size, and emulsifier concentrations. It is crucial to identify the most effective demulsification approach for oil/water separation while adhering to environmental regulations and minimizing costs for the petroleum sector. Therefore, this study aims to explore and review recent advancements in two popular demulsification techniques: chemical demulsification and magnetic nanoparticles-based (MNP) demulsification. The advantages and disadvantages of each technique are assessed, with the magnetic approach emerging as the most promising due to its desirable efficiency and compliance with environmental and economic concerns. The findings of this report are expected to have a significant impact on the overall process of separating oil and water, benefiting the oil and gas industry, as well as other relevant sectors in achieving the circular economy.

Ultra-high flux mesh membranes coated with tannic acid-ZIF-8@MXene composites for efficient oil-water separation.

Oil/water separation has become a global concern due to the increasing discharge of multi-component harmful oily wastewater. Super wetting membranes have been shown to be an effective material for oil/water separation. Ultra-high flux stainless-steel meshes (SSM) with superhydrophilicity and underwater superoleophobicity were fabricated by tannic acid (TA) modified ZIF-8 nanoparticles (TZIF-8) and two-dimensional MXene materials for oil/water separation. The TZIF-8 increased the interlayer space of MXene, enhancing the flux permeation (69,093 L m-2h-1) and rejection of the composite membrane (TZIF-8@MXene/SSM). The TZIF-8@MXene/SSM membrane showed an underwater oil contact angle of 154.2°. The membrane maintained underwater superoleophobic after stability and durability tests, including various pH solutions, organic solvents, reusability, etc. In addition, the oil/water separation efficiency of TZIF-8@MXene/SSM membranes was higher than 99% after treatment in harsh conditions and recycling. The outstanding anti-fouling, stability, durability, and recyclability properties of TZIF-8@MXene/SSM membrane highlight the remarkable potential of membranes for complex oil/water separation process.

Hydrophobic Carbon Nitride Nanolayer Enables High-Flux Oil/Water Separation with Photocatalytic Antifouling Ability.

Efficient oil/water separation tackles various issues in occasions of oil leakage and oil discharge, such as environmental pollution, recollection of the oil, and saving the water. Herein, a compact superhydrophobic/superoleophilic graphitic carbon nitride nanolayer coated on carbon fiber networks (CNBA/CF) is designed and synthesized for efficient gravity-driven oil/water separation. The CNBA/CF shows excellent oil absorption and an impressive oil/water filtration separation performance. The flux reaches the state-of-art value of 4.29 × 105 L/m2/h for dichloromethane with separation efficiency up to 99%. Successive oil absorption tests, long-term filtration separation, and harsh conditions experiments confirm the remarkable separation and chemical structure stability of the CNBA/CF filter. Besides, the CNBA/CF demonstrates good photocatalytic antifouling ability thanks to the extended visible light absorption and improved charge separation. This work combines the material surface wettability modulation with a photocatalytic self-cleaning property in the fabrication of efficient oil/water separation materials while overcoming the filter fouling issue.

Nanosheet BiOBr Modified Rock Wool Composites for High Efficient Oil/Water Separation and Simultaneous Dye Degradation by Activating Peroxymonosulfate.

The development of superlyophobic materials in liquid systems, enabling synchronous oil/water separation and dye removal from water, is highly desirable. In this study, we employed a novel superwetting array-like BiOBr nanosheets anchored on waste rock wool (RW) fibers through a simple neutralization alcoholysis method. The resulting BiOBr/RW fibers exhibited superoleophilic and superhydrophilic properties in air but demonstrated underwater superoleophobic and underoil superhydrophobic characteristics. Utilizing its dual superlyophobicity, the fiber layer demonstrated high separation efficiencies and flux velocity for oil/water mixtures by prewetting under a gravity-driven mechanism. Additionally, the novel BiOBr/RW fibers also exhibited excellent dual superlyophobicity and effective separation for immiscible oil/oil systems. Furthermore, the BiOBr/RW fibers could serve as a filter to continuously separate oil/water mixtures with high flux velocity and removal rates (>93.9%) for water-soluble dye rhodamine B (RhB) simultaneously by directly activating peroxymonosulfate (PMS) in cyclic experiments. More importantly, the mechanism of simultaneous oil/water separation and RhB degradation was proposed based on the reactive oxygen species (ROS) quenching experiments and electron paramagnetic resonance (EPR) analysis. Considering the simple modified process and the waste RW as raw material, this work may open up innovative, economical, and environmentally friendly avenues for the effective treatment of wastewater contaminated with oil and water-soluble pollutants.

