Techniques for recovery and recycling of ionic liquids: A review.

Due to beneficial properties like non-flammability, thermal stability, low melting point and low vapor pressure, ionic liquids (ILs) have gained great interest from engineers and researchers in the past decades to replace conventional solvents. The superior characteristics of ILs make them promising for applications in fields as wide-ranging as pharmaceuticals, foods, nanoparticles synthesis, catalysis, electrochemistry and so on. To alleviate the high cost and environmental impact of ILs, various technologies have been reported to recover and purify the used ILs, as well as recycling the ILs. The aim of this article is to overview the state-of-the-art research on the recovery and recycling technologies for ILs including membrane technology, distillation, extraction, aqueous two-phase system (ATPS) and adsorption. In addition, challenges and future perspectives on ILs recovery are discussed. This review is expected to provide valuable insights for developing effective and environmentally friendly recovery methods for ILs.

Synergistic effect of graphene oxide/zinc oxide nanocomposites on polylactic acid-based active packaging film: Properties, release kinetics and antimicrobial efficiency.

Incorporating two different nanoparticles in nanocomposite films is promising as their synergistic effects could significantly enhance polymer performance. Our previous work conferred the remarkable antimicrobial (AM) properties of the polylactic acid (PLA)-based film using optimal formulations of synergistic graphene oxide (GO)/zinc oxide (ZnO) nanocomposites. This study further explores the release profile of GO/ZnO nanocomposite and their impact on the antimicrobial properties. A fixed 1.11 wt% GO and different ZnO concentrations were well dispersed in the PLA matrix. Increasing ZnO concentrations tended to increase agglomeration, as evident in rougher surfaces. Agglomeration inhibited water penetration, leading to a significant reduction in water permeability (46.3 %), moisture content (31.6 %) but an improvement in Young's Modulus (52.6 %). The overall and specific migration of GO/ZnO nanocomposites was found to be within acceptable limits. It is inferred that the release of Zn2+ ions followed pseudo-Fickian behavior with an initial burst effect. AM film with the highest concentration of ZnO (1.25 wt%) exhibited the highest inhibition rate against Escherichia coli (68.0 %), Bacillus cereus (66.5 %), Saccharomyces cerevisiae (70.9 %). Results suggest that GO/ZnO nanocomposites with optimal ZnO concentrations have the potential to serve as promising antimicrobial food packaging materials, offering enhanced barrier, antimicrobial properties and a controlled release system.

Progress on Improved Fouling Resistance-Nanofibrous Membrane for Membrane Distillation: A Mini-Review.

Nanofibrous membranes for membrane distillation (MD) have demonstrated promising results in treating various water and wastewater streams. Significant progress has been made in recent decades because of the development of sophisticated membrane materials, such as superhydrophobic, omniphobic and Janus membranes. However, fouling and wetting remain crucial issues for long-term operation. This mini-review summarizes ideas as well as their limitations in understanding the fouling in membrane distillation, comprising organic, inorganic and biofouling. This review also provides progress in developing antifouling nanofibrous membranes for membrane distillation and ongoing modifications on nanofiber membranes for improved membrane distillation performance. Lastly, challenges and future ways to develop antifouling nanofiber membranes for MD application have been systematically elaborated. The present mini-review will interest scientists and engineers searching for the progress in MD development and its solutions to the MD fouling issues.

Electrosorption performance on graphene-based materials: a review.

Due to its unique advantages such as flexible planar structure, ultrahigh specific surface area, superior electrical conductivity and electrical double-layer capacitance in theory, graphene has unparalleled virtues compared with other carbon materials. This review summarizes the recent research progress of various graphene-based electrodes on ion electrosorption fields, especially for water desalination utilizing capacitive deionization (CDI) technology. We present the latest advances of graphene-based electrodes, such as 3D graphene, graphene/metal oxide (MO) composites, graphene/carbon composites, heteroatom-doped graphene and graphene/polymer composites. Furthermore, a brief outlook on the challenges and future possible developments in the electrosorption area are also addressed for researchers to design graphene-based electrodes towards practical application.

Impact of Particle Shape and Surface Group on Membrane Fouling.

Membrane fouling remains one of the most critical drawbacks in membrane filtration processes. Although the effect of various operating parameters-such as flow velocity, concentration, and foulant size-are well-studied, the impact of particle shape is not well understood. To bridge this gap, this study investigated the effect of polystyrene particle sphericity (sphere, peanut and pear) on external membrane fouling, along with the effect of particle charge (unmodified, carboxylated, and aminated). The results indicate that the non-spherical particles produce higher critical fluxes than the spherical particles (i.e., respectively 24% and 13% higher for peanut and pear), which is caused by the looser packing in the cake due to the varied particle orientations. Although higher crossflow velocities diminished the differences in the critical flux values among the particles of different surface charges, the differences among the particle shapes remained distinct. In dead-end filtration, non-spherical particles also produced lower flux declines. The shear-induced diffusion model predicts all five particle types well. The Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (XDLVO) models were used to quantify the interaction energies, and the latter agreed with the relative critical flux trends of all of the PS particles. As for the flux decline trends, both the DLVO and XDLVO results are in good agreement.

