Recent Studies of Membranes for Liquids Separation and Water Treatment.

Rapid urbanization and industrialization in the past decades have resulted in vast amounts of wastewater containing pollutants such as inorganic chemicals, pathogens, pharmaceuticals, plant nutrients, petrochemical products, and microplastics [...].

Recent Developments in Two-Dimensional Materials-Based Membranes for Oil-Water Separation.

The industrialization witnessed in the last century has resulted in an unprecedented increase in water pollution. In particular, the water pollution induced by oil contaminants from oil spill accidents, as well as discharges from pharmaceutical, oil/gas, and metal processing industries, have raised concerns due to their potential to pose irreversible threats to the ecosystems. Therefore, the effective treating of these large volumes of oily wastewater is an inevitable challenge to address. Separating oil-water mixtures by membranes has been an attractive technology due to the high oil removal efficiency and low energy consumption. However, conventional oil-water separation membranes may not meet the complex requirements for the sustainable treatment of wastewater due to their relatively shorter life cycle, lower chemical and thermal stability, and permeability/selectivity trade-off. Recent advancements in two-dimensional (2D) materials have provided opportunities to address these challenges. In this article, we provide a brief review of the most recent advancements in oil-water separation membranes modified with 2D materials, with a focus on MXenes, graphenes, metal-organic frameworks, and covalent organic frameworks. The review briefly covers the backgrounds, concepts, fabrication methods, and the most recent representative studies. Finally, the review concludes by describing the challenges and future research directions.

Autonomous-Strengthening Adhesive Provides Hydrolysis-Resistance and Enhanced Mechanical Properties in Wet Conditions.

The low-viscosity adhesive that is used to bond composite restorative materials to the tooth is readily damaged by acids, enzymes, and oral fluids. Bacteria infiltrate the resulting gaps at the composite/tooth interface, demineralize the tooth, and further erode the adhesive. This paper presents the preparation and characterization of a low-crosslink-density hydrophilic adhesive that capitalizes on sol-gel reactions and free-radical polymerization to resist hydrolysis and provide enhanced mechanical properties in wet environments. Polymerization behavior, water sorption, and leachates were investigated. Dynamic mechanical analyses (DMA) were conducted using water-saturated adhesives to mimic load transfer in wet conditions. Data from all tests were analyzed using appropriate statistical tests (α = 0.05). The degree of conversion was comparable for experimental and control adhesives at 88.3 and 84.3%, respectively. HEMA leachate was significantly lower for the experimental (2.9 wt%) compared to control (7.2 wt%). After 3 days of aqueous aging, the storage and rubbery moduli and the glass transition temperature of the experimental adhesive (57.5MPa, 12.8MPa, and 38.7 °C, respectively) were significantly higher than control (7.4MPa, 4.3 MPa, and 25.9 °C, respectively). The results indicated that the autonomic sol-gel reaction continues in the wet environment, leading to intrinsic reinforcement of the polymer network, improved hydrolytic stability, and enhanced mechanical properties.

Frost Delay of a Water-Absorbing Surface with Engineered Wettability via Nonfreezing Water.