Formation of Microporous Poly Acrylonitrile-Co-Methyl Acrylate Membrane via Thermally Induced Phase Separation for Immiscible Oil/Water Separation.

An interconnected sponge structure and porous surface poly (acrylonitrile-co-methyl acrylate) (P(AN-MA)) microfiltration membranes (MF) were fabricated via thermally induced phase separation (TIPS) by using caprolactam (CPL), and acetamide (AC) as the mixed diluent. When the ternary system was composed of 15 wt.% P(AN-MA), 90 wt.% CPL, and 10 wt.% AC and formed in a 25 °C air bath, the membrane exhibited the highest water flux of 8107 L/m2·h. The P(AN-MA) membrane contained hydrophobic groups (-COOCH3) and hydrophilic groups (-CN), leading it to exhibit oleophobic properties underwater and hydrophobic properties in oil. The membrane demonstrates efficient separation of immiscible oil/water mixtures. The pure water flux of the petroleum ether/water mixture measured 870 L/m2·h, and the pure oil flux of the petroleum tetrachloride/water mixture measured 1230 L/m2·h under the influence of gravity. Additionally, the recovery efficiency of diluents through recrystallization was 85.3%, significantly reducing potential pollution and production costs.

An eco-friendly and facile method for oil-water separation using the bio-Zn oxide-based superhydrophobic membrane.

This manuscript presents a novel approach for developing an environmentally friendly and effective oil-water separation membrane. Achieving a superhydrophobic (SH) coating on textile fabric (TF) involved a two-step process. Initially, the surface roughness was enhanced by applying bio-zinc oxide (ZnO) nanoparticles obtained from Thymbra spicata L. Subsequently, the roughened surface was modified with stearic acid, a material known for its low surface energy. The bio-ZnO nanoparticles exhibit a circular morphology with an average size of 21 nm. The coating demonstrated remarkable mechanical stability, maintaining SH properties even after an abrasion length of 300 mm. Chemical stability studies revealed that the prepared membrane retained SH properties within a pH range of 5-11, which ensures robust performance. Absorption capacity measurements showcased different capacities for n-hexane (Hex), corn oil (C.O), and silicone oil (S.O), with consistent performance over 10 absorption-desorption cycles. High oil-water separation efficiencies were achieved for hexane, C.O, and S.O, emphasizing the coating's versatility. Flux rate measurements demonstrated that oil passed through the membrane efficiently, with the highest flux observed for Hex. The prepared SH membrane has superior mechanical and chemical stability and high separation efficiencies, which positions it as a promising candidate for diverse industrial applications.

Enhancing oil-water emulsion separation via synergistic filtration using graphene oxide-silver oxide nanocomposite-embedded polyethersulfone membrane.

This study introduces an innovative approach for enhancing oil-water emulsion separation using a polyethersulfone (PES) membrane embedded with a nanocomposite of graphene oxide (GO) and silver oxide (AgO). The composite membrane, incorporating PES and polyvinyl chloride (PVC), demonstrates improved hydrophilicity, structural integrity and resistance to fouling. Physicochemical characterization confirms successful integration of GO and AgO, leading to increased tensile strength, porosity and hydrophilicity. Filtration tests reveal substantial improvements in separating various oils from contaminated wastewater, with the composite membrane exhibiting superior efficiency and reusability compared to pristine PES membranes. This research contributes to the development of environmentally friendly oil-water separation methods with broad industrial applications.

Superhydrophobic magnetic Fe3O4 polyurethane sponges for oil-water separation and oil-spill recovery.

The effective and affordable separation of oil and water, a crucial process in the safe handling of environmental disasters such as crude oil spills and recovery of valuable resources, is a highly sought-after yet challenging task. Herein, superhydrophobic PU sponge was fabricated for the fast and cost-effective adsorptive separation of oil and different organic solvents from water. Octadecyltrichlorosilane (OTS)-functionalized Fe3O4@SiO2 core-shell microspheres were dip-coated on the surface of porous materials via a dip-coating process, thereby endowing them with superhydrophobicity. Owing to the hydrophobic interaction between OTS molecules and oil and increased capillary force in the micropores, the resulting superhydrophobic sponge served as a selective oil-sorbent scaffold for absorbing oil from oil-water mixtures, including oil-water suspensions and emulsions. Remarkably, after the recovery of the adsorbed oil via mechanical extrusion, these superhydrophobic materials could be reused multiple times and maintain their oil-water separation efficacy even after 10 oil-water separation cycles.

Macrocycle Self-Assembly Hydrogel for High-Efficient Oil-Water Separation.