Enantiomeric Separation of Racemic Mixtures Using Chiral-Selective and Organic-Solvent-Resistant Thin-Film Composite Membranes.

Membrane-based chiral separation has emerged as a promising method for the efficient separation of chiral molecules. Ideally, the membranes should be able to achieve good enantioselectivity, while maintaining high stability in harsh solvents. However, engineering membranes for chiral molecular separation in harsh organic solvent environments is still a big challenge. In this study, we fabricated a novel thin-film composite nanofiltration membrane composed of (2-hydroxypropyl)-beta-cyclodextrin (HP-ß-CD) as the chiral selector for the enantiomeric separation of racemic 1-phenylethanol chiral compounds in organic solvents. The fabricated membrane achieved 60-80% enantioselectivity of R-phenylethanol over S-phenylethanol in nonpolar n-hexane. It was found that HP-ß-CD played a critical role in the enantioselective performance, as the membrane without HP-ß-CD showed no chiral selectivity. Molecular docking calculations substantiate the experiments by showing that the average free binding energy of S-phenylethanol with HP-ß-CD is stronger than that of R-phenylethanol, indicating that the complex of S-phenylethanol with HP-ß-CD has a higher thermodynamic stability and greater interaction. Furthermore, the crosslinked network between HP-ß-CD and the polyamide layer conferred the membrane with solvent stability in nonpolar solvents. Moreover, this new membrane exhibited good solvent permeance and a molecular weight cutoff of around 650 g mol-1.

Highly Robust Interfacially Polymerized PA Layer on Thermally Responsive Semi-IPN Hydrogel: Toward On-Demand Tuning of Porosity and Surface Charge.

Hydrogel composites with skin layer that allows fast and selective rejection of molecules possess high potential for numerous applications, including sample preconcentration for point-of-use detection and analysis. The stimuli-responsive hydrogels are particularly promising due to facile regenerability. However, poor adhesion of the skin layer due to swelling-degree difference during continuous swelling/deswelling of the hydrogel hinders its further development. In this work, a polyamide skin layer with strong adhesion was fabricated via gel-liquid interfacial polymerization (GLIP) of branched polyethyleneimine (PEI) with trimesoyl chloride (TMC) on a cross-linked N-isopropyl acrylamide hydrogel network containing dispersed poly sodium acrylate (PSA), while the traditional m-phenylenediamine (MPD)-TMC polyamide layer readily delaminates. We investigated the mechanistic design principle, which not only resulted in strong anchoring of the polyamide layer to the hydrogel surface but also enabled manipulation of the surface morphology, porosity, and surface charge by tailoring interfacial reaction conditions. The polyamide/hydrogel composite was able to withstand 100 cycles of swelling/deswelling without any delamination or a significant decrease in its rejection performance of the model dye, i.e., methylene blue. Regeneration can be done by deswelling the swollen beads at 60 °C, which also releases any loosely bound molecules together with absorbed water. This work provides insights into the development of a physically and chemically robust skin layer on various types of hydrogels for applications such as preconcentration, antifouling-coating, selective compound extraction, etc.

Competitive and Synergistic Adsorption of Mixtures of Polar and Nonpolar Gases in Carbonaceous Nanopores.

Most adsorption applications involve mixtures, yet accurate predictions of the adsorption of mixtures remain challenging, in part due to the inability to account for the interplay between adsorbate-adsorbate and adsorbate-adsorbent interactions. This study involves a comprehensive Monte Carlo simulation of the adsorption of two groups of mixtures (namely, supercritical and subcritical ones) in carbon nanopores and quantifies Henry's constants, isotherms, energetics, and density distributions in the pores. When interadsorbate interactions are negligible (e.g., in supercritical mixtures such as mixtures of nonpolar gases), adsorbates behave like ideal gases and the adsorption isotherm can be predicted with the ideal adsorbed solution theory (IAST). However, when interadsorbate interactions become significant, IAST fails. This study reveals that (1) in mixtures of polar and nonpolar gases, the stronger intermolecular interaction for the polar constituent leads to synergistic adsorption that causes the nonpolar adsorbate to desorb and (2) for mixtures of polar gases, such as ethanol and water, the adsorbate-adsorbate interactions are so dominant that the unfavorable adsorbate-adsorbent interactions are overcome, such that water adsorbs onto the hydrophobic adsorbent. The competitive and synergistic interactions highlighted here are expected to be valuable in enhancing gas separations.

Microfiltration of saline crude oil emulsions: Effects of dispersant and salinity.

