Fabrication of Tailored Membranes with Special Surface Wettability Features for Highly Efficient Crude Oil-in-Water Emulsion Separation.

Treating oily wastewater streams such as produced water has a huge potential to resolve the issue of wastewater disposal and generate useful water for reuse. Among different techniques employed for oily wastewater (oil-in-water; O/W emulsion) treatment, membrane-based separation is advantageous owing to its lower energy consumption, recycling, ease of operation, and wider scope of tuning the active layer chemistry for enhanced performance. In line with the possibilities of enhancing the performance of the membranes for efficient O/W emulsion separation, the current work is designed to yield five different variants of polyaniline (PANI) active layers with special surface wettability features (superhyrophilic and underwater superoleophobic) on a ceramic alumina support. To achieve variants of PANI on ceramic alumina supports, emulsion polymerization was carried out, and different concentrations of initiator ammonium persulfate (APS) were applied to lead to PANI-A@Aluminum Oxide membrane, PANI-B@Aluminum Oxide membrane, PANI-C@Aluminum Oxide membrane, PANI-D@Aluminum Oxide membrane, and PANI-E@Aluminum Oxide membrane corresponding to 0.15, 0.25, 0.35, 0.5, and 1.0 M concentrations of initiator. The variation in initiator concentration resulted in different PANI growth patterns; hence, the resultant membranes showed different structural, physical, and performance features. Different characterization techniques including 1H NMR, SEM, FE-TEM, AFM, water contact angle, XRD, EDX, and ATR-FTIR confirmed a more uniform and continuous growth of PANI (PANI-B) using a 0.25 M initiator concentration. The resultant PANI-B@Aluminum Oxide membrane showed an excellent surfactant stabilized crude O/W emulsion separation reaching >99% with a permeate flux of 2154 L m-2 h-1 (LMH) at 4 bar using a 100 ppm surfactant stabilized crude oil-in-water emulsion. The fouling and cleaning cycles revealed that the membrane can be reused with a 70% recovery of the initial permeate flux.

Natural-inspired hierarchic double-Janus solar evaporator for stable clean water production from high-salinity emulsions.

Interfacial solar evaporation shows great potential in clean water production, emulsions separation, and high-salinity brine treatment. However, it remains challenging for the evaporators to maintain a high evaporation rate in the high-salinity emulsions due to the co-pollution of salt and oil. Herein, we first proposed a hierarchic double-Janus solar evaporator (HDJE) with a hydrophobic salt-rejecting top layer and oil-rejecting bottom layer. Compared to the traditional one, HDJE could treat industrial high-salinity oil-in-water emulsions stably for over 70 h, with a stable average evaporation rate of 1.73 kg m-2 h-1 and a high purification efficiency of up to 99.8 % for oil and ions. It was also verified that HDJE could be used for high-efficiency purification of oily concentrated seawater outdoor. An average water production rate of 3.59 kg m-2 d-1 and a TOC removal ratio of over 98 % was obtained. In conclusion, this study provides a novel way to effectively dispose of high-salinity oily wastewater.

In situ reaction enabled surface segregation toward dual-heterogeneous antifouling membranes for oil-water separation.

Fabricating membranes with superior antifouling property and long-term high performance is in great demand for efficient oil-water separation. Herein, we reported a reaction enabled surface segregation method for antifouling membrane fabrication, in which the pre-synthesized fluorinated ternary copolymer Pluronic F127 was coordinated with Ti4+ as segregation additive in the membrane casting bath. Additionally, tannic acid was utilized to enhance the self-assembly of the copolymer in the coagulation bath, and freshly-biomineralized TiO2 was anchored into the membrane surface through hydrogen bond. A hydrogel layer was constructed onto the membrane surface with synergistically tailored heterogeneous chemical composition and heterogeneous geometrical roughness. The dual-heterogeneous membrane exhibited hydrophilic and underwater superoleophobic features, resulting in high water flux (621.7 L m-2 h-1) at low operation pressure of 0.05 MPa and an excellent antifouling property (only 4.8% flux decline during 24-hour filtration). In situ reaction enabled surface segregation method will accelerate the development of antifouling membranes for oil-in-water emulsion separation.