Supramolecular hydrogels involved macrocycles have been explored widely in recent years, but it remains challenging to develop hydrogel based on solitary macrocycle with super gelation capability. Here, the construction of lantern[33 ]arene-based hydrogel with low critical gelation concentration (0.05 wt%), which can be used for efficient oil-water separation, is reported. The lantern[33 ]arenes self-assemble into hydrogen-bonded organic nanoribbons, which intertwine into entangled fibers to form hydrogel. This hydrogel which exhibits reversible pH-responsiveness characteristics can be coated on stainless-steel mesh by in situ sol-gel transformation. The resultant mesh exhibits excellent oil-water separation efficiency (>99%) and flux (>6 × 104 L m-2 h-1 ). This lantern[33 ]arene-based hydrogel not only sheds additional light on the gelation mechanisms for supramolecular hydrogels, but also extends the application of macrocycle-based hydrogels as functional interfacial materials.

Scalable Fabrication of Superhydrophobic Coating with Rough Coral Reef-Like Structures for Efficient Self-Cleaning and Oil-Water Separation: An Experimental and Molecular Dynamics Simulation Study.

Superhydrophobic coating has a great application prospect in self-cleaning and oil-water separation but remains challenging for large-scale preparation of robust and weather-resistant superhydrophobic coatings via facile approaches. Herein, this work reports a scalable fabrication of weather-resistant superhydrophobic coating with multiscale rough coral reef-like structures by spraying the suspension containing superhydrophobic silica nanoparticles and industrial coating varnish on various substrates. The coral reef-like structures effectively improves the surface roughness and abrasion resistance. Rapid aging experiments (3000 h) and the outdoor building project application (3000 m2 ) show that the sprayed superhydrophobic coating exhibits excellent self-cleaning properties, weather resistance, and environmental adaptability. Moreover, the combined silica-coating varnish-polyurethane (CSCP) superhydrophobic sponge exhibits exceptional oil-water separation capabilities, selectively absorbing the oils from water up to 39 times of its own weight. Furthermore, the molecular dynamics (MD) simulation reveals that the combined effect of higher surface roughness, smaller diffusion coefficient of water molecules, and weaker electrostatic interactions between water and the surface jointly determines the superhydrophobicity of the prepared coating. This work deepens the understanding of the anti-wetting mechanism of superhydrophobic surfaces from the perspective of energetic and kinetic properties, thereby paving the way for the rational design of superhydrophobic materials and their large-scale applications.

Preparation of pH-responsive reversible wettable surfaces and application for oil-water separation.

With the continuous development of society, the discharge of oily wastewater in daily life and industry has gradually increased, causing considerable damage to the environment, and how to effectively treat oily wastewater is an urgent problem. In this paper, a simple method is proposed to prepare superhydrophobic stainless steel mesh with pH response. The relationship between the ratio of mixed thiols and the surface wettability was explored, as well as the morphology, chemical composition, and pH-responsive mechanism of the stainless steel mesh surface were analyzed, and the separation efficiency, recycling ability, and backwashing ability of the mesh were explored by oil-water separation experiments. It was found that when the molar fraction of 11-mercaptoundecanoic acid and 1-decanethiol in the mixed mercaptan was 2:3, the water contact angle of the surface at this point was 156.5 ± 1°, with pH response characteristics and good oil-water separation efficiency, backwashing and recycling capabilities.

Facile Fabrication of Superelastic, Hydrophobic, and Hierarchical Polydimethylsiloxane@nanocelluloses Aerogels for Durable Oil/Water Separation.

Nanocelluloses (NCs)-based aerogels have gradually attracted attention due to their excellent performance in oil recovery for mitigating environmental pollution caused by oil spillages. However, hydrophobicity due to polyhydroxy groups and fragile in water, as well as a complicated fabricating process, significantly restrict their practical applications. Herein, a facile route is reported to fabricate superelastic polydimethylsiloxane (PDMS)@NCs aerogels through a Pickering emulsion strategy. The hierarchical PDMS@NCs aerogels exhibit function-dependent porous structures and integrated properties of hydrophobicity and lipophilicity, stemming from the synergistic effect of the hydrophobic skin layer and porous matrix. The resulting aerogels are capable of continuous oil/water filtration by adsorption-extrusion with a flux up to 4300 L m-2 h-1 and a separation efficiency of 99.9%. Therefore, this provides a new route for the rational design of morphology-tunable NCs-based aerogels and affords a reference for its practical application in durable oil/water separation.

Superhydrophobic Thermoplastic Polyurethane Foam Fabricated by Phase Separation and Silica Coating for Oil-Water Separation.

