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An electrochemical nitrogen reduction reaction (ENRR) is considered a promising alternative for the traditional Haber-Bosch process. In this study, we present a method for improving the ENRR by controlling the wettability of the catalyst surface, suppressing the hydrogen evolution reaction (HER) while facilitating N

This study reports the superior performance of graphene nanosheet (GNS) materials over Vulcan XC incorporated as a cathode catalyst in Li–O2 battery. The GNSs employed were synthesized from a novel, eco-friendly, and cost-effective technique involving chamber detonation of oxygen (O2) and acetylene (C2H2) precursors. Two GNS catalysts i.e., GNS-1 and GNS-2 fabricated with 0.3 and 0.5 O2/C2H2 precursor molar ratios, respectively, were utilized in this study. Specific surface area (SSA) analysis revealed significantly higher SSA and total pore volume for GNS-1 (180 m2 g−1, 0.505 cm3 g−1) as compared with GNS-2 (19 m2 g−1, 0.041 cm3 g−1). GNS-1 exhibited the highest discharge capacity (4.37 Ah g-1) and superior cycling stability compared with GNS-2 and Vulcan XC. Moreover, GNS-1 demonstrated promising performance at higher current densities (0.2 and 0.3 mA cm−2) and with various organic electrolytes. The superior performance of GNS-1 can be ascribed to its higher mesopore volume, SSA, and optimum wettability compared to its counterparts.

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 (1

Separation operations are critical across a wide variety of manufacturing industries and account for about one-quarter of all in-plant energy consumption in the United States. Conventional liquid-liquid separation operations require either thermal or chemical treatment, both of which have a large environmental impact and carbon footprint. Consequently, there is a great need to develop sustainable, clean methodologies for separation of miscible liquid mixtures. The greatest opportunities to achieve this lie in replacing high-energy separation operations (e.g., distillation) with low-energy alternatives such as liquid-liquid extraction. One of the primary design challenges in liquid-liquid extraction is to maximize the interfacial area between two immiscible (e.g., polar and nonpolar) liquids for efficient mass transfer. However, this often involves energy-intensive methods including ultrasonication, pumping the feed and the extractant through packed columns with high tortuosity, or using a supercritical fluid as an extractant. Emulsifying the feed and the extractant, especially with a surfactant, offers a large interfacial area, but subsequent separation of emulsions can be energy-intensive and expensive. Thus, emulsions are typically avoided in conventional extraction operations. Herein, we discuss a novel, easily scalable, platform separation methodology termed CLEANS (continuous liquid-liquid extraction and in-situ membrane separation). CLEANS integrates emulsion-enhanced extraction with continuous, gravity-driven, membrane-based separation of emulsions into a single unit operation. Our results demonstrate that the addition of a surfactant and emulsification significantly enhance extraction (by >250% in certain cases), even for systems where the best extractants for miscible liquid mixtures are known. Utilizing the CLEANS methodology, we demonstrate continuous separation of a wide range of miscible liquid mixtures, including soluble organic molecules from oils, alcohols from esters, and even azeotropes.

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.

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.

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 NOx removal efficiency of over 90% at 350–380 °C which is the general operating temperature range of catalysis in power plants.

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.

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 m

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., An apparatus enables continuous separation of surfactant‐stabilized oil‐in‐water emulsion and in situ photocatalytic degradation of organic matter in the water‐rich permeate upon visible light irradiation. The membrane demonstrates recovery of its intrinsic water‐rich permeate flux upon continuous light irradiation after contamination with oil. The predictions using the first‐order kinetic model match well with the experimental data of photocatalytic degradation.

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 m

Herein, we report electrochemically durable oxygen reduction reaction catalysts for proton exchange membrane fuel cells under conditions of hydrogen starvation. Insufficient hydrogen supply during transient conditions leads to a cell reversal state in a proton exchange membrane fuel cell, and oxidation of the carbon support severely decreases the cell performance. The use of carbon nanotubes as a support for the oxygen reduction reaction catalyst is found to suppress carbon oxidation due to the high crystallinity, low defect density, and high aspect ratio, which results in a consistent cell voltage, electrochemical surface area, and electrical resistance, even after 100 rounds of cell reversal. This study demonstrates the excellent durability of proton exchange membrane fuel cells with a Pt/Carbon nanotube electrode, as confirmed by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and cyclic voltammetry analysis.