Solar-Driven Evaporators with Thin-Film-Composite Architecture Inspired by Plant Roots for Treating Concentrated Nano-/Submicrometer Emulsions.

Oil/water separation by porous materials has received growing interest over the past years since the ever-increasing oily wastewater discharges seriously threaten our living environment. Purification of nano-sized and concentrated emulsions remains a big challenge because of the sharp flux decline by blocking the pores and fouling the surfaces of those porous materials. Herein, we propose a solar-driven evaporator possessing thin-film-composite architecture to deal with these two bottlenecks. Inspired by plant roots, our evaporator composes of a large-pore sponge wrapped by a thin hydrogel film, which is constructed by the contra-diffusion and cross-linking of alginate and calcium ions at the sponge surface. The dense superoleophobic hydrogel layer serves as a selective barrier that prevents oil emulsions but allows water permeation, while the inner sponge with large pores facilitates water transport within the evaporator, ensuring sufficient water supply for evaporation. By splitting the single evaporator into an array, the evaporator performs a high evaporation rate of ∼3.10 kg·m-2·h-1 and oil removal efficiency above 99.9% for a variety of oil emulsions. Moreover, it displays a negligible decline in the evaporation rate when treating concentrated emulsions for 8 h.

Large-scale preparation of a versatile bioinspired sponge with physic-mechanochemical robustness for multitasking separation.

Developing novel biomaterials integrating robustness and multitasking separation performance are of importance. However, those were limited in application due to the expensive, time-consuming and complex fabrication process. In this work, with the inspiration from high porosity and surface area of natural materials, the porous superhydrophobic melamine sponges (SMS) coated hydrophobic TiO2 and epoxy copolymer were fabricated via a facile, inexpensive, eco-friendly and large-scale strategy. The SMS showed excellent superhydrophobic property, and could well resist the harsh mechanical damage, chemical corrosion, extreme temperature, and irradiation of UV without losing antiwetting ability. Besides, it displayed selective oil absorbing ability, recyclability, and self-cleaning ability. Moreover, the SMS displayed superior multitasking performance for continuous oil/water separation, surfactant-stabilized O/W emulsions separation (separation efficiency above 99%), and bacterial/fungus containing filtration (filtration efficiency over 60% for S. aureus, 90% for E. coli and C. albicans). With the multifaceted features, the SMS is a promising sponge material for treatment of industry oily or bacterial/fungus-containing wastewater in practical application.

Cracked-earth-like titanium carbide MXene membranes with abundant hydroxyl groups for oil-in-water emulsion separation.

Membrane separation technology is one of the best methods to deal with wastewater released from oil spills and industrial wastewater. Therefore, we designed and prepared hydroxyl-rich titanium carbide MXene materials and filtered them onto a commercial polyvinylidene fluoride substrate membrane to obtain a cracked-earth-like MXene membrane with abundant hydroxyl groups and excellent underwater wettability. The underwater oil contact and sliding angles were approximately 157° and less than 3°, respectively. Moreover, the membrane effectively separated a variety of surfactant-stabilized stable emulsions with a high permeation flux of up to 6385 L m-2h-1 bar-1 and offered adequate performance after five cycles of the separation experiment. Additionally, the membrane exhibited remarkable resistance toward corrosive chemicals without any decrease in its underwater wettability performance. For example, the membrane was used to separate the emulsions containing alkali, salt, and acid. This study provides a new strategy to resolve the oily wastewater disposal problem by fabricating a cracked-earth-like MXene membrane with abundant hydroxyl groups.

Suspended Membrane Evaporators Integrating Environmental and Solar Evaporation for Oily Wastewater Purification.