Frost is common when a solid surface is subjected to a humid and cold environment. It can cause various inconveniences, complications, or fatal accidents. Water-repellent surfaces have demonstrated an antifreezing capability by enabling the water droplets to roll or bounce off before they freeze. However, these surfaces are often limited by their inability to shed the small water condensates, which can eventually grow and freeze. Recently, surfaces that can rapidly absorb and hydrogen bond with these water condensates have demonstrated significant delay in frost formation and growth. This is attributed to a lower freezing temperature of the absorbed water which makes it stay in a nonfreezing state. Herein, we report a surface with preferential wettability of water over oil (i.e., superhydrophilic and oleophobic wettability) that can significantly delay frost formation. The surface is fabricated by copolymerizing poly(ethylene glycol) diacrylate (PEGDA) and perfluorinated acrylate (1H,1H,2H,2H-heptadecafluorodecyl acrylate, HDF-acrylate) applied to a silane-grafted glass substrate (HDF-PEGDA). An HDF-PEGDA surface can quickly absorb condensed water which enables it to delay frost formation and growth for up to 20 min at a surface temperature of -35 °C. Also, the surface demonstrates that its frost-resistant capability remains almost unaffected even after being submerged in an oil bath due to its in-air oil repellency. Differential scanning calorimetry (DSC) measurements reveal that the significant quantity of absorbed water in an HDF-PEGDA surface remains in a nonfreezing state with a Tm value as low as -33 °C. A mathematical model that can predict the time at which the surface begins to be covered with frost is developed. Finally, an HDF-PEGDA is layered with a PEGDA copolymerized with sodium acrylate (Na-acrylate) that enables the continuous release of the absorbed water by posing forward osmotic pressure and regeneration of an HDF-PEGDA surface.

Water-Responsive Self-Repairing Superomniphobic Surfaces via Regeneration of Hierarchical Topography.

Superomniphobic surfaces that can self-repair physical damage are desirable for sustainable performance over time in many practical applications that include self-cleaning, corrosion resistance, and protective gears. However, fabricating such self-repairing superomniphobic surfaces has thus far been a challenge because it necessitates the regeneration of both low-surface-energy materials and hierarchical topography. Herein, a water-responsive self-repairing superomniphobic film is reported by utilizing cross-linked hydroxypropyl cellulose (HPC) composited with silica (SiO2) nanoparticles (HPC-SiO2) that is treated with a low-surface-energy perfluorosilane. The film can repair physical damage (e.g., a scratch) in approximately 10 s by regenerating its hierarchical topography and low-surface-energy material upon the application of water vapor. The repaired region shows an almost complete recovery of its inherent superomniphobic wettability and mechanical hardness. The repairing process is driven by the reversible hydrogen bond between the hydroxyl (-OH) groups which can be dissociated upon exposure to water vapor. This results in a viscous flow of the HPC-SiO2 film into the damaged region. A mathematical model composed of viscosity and surface tension of the HPC-SiO2 film can describe the experimentally measured viscous flow with reasonable accuracy. Finally, we demonstrate that the superomniphobic HPC-SiO2 film can repair physical damage by a water droplet pinned on a damaged area or by sequential rolling water droplets.

Predicting kinetics of water-rich permeate flux through photocatalytic mesh under visible light illumination.

Membrane-based separation technologies are attractive to remediating unconventional water sources, including brackish, industrial, and municipal wastewater, due to their versatility and relatively high energy efficiency. However, membrane fouling by dissolved or suspended organic substances remains a primary challenge which can result in an irreversible decline of the permeate flux. To overcome this, membranes have been incorporated with photocatalytic materials that can degrade these organic substances deposited on the surface upon light illumination. While such photocatalytic membranes have demonstrated that they can recover their inherent permeability, less information is known about the effect of photocatalysis on the kinetics of the permeate flux. In this work, a photocatalytic mesh that can selectively permeate water while repelling oil was fabricated by coating a mixture of nitrogen-doped TiO2 (N-TiO2) and perfluorosilane-grafted SiO2 (F-SiO2) nanoparticles on a stainless steel mesh. Utilizing the photocatalytic mesh, the time-dependent evolution of the water-rich permeate flux as a result of photocatalytic degradation of the oil was studied under the visible light illumination. A mathematical model was developed that can relate the photocatalytic degradation of the organic substances deposited on a mesh surface to the evolution of the permeate flux. This model was established by integrating the Langmuir-Hinshelwood kinetics for photocatalysis and the Cassie-Baxter wettability analysis on a chemically heterogeneous mesh surface into a permeate flux relation. Consequently, the time-dependent water-rich permeate flux values are compared with those predicted by using the model. It is found that the model can predict the evolution of the water-rich permeate flux with a goodness of fit of 0.92.