Separating oil-water mixtures is critical in a variety of practical applications, including the treatment of industrial wastewater, oil spill cleanups, as well as the purification of petroleum products. Among various methodologies that have been utilized, membranes are the most attractive technology for separating oil-water emulsions. In recent years, selective wettability membranes have attracted particular attention for oil-water separations. The membrane surfaces with hydrophilic and in-air oleophobic wettability have demonstrated enhanced effectiveness for oil-water separations in comparison with underwater oleophobic membranes. However, developing a hydrophilic and in-air oleophobic surface for a membrane is not a trivial task. The coating delamination process is a critical challenge when applying these membranes for separations. Inspired by the above, in this study we utilize poly(ethylene glycol)diacrylate (PEGDA) and 1H,1H,2H,2H-heptadecafluorodecyl acrylate (F-acrylate) to fabricate a hydrophilic and in-air oleophobic coating on a filter. We utilize methacryloxypropyl trimethoxysilane (MEMO) as an adhesion promoter to enhance the adhesion of the coating to the filter. The filter demonstrates robust oil repellency preventing oil adhesion and oil fouling. Utilizing the filter, gravity-driven and continuous separations of surfactant-stabilized oil-water emulsions are demonstrated. Finally, we demonstrate that the filter can be reused multiple times upon rinsing for further oil-water separations.

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.

Precise control over micro- and nano-particle composition, size and shape is critical for developing the next generation of successful drug carriers. Fabrication methods also need to be able to create charged and multiphasic particles with ease in order to improve the overall efficiency of drug delivery systems. Multiple phases in a single particle allow for the delivery of multiple payloads without negative payload interactions. The addition of charged polyelectrolyte (PEL) multilayers can improve particle stability, targeting efficacy, drug-release kinetics, and increase the types of payloads that can be delivered. Many of the traditional methods for PEL functionalization of multiphasic particles are time and energy intensive which significantly limits their scalability, and therefore therapeutic potential. In this work, we combine the bulk layer-by-layer PEL application methodology with our previously developed technique of fabricating multiphasic particles on substrates with patterned wettability to synthesize biocompatible, monodisperse, Janus polymer-PEL particles.

The separation of oil-water mixtures is a widely utilized unit operation, used for handling a wide variety of mixtures from industry including: petroleum drilling and refining, fracking, waste-water treatment, mining, metal fabrication and machining, textile and leather processing, and rendering. Membrane-based methods have become increasingly attractive for the separation of oil-water mixtures because they are relatively energy-efficient, can be readily used to separate a variety of industrial feed streams, and provide consistent permeate quality. In this perspective, we discuss the design strategies for membranes with selective wettability i.e., membranes that are either selectively wet by, or prevent wetting by, the oil or water phase. The design strategies include the parameterization of two important physical characteristics: the surface porosity and the breakthrough pressure. We also discuss how they are related for membranes with a periodic geometry. On the basis of this understanding, we explore principles that allow for the systematic design of membranes with selective wettability. A review of the current literature on the separation of oil-water mixtures using membranes with differing wettabilities is also presented. Finally, we conclude by discussing the current challenges and outlook for the future of the field.

Precise control over the geometry and chemistry of multiphasic particles is of significant importance for a wide range of applications. In this work, we have developed one of the simplest methodologies for fabricating monodisperse, multiphasic micro- and nanoparticles possessing almost any composition, projected shape, modulus, and dimensions as small as 25 nm. The synthesis methodology involves the fabrication of a nonwettable surface patterned with monodisperse, wettable domains of different sizes and shapes. When such patterned templates are dip-coated with polymer solutions or particle dispersions, the liquids, and consequently the polymer or the particles, preferentially self-assemble within the wettable domains. Utilizing this phenomenon, we fabricate multiphasic assemblies with precisely controlled geometry and composition through multiple, layered depositions of polymers and/or particles within the patterned domains. Upon releasing these multiphasic assemblies from the template using a sacrificial layer, we obtain multiphasic particles. The templates can then be readily reused (over 20 times in our experiments) for fabricating a new batch of particles, enabling a rapid, inexpensive, and easily reproducible method for large-scale manufacturing of multiphasic particles.

Photoresponsive titania surfaces are of great interest due to their unique wettability change upon ultraviolet light illumination. However, their applications are often limited either by the inability to respond to visible light or the need for special treatment to recover the original wettability. Sensitizing TiO2 surfaces with visible light-absorbing materials has been utilized in photovoltaic applications. Here we demonstrate that a dye-sensitized TiO2 surface can selectively change the wettability towards contacting liquids upon visible light illumination due to a photo-induced voltage across the liquid and the underlying surface. The photo-induced wettability change of our surfaces enables external manipulation of liquid droplet motion upon illumination. We show demulsification of surfactant-stabilized brine-in-oil emulsions via coalescence of brine droplets on our dye-sensitized TiO2 surface upon visible light illumination. We anticipate that our surfaces will have a wide range of applications including microfluidic devices with customizable wettability, solar-driven oil–water clean-up and demulsification technologies., Controlling surface wettability using visible light is highly attractive for a range of liquid separation technologies. Here, Varanasi, McKinley and colleagues fabricate dye-sensitized photocatalytic TiO2 surfaces on which liquid droplet motion can be externally manipulated by visible light illumination.