Solar-driven evaporation is promising in oily wastewater treatment, in particular for emulsions, but conventional evaporators suffer from pore blocking by residual oil or contamination by volatile oil compounds in the condensed water. In the current research, we develop a suspended membrane evaporator integrating solar evaporation with oil-in-water emulsion separation. The heating and evaporating interface is separated from the rejecting interface to avoid oil escape and improve heat management. A temperature gradient forms on the membrane surface that can promote evaporation performance by combining both solar and environmental evaporation. Such an evaporator achieves a maximum evaporation rate of 1.645 kg/(m2·h) as well as an apparent evaporation efficiency of 111.9%. Moreover, the superhydrophilic and superoleophobic membrane shows excellent oil repellence and emulsion rejection, which can achieve an oil removal efficiency above 98.8% in oil-in-water emulsion separation, and high evaporation rate recovery in cycling tests. A scaled-up membrane evaporator array produces ∼8 kg/(m2·d) of clean water from oily wastewater in outdoor experiments, further demonstrating the strong purification performance of this evaporator in oily wastewater treatment.

Designing of bacterial cellulose-based superhydrophilic/underwater superoleophobic membrane for oil/water separation.

The oil/water (o/w) separation is a global challenge because of the increasing water contamination by oil spill accidents, and oil-containing wastewater produced by food, textile, and petrochemical industries. In this study, we have developed bacterial cellulose (BC) based superhydrophilic/underwater superoleophobic (SUS) membrane for o/w separation. The membrane was designed through a facile method by blending BC nanofibers with silica microparticles (SiO2-MPs), which was further modified by bio-inspired polydopamine (PDA) coatings. The composite membrane exhibited SiO2-MPs dependent o/w separation with a high separation efficiency of >99.9 % and a high flux rate of ∼10,660 Lm-2 h-1 while applying a small negative pressure (0.3-0.5 bar). The membrane with different content of SiO2-MPs also showed the potential to separate oil-in-water emulsion with the highest oil rejection of 98.2 % and the highest flux rate of ∼1250 Lm-2 h-1 on an ultra-low pressure <0.1 bar. Moreover, the membrane showed antifouling properties, recyclability, and stability in harsh conditions.

Bifunctional NiAlFe LDH-coated membrane for oil-in-water emulsion separation and photocatalytic degradation of antibiotic.

A new NiAlFe layered double hydroxide/polydopamine/polyvinylidene fluoride (NiAlFe LDH/PDA/PVDF) membrane was fabricated by in-situ growth of LDH on the PDA modified PVDF membrane. The as-prepared membrane possesses a nano/microscale rough structural surface and displays the superior wettability of superhydrophilicity in air and underwater superoleophobicity. Combining the favourable features of superwettability and hierarchical rough structure, the NiAlFe LDH/PDA/PVDF membrane could effectively separate a series of oil-in-water emulsions with high efficiency (>99%) and high permeation flux (925-1913 L m-2 h-1 bar-1). Besides, owing to the light harvest ability of NiAlFe LDH, the relevant membrane also can be applied as a photocatalysis paper for the light-driven treatment of antibiotic residue in aqueous solution. In which, NiAlFe LDH/PDA/PVDF membrane can effectively degrade typical antibiotic tetracycline within 20 min under UV light irradiation, exhibiting excellent photocatalytic activity. In addition, cyclic experiments demonstrate that NiAlFe LDH/PDA/PVDF membrane has excellent stability and reusability both in oil-in-water emulsion separation and photocatalytic reaction. In general, the findings of this research demonstrate that photo-response LDH modified membranes have potential multiple applications in wastewater treatment.

Fabrication of superhydrophilic PVDF membranes by one-step modification with eco-friendly phytic acid and polyethyleneimine complex for oil-in-water emulsions separation.

Superhydrophilic membranes with simultaneous underwater superoleophobicity are highly desirable and worth exploring for separation of emulsified oil from water. In this work, combining the strong negative charges of phytic acid (PA) and the high cationic charge density of polyethyleneimine (PEI), an eco-friendly PA@PEI polyelectrolyte complex was synthetized in aqueous solution. And then the polyelectrolyte complex was deposited onto hydrophobic PVDF membranes through a one-step assembly approach with high convenience, endowing the membranes with superhydrophilic and underwater superoleophobic property. The as-prepared PA@PEI/PVDF membrane shows outstanding static and dynamic water stability, and was successfully used to separate multiple oil-in-water emulsions, with an average rejection rate exceeding 98.5% and a water flux up to 12203.6 L m-2∙h-1∙bar-1. Furthermore, the water flux can be recovered to a high level after four separation-washing cycles, showing excellent antifouling performance and recovery capability. Together with its natural raw materials and environmentally friendly preparation strategy, the PA@PEI/PVDF membrane shows great potential in practical treatment of emulsified oily wastewater.