Engineered Nanoparticles with Decoupled Photocatalysis and Wettability for Membrane-Based Desalination and Separation of Oil-Saline Water Mixtures.

Membrane-based separation technologies are the cornerstone of remediating unconventional water sources, including brackish and industrial or municipal wastewater, as they are relatively energy-efficient and versatile. However, membrane fouling by dissolved and suspended substances in the feed stream remains a primary challenge that currently prevents these membranes from being used in real practices. Thus, we directly address this challenge by applying a superhydrophilic and oleophobic coating to a commercial membrane surface which can be utilized to separate and desalinate an oil and saline water mixture, in addition to photocatalytically degrading the organic substances. We fabricated the photocatalytic membrane by coating a commercial membrane with an ultraviolet (UV) light-curable adhesive. Then, we sprayed it with a mixture of photocatalytic nitrogen-doped titania (N-TiO2) and perfluoro silane-grafted silica (F-SiO2) nanoparticles. The membrane was placed under a UV light, which resulted in a chemically heterogeneous surface with intercalating high and low surface energy regions (i.e., N-TiO2 and F-SiO2, respectively) that were securely bound to the commercial membrane surface. We demonstrated that the coated membrane could be utilized for continuous separation and desalination of an oil-saline water mixture and for simultaneous photocatalytic degradation of the organic substances adsorbed on the membrane surface upon visible light irradiation.

Reversible adsorption and desorption of PFAS on inexpensive graphite adsorbents via alternating electric field.

Per- and polyfluoroalkyl substances (PFAS) have been extensively utilized in practical applications that include surfactants, lubricants, and firefighting foams due to their thermal stability and chemical inertness. Recent studies have revealed that PFAS were detected in groundwater and even drinking water systems which can cause severe environmental and health issues. While adsorbents with a large specific surface area have demonstrated effective removal of PFAS from water, their capability in desorbing the retained PFAS has been often neglected despite its critical role in regeneration for reuse. Further, they have demonstrated a relatively lower adsorption capacity for PFAS with a short fluoroalkyl chain length. To overcome these limitations, electric field-aided adsorption has been explored. In this work, reversible adsorption and desorption of PFAS dissolved in water upon alternating voltage is reported. An inexpensive graphite adsorbent is fabricated by using a simple press resulting in a mesoporous structure with a BET surface area of 132.9 ± 10.0 m2 g-1. Electric field-aided adsorption and desorption experiments are conducted by using a custom-made cell consisting of two graphite electrodes placed in parallel in a polydimethylsiloxane container. Unlike the conventional sorption process, a graphite electrode exhibits a higher adsorption capacity for PFAS with a short fluoroalkyl chain (perfluoropentanoic acid, PFPA) in comparison to that with a long fluoroalkyl chain (perfluorooctanoic acid, PFOA). Upon alternating the voltage to a negative value, the retained PFPA or PFOA is released into the surrounding water. Finally, we engineered a device module mounted on a gravity-assisted apparatus to demonstrate electrosorption of PFAS and collection of high purity water.

Selective Wettability Membrane for Continuous Oil-Water Separation and In Situ Visible Light-Driven Photocatalytic Purification of Water.

Membrane-based technologies are attractive for remediating oily wastewater because they are relatively energy-efficient and are applicable to a wide range of industrial effluents. For complete treatment of oily wastewater, removing dissolved contaminants from the water phase is typically followed by adsorption onto an adsorbent, which complicates the process. Here, an in-air superhydrophilic and underwater superoleophobic membrane-based continuous separation of surfactant-stabilized oil-in-water emulsions and in situ decontamination of water by visible-light-driven photocatalytic degradation of dissolved organic contaminants is reported. The membrane is fabricated by utilizing a thermally sensitized stainless steel mesh coated with visible light absorbing iron-doped titania nanoparticles. Post annealing of the membrane can enhance the adhesion of nanoparticles to the membrane surface by formation of a bridge between them. An apparatus that enables continuous separation of surfactant-stabilized oil-in-water emulsion and in situ photocatalytic degradation of dissolved organic matter in the water-rich permeate upon irradiation of visible light on the membrane surface with greater than 99% photocatalytic degradation is developed. The membrane demonstrates the recovery of its intrinsic water-rich permeate flux upon continuous irradiation of light after being contaminated with oil. Finally, continuous oil-water separation and in situ water decontamination is demonstrated by photocatalytically degrading model toxins in water-rich permeate.