Every day millions of gallons of oil–water mixtures are produced in industries ranging from oil extraction, fracking and mining, to wastewater treatment. Separating these mixtures involves multiple unit operations, which can be expensive and sometimes insufficient, especially as environmental restrictions become increasingly strict on contaminants in discharged water. Other occurrences, such as large oil spills, also require new technologies that enable effective yet economic clean-up. Energy efficient, selective wettability-based membrane technology has the potential to meet these needs. In this chapter, we discuss the fundamentals of wettability and how they can be applied to systematically design membranes with selective wettability that can readily separate free oil and water, as well as emulsions. We also look at membrane surface morphology, surface energy, and the relationships that govern the selective breakthrough of an oil or water phase. Finally, we discuss the recent work in developing oil–water separation membranes based on the idea of selective wettability, the merits and shortcomings of each approach, and the potential areas of future interest in the field.

Titanium dioxide (titania or TiO₂) is well known for its photocatalytic properties and its ability to remove organic contaminants under UV light illumination. It is also known to switch its surface wetting characteristics from being hydrophilic to superhydrophilic under exposure to UV light in air. However, less is known about the switching of the hydrophilicity of TiO₂ surfaces immersed in an oil medium. In this work, self-assembled TiO₂ nanoparticle surfaces are immersed in an oil environment, and the kinetics of contamination-induced hydrophobicity and photoinduced hydrophilicity are studied using in situ contact angle measurements. A simple model is developed to relate the evolution in the measured contact angle to photocatalytically induced changes on the surface of nanoporous titania by integrating the Langmuir–Hinshelwood adsorption isotherm with the Cassie–Baxter analysis of the effective contact angle of a drop sitting on a composite surface. The resulting model can be used to predict and control wetting kinetics in drop coalescence applications. Moreover, it is shown that immersed oil–water separation membranes which have been fouled by low surface tension contaminants can be rapidly recovered in situ using this underwater photocatalytic reaction without the need for backwashing or harsh chemical reagents. Keywords: oil-water; photocatalysis; self-cleaning; titanium dioxide; wetting, Center for Clean Water and Clean Energy at MIT and KFUPM (Grant R15-CW-11)

Superhydrophobic surfaces (i.e., surfaces extremely repellent to water) allow water droplets to bead up and easily roll off from the surface. While a few methods have been developed to fabricate metallic superhydrophobic surfaces, these methods typically involve expensive equipment, environmental hazards, or multi-step processes. In this work, we developed a universal, scalable, solvent-free, one-step methodology based on thermal sensitization to create appropriate surface texture and fabricate metallic superhydrophobic surfaces. To demonstrate the feasibility of our methodology and elucidate the underlying mechanism, we fabricated superhydrophobic surfaces using ferritic (430) and austenitic (316) stainless steels (representative alloys) with roll off angles as low as 4° and 7°, respectively. We envision that our approach will enable the fabrication of superhydrophobic metal alloys for a wide range of civilian and military applications.

There is a critical need for new energy-efficient solutions to separate oil-water mixtures, especially those stabilized by surfactants. Traditional membrane-based separation technologies are energy-intensive and limited, either by fouling or by the inability of a single membrane to separate all types of oil-water mixtures. Here we report membranes with hygro-responsive surfaces, which are both superhydrophilic and superoleophobic, in air and under water. Our membranes can separate, for the first time, a range of different oil-water mixtures in a single-unit operation, with >99.9% separation efficiency, by using the difference in capillary forces acting on the two phases. Our separation methodology is solely gravity-driven and consequently is expected to be highly energy-efficient. We anticipate that our separation methodology will have numerous applications, including the clean-up of oil spills, wastewater treatment, fuel purification and the separation of commercially relevant emulsions.

In this work, the first-ever membrane-based single unit operation that enables gravity driven, on-demand separation of various oil-water mixtures is developed. Using this methodology, the on-demand separation of free oil and water, oil-in-water emulsions, and water-in-oil emulsions is demonstrated, with ≥99.9% separation efficiency. A scaled-up apparatus to separate larger quantities (several liters) of oil-water emulsions is also developed.