A Self-Cleaning Heterostructured Membrane for Efficient Oil-in-Water Emulsion Separation with Stable Flux.

Lack of clean water is a major global challenge. Membrane separation technology is an ideal choice for the treatment of industrial, domestic sewage owing to its low energy consumption and cost. However, membranes are highly susceptible to contamination, particularly during wastewater treatment, which has limited their practical applications in this field. Similarly, the flux of the membrane decreases with prolonged use due to its reduced interlayer spacing. Preparation of membranes with anticontamination properties and stable flux is the key to addressing this problem. In this study, a 2D heterostructure membrane with visible-light-driven self-cleaning performance is prepared via a self-assembly process. Notably, the addition of palygorskite increases the interlayer spacing of the graphene and heterojunction structures, which increases the flux of the membrane and avoids a decrease of the interlayer spacing of the membrane under pressure. The presence of a heterojunction with visible light catalytic properties effectively avoids membrane fouling and avoids a sharp decrease of the permeation flux. Importantly, the prepared 2D membrane has excellent separation performance for oil-water emulsions with both high flux and efficiency. These features suggest great potential for the prepared 2D membrane in wastewater treatment applications.

Biomimetic Silicification on Membrane Surface for Highly Efficient Treatments of Both Oil-in-Water Emulsion and Protein Wastewater.

The worldwide water crisis and water pollution have put forward great challenges to the current membrane technology. Although poly(vinylidene fluoride) (PVDF) porous membranes can find diverse applications for water treatments, the inherent hydrophilicity must be tuned for an energy-/time-saving process. Herein, the surface wettability of PVDF membranes transforming from highly hydrophobicity to highly hydrophilicity was realized via one-step reaction of plant-derived phenol gallic acid and γ-aminopropyltriethoxysilane in aqueous solutions. The surface hydrophilicization can be achieved on porous PVDF membranes by virtue of integration of a mussel-inspired coating and in situ silicification via a "pyrogallol-amino covalent bridge" toward excellent antifouling performance and highly efficient infiltration ability for oily emulsion and protein wastewater treatment. The water flux of a surface-manipulated microfiltration membrane can reach ca. 9246 L m-2 h-1 (54-fold increment compared to that of pristine membrane), oil rejection >99.5% in a three-cycle emulsion separation; the modified ultrafiltration membrane demonstrated benign performance in bovine serum albumin protein interception (rejection as high as ca. 96.6% with water flux of ca. 278.2 L m-2 h-1) and antifouling potential (increase of ca. 70.8%). Our in situ biomimetic silicification under "green" conditions exhibits the great potential of the developed strategy in fabrication of similar multifunctional membranes toward environmental remediation.

Biomimetic Multilayer Nanofibrous Membranes with Elaborated Superwettability for Effective Purification of Emulsified Oily Wastewater.

Creating a porous membrane to effectively separate the emulsified oil-in-water emulsions with energy-saving property is highly desired but remains a challenge. Herein, a multilayer nanofibrous membrane was developed with the inspiration of the natural architectures of earth for gravity-driven water purification. As a result, the obtained biomimetic multilayer nanofibrous membranes exhibited three individual layers with designed functions; they were the inorganic nanofibrous layer to block the serious intrusion of oil to prevent the destructive fouling of the polymeric matrix; the submicron porous layer with designed honeycomb-like cavities to catch the smaller oil droplets and ensures a satisfactory water permeability; and the high porous fibrous substrate with larger pore size provided a template support and allows water to pass through quickly. Consequently, with the cooperation of these three functional layers, the resultant composite membrane possessed superior anti-oil-fouling property and robust oil-in-water emulsion separation performance with good separation efficiency and competitive permeation flux solely under the drive of gravity. The permeation flux of the membrane for the emulsion was up to 5163 L m-2 h-1 with a separation efficiency of 99.5%. We anticipate that our strategy could provide a facile route for developing a new generation of specific membranes for oily wastewater remediation.