Thermally Sensitized Membranes for Crude Oil-Water Remediation under Visible Light.

Effective remediation of produced water requires separating crude oil-water mixture and removing the dissolved organic pollutants. Membranes with selective wettability for water over oil enable the gravity-driven separation of an oil-water mixture by allowing water to permeate through while repelling oil. However, these membranes are often limited by their inability to remove the dissolved organic pollutants. In this work, a membrane with in-air superhydrophilic and underwater superoleophobic wettability is fabricated by thermal annealing of a stainless steel mesh. The resulting membrane possesses a hierarchical surface texture covered with a photocatalytic oxide layer composed of iron oxide and chromium oxide. The membrane exhibits chemical and mechanical robustness, which makes it suitable for remediation of crude oil and water mixture. Further, after being fouled by crude oil, the membrane can recover its inherent water-rich permeate flux upon visible light irradiation. Finally, the membrane demonstrates that it can separate surfactant-stabilized crude oil-in-water emulsion under gravity and decontaminate water-rich permeate by photocatalytic degradation of dissolved organic pollutants upon continuous irradiation of visible light.

Synthesis of oxygen functionalized carbon nanotubes and their application for selective catalytic reduction of NO x with NH3.

Oxygen functionalized carbon nanotubes synthesized by surface acid treatment were used to improve the dispersion properties of active materials for catalysis. Carbon nanotubes have gained attention as a support for active materials due to their high specific surface areas (400-700 m2 g-1) and chemical stability. However, the lack of surface functionality causes poor dispersion of active materials on carbon nanotube supports. In this study, oxygen functional groups were prepared on the surface of carbon nanotubes as anchoring sites for decoration with catalytic nanoparticles. The oxygen functional groups were prepared through a chemical acid treatment using sulfuric acid and nitric acid, and the amount of functional groups was controlled by the reaction time. Vanadium, tungsten, and titanium oxides as catalytic materials were dispersed using an impregnation method on the synthesized carbon nanotube surfaces. Due to the high density of oxygen functional groups, the catalytic nanoparticles were well dispersed and reduced in size on the surface of the carbon nanotube supports. The selective catalytic reduction catalyst with the oxygen functionalized carbon nanotube support exhibited enhanced NO x removal efficiency of over 90% at 350-380 °C which is the general operating temperature range of catalysis in power plants.

Self-Healable Superomniphobic Surfaces for Corrosion Protection.

Corrosion-protective surfaces are of the utmost relevance to ensure long-term stability and reliability of metals and alloys by limiting their interactions with corrosive species, such as water and ions. However, their practical applications are often limited either by the inability to repel low surface tension liquids such as oils and alcohols or by poor mechanical durability. Here, a superomniphobic surface is reported that can display very high contact angles for both high and low surface tension liquids as well as for concentrated acids and bases. Such extreme repellency allowed for approximately 20% of the corrosion rate compared to the conventional superhydrophobic corrosion protective coatings. Furthermore, the superomniphobic surface can autonomously repair mechanical damage at an elevated temperature (60 °C) within a short period of time (60 s), and the surface can restore its intrinsic corrosion protection performance. Such superomniphobic surfaces thus offer a wide range of potential applications, including pipelines, with sustainable corrosion protection and rust inhibitors for steel in reinforced concrete.