Oil spills and the presence of oily wastewater have resulted in substantial ecological damage. Superhydrophobic polymer foam with selectivity and adsorption capacity is a promising candidate for efficient oil-water separation. In this study, a method that combines phase separation and silica coating to produce superhydrophobic thermoplastic polyurethane (TPU) foam is proposed. The TPU foam demonstrates superhydrophobicity with a water contact angle of 155.62°, and exhibits a maximum saturated adsorption capacity of 54.11 g g-1 . Furthermore, the foam can be utilized as a filter for oil-water separation, maintaining its filtration efficiency (41.2 m3  m2  h-1 ) even after ten filtration cycles.

A Superhydrophobic Trifluoromethyl-Containing Covalent Organic Framework Membrane for Efficient Oil/Water Separation.

Oily water caused in the process of industry leads to not only the waste of resources, but also environmental pollution. Membrane separation, as a facile and efficient separation technology, has attracted widespread attention in the field of oil/water separation. The development of membrane materials with high separation performance is one of the key elements to improve separation efficiency. In this work, a superhydrophobic membrane composited with a trifluoromethyl-containing covalent organic framework (COF) is prepared, which exhibits excellent performance on separations of oil/water mixtures and water-in-oil emulsions. For different composition of oil/water mixtures, the highest flux of oil is up to 32 000 L m-2  h-1 and oil/water separation efficiency is above 99%. Moreover, the high oil/water separation efficiency remains unchanged after successive cycles. This work provides a feasible scheme for the design of high-efficiency oil/water separation membranes.

MOF@Polydopamine-incorporated membrane with high permeability and mechanical property for efficient fouling-resistant and oil/water separation.

Metal organic frameworks (MOFs) have demonstrated great potential for their favorable impacts on the performance of water treatment membranes. Herein, the novel nanoparticles based on both nanoporous MOFs and organic PDA layer was exploited as a novel dopant for the fabrication of PES ultrafiltration (UF) membranes. The PDA was synthesized via oxidative self-polymerization under alkaline conditions and formed adhesive coatings on dispersed MOF. The properties of resulting membranes on the porosity, membrane morphology, hydrophilicity, permeability and anti-fouling performance were adequately investigated. The membranes incorporated with MOF@PDA exhibited exceptionally high permeability (209.02 L m-2·h-1), which is approximately 6 times higher than that of the pure PES membrane, and high BSA rejection (99.12%). Notably, the mechanical property and hydrophilicity of the PES membrane were both enhanced by MOF@PDA, and it has been demonstrated that greater hydrophilicity prevents fouling under practical conditions, which results in significant improvements in flux recovery ratio (FRR) (82%). In addition, the modified PES membranes were used to purify the oil/water emulsion, and the results indicates that the membranes have high permeability and rejection of oil/water emulsion, showing its great promise in practical oily sewage remediation.

Hierarchical Ni-Mn LDHs@CuC2O4 Nanosheet Arrays-Modified Copper Mesh: A Dual-Functional Material for Enhancing Oil/Water Separation and Supercapacitors.

The pursuit of superhydrophilic materials with hierarchical structures has garnered significant attention across diverse application domains. In this study, we have successfully crafted Ni-Mn LDHs@CuC2O4 nanosheet arrays on a copper mesh (CM) through a synergistic process involving chemical oxidation and hydrothermal deposition. Initially, CuC2O4 nanosheets were synthesized on the copper mesh, closely followed by the growth of Ni-Mn LDHs nanosheets, culminating in the establishment of a multi-tiered surface architecture with exceptional superhydrophilicity and remarkable underwater superoleophobicity. The resultant Ni-Mn LDHs@CuC2O4 CM membrane showcased an unparalleled amalgamation of traits, including superhydrophilicity, underwater superoleophobicity, and the ability to harness photocatalytic forces for self-cleaning actions, making it an advanced oil-water separation membrane. The membrane's performance was impressive, manifesting in a remarkable water flux range (70 kL·m-2·h-1) and an efficient oil separation capability for both oil/water mixture and surfactant-stabilized emulsions (below 60 ppm). Moreover, the innate superhydrophilic characteristics of the membrane rendered it a prime candidate for deployment as a supercapacitor cathode material. Evidenced by a capacitance of 5080 mF·cm-2 at a current density of 6 mA cm-2 in a 6 M KOH electrolyte, the membrane's potential extended beyond oil-water separation. This work not only introduces a cutting-edge oil-water separation membrane and supercapacitor electrode but also offers a promising blueprint for the deliberate engineering of hierarchical structure arrays to cater to a spectrum of related applications.