A Simple, Green Method to Fabricate Composite Membranes for Effective Oil-in-Water Emulsion Separation.

Most factories discharge untreated wastewater to reduce costs, causing serious environmental problems. Low-cost, biological, environmentally friendly and highly effective materials for the separation of emulsified oil/water mixtures are thus in great demand. In this study, a simple, green method was developed for separating oil-in-water emulsions. A corn straw powder (CSP)-nylon 6,6 membrane (CSPNM) was fabricated by a phase inversion process without any further chemical modification. The CSPNM showed superhydrophilic and underwater superoleophobic properties and could be used for the separation of oil-in-water emulsion with high separation efficiency and flux. The CSPNM maintained excellent separation ability after 20 cycles of separation with an oil rejection >99.60%, and the oil rejection and flux have no obvious change with an increasing number of cycles, suggesting a good antifouling property and the structural stability of CSPNM. In addition, the CSPNM exhibited excellent thermal and chemical stability under harsh conditions of high temperature and varying pH.

Polyaniline coated membranes for effective separation of oil-in-water emulsions.

Polyaniline (PANI) decorated commercial filtration membranes, such as stainless steel meshes (SSMs) with 5µm pore size and polyvinylidene fluoride (PVDF) membranes with 2-0.22µm pore sizes, were fabricated by a simple one-step dilute polymerization at low temperature. Lots of short PANI nanofibers were firmly and uniformly coated onto the membrane surfaces, forming rough micro- and nanoscale structures and leading to underwater superoleophobicity with low oil-adhesion characteristic. Furthermore, we systematically studied the effect of pore size and pressure difference on oil-water separation ability of the obtained membranes. It was found that the PANI-modified SSMs with 5µm pore size were suitable for the separation of non-surfactant emulsions with water fluxes of more than 1000Lm(-2)h(-1) under gravity only. The PANI-modified PVDF membranes were used for the effective separation of surfactant-stabilized emulsions with water fluxes up to 3000Lm(-2)h(-1) for 2µm pore size under 0.1bar or 0.22µm pore size under 0.6bar. In addition, the superhydrophilic membranes with PANI coatings were demonstrated for high oil rejection, stable underwater superoleophobic properties after ultrasonic treatment and immersing in oils and various harsh conditions, and high and steady water permeation flux after several cycles.

Mussel-Inspired Hybrid Coatings that Transform Membrane Hydrophobicity into High Hydrophilicity and Underwater Superoleophobicity for Oil-in-Water Emulsion Separation.

We first report here mussel-inspired, hybrid coatings formed in a facile manner via simultaneous polymerization of mussel-inspired dopamine and hydrolysis of commercial tetraethoxysilane in a single-step process. The hybrid coatings can firmly adhered on hydrophobic polyvinylidene fluoride (PVDF) substrate, and the hydrophilicity of the coating can be tuned by adjusting silane concentration. The reason for the changed hydrophilicity of the coating is disclosed by a series of characterization, and was applied to rationally design optimized hybrid coatings that transform commercial PVDF microfiltration (MF) membrane hydrophobicity into high hydrophilicity with excellent water permeability and underwater superoleophobicity for oil-in-water emulsion separation. The PVDF MF membrane decorated with optimized coatings has ultrahigh water flux (8606 L m(-2) h(-1) only under 0.9 bar, which is 34 times higher than that of pristine membrane), highly efficient oil-in-water emulsion separation ability at atmospheric pressure (filtrate flux of 140 L m(-2) h(-1)) and excellent antifouling performance. More importantly, these membranes are extremely stable as underwater superoleophobicity are maintained, even after rigorous washings or cryogenic bending, disclosing outstanding stability. The simplicity and versatility of this novel mussel-inspired one-step strategy may bridge the material-induced technology gap between academia and industry, which makes it promising for eco-friendly applications.