Dispersants reduce oil-water interfacial tension making the separation of oil-water emulsions challenging. In this study, crude oil stabilized by the dispersant, Corexit EC9500A, was emulsified in synthetic sea water using a range of Corexit/crude oil concentration ratios (up to 10% by volume). With an interfacial tension of only 8.0 mJ/m2 at 0.5 mL(Corexit)/L, approximately 50% of the crude was dispersed into droplets <10 µm. Near complete rejection of oil in crossflow separation tests was accompanied by a precipitous flux decline attributable in part to dispersant- and salinity-induced decrease in membrane's oleophobicity (4.2 mJ/m2 decrease in surface energy). Screening of electrostatic interactions prompted oil coalescence that occurred at the membrane surface but not in the bulk of the emulsion. Real-time in situ visualization by Direct Observation Through Membrane gave direct evidence of surface coalescence pointing to both its detrimental effects (spread of contiguous films) and possible advantages (removal of large droplets by crossflow shear).

Cross-Linked Polycarbonate Microfiltration Membranes with Improved Solvent Resistance.

In this study, we report a facile preparation of an organic solvent-resistant membrane through the formation of urethane bonds between polycarbonate and polyethyleneimine groups. The modified membrane was further cross-linked with 1,4-butanediol diglycidyl ether (BDG) to enhance its solvent resistance as well as its thermal and mechanical stability. The cross-linked polycarbonate membranes exhibited improved solvent resistance with various organic solvents, giving a maximum swelling degree of 6%. It also showed better mechanical and thermal stability, as well as excellent permeance and rejection performance. This study demonstrates BDG as an attractive cross-linker for polycarbonate microfiltration membranes to transform them toward organic solvent filtration applications.

Assembly of three-dimensional ultralight poly(amidoxime)/graphene oxide nanoribbons aerogel for efficient removal of uranium(VI) from water samples.

Assembling graphene oxide nanoribbons (GONRs) into three-dimensional (3D) materials with controllable and desired structure is an effective way to expand their structural features and enable their practical applications. In this work, an ultralight 3D porous amidoxime functionalized graphene oxide nanoribbons aerogel (PAO/GONRs-A) was prepared via solvothermal polymerization method using acrylonitrile as monomer and GONRs as solid matrices for selective separation of uranium(VI) from water samples. The PAO/GONRs-A possessed a high nitrogen content (13.5%), low density (8.5 mg cm-3), and large specific surface area (494.9 m2 g-1), and presented an excellent high adsorption capacity of uranium, with a maximum capacity of 2.475 mmol g-1 at a pH of 4.5, and maximum uranium-selectivity of 65.23% at a pH of 3.0. The results of adsorption experiments showed that U(VI) adsorption on PAO/GONRs-A was a pH-dependent, spontaneous and endothermic process, which was better fitted to the pseudo-second-order kinetic model and Langmuir isotherm model. Both X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations revealed that U(VI) adsorption on PAO/GONRs-A mainly did rely on the amidoxime groups anchored on the aerogel while UO2(PAO)2(H2O)3 was dominant after interaction of uranyl with PAO/GONRs-A. Therefore, as a candidate adsorbent, PAO/GONRs-A has a high potential for the removal of uranium from aqueous solutions.

The physisorption mechanism of SO2 on graphitized carbon.

Sulfur dioxide (SO2) in flue gases emitted from fossil fuel power plants dramatically reduces the CO2 capture efficiency via adsorption, which is due to the potential reaction of SO2 with basic functional groups on the adsorbent. Physisorption rather than chemisorption is preferred, because adsorbents can be more easily regenerated by either reducing the pressure or increasing the temperature. Carbon is a suitable adsorbent for SO2 capture and widely used, and therefore it is important to study SO2 adsorption onto carbon with the Monte Carlo simulation to provide microscopic details to demarcate the roles of the basal plane of the graphene layer and the functional groups in adsorption. SO2 is a polar molecule like water, as they both carry partial charges, but they interact differently with functional groups. Instead of 3D-clusters in the case of water, SO2 is localized around the functional groups and spreads over the basal plane to form 2D-molecular layers because of the strong dispersive interactions with graphite. The results indicate that the functional group has a negligible effect on the enhancement of adsorption and its role is to localize 2D-clusters of SO2 molecules. For non-graphitized carbon, we have found that the greater loadings at low pressure compared to the highly graphitized carbon is due to the presence of defects (crevices) on the basal plane surface. Finally, to describe better the experimental data, we have found that the reduction in the interactions between adsorbed molecules in the first layer is because of the repulsion of their dipoles pointing normal to the surface, a phenomenon called surface mediation and is widely used in the description of gas adsorption on surfaces.

Development of an integrated aerobic granular sludge MBR and reverse osmosis process for municipal wastewater reclamation.

The reclamation of municipal wastewater to obtain high-grade product water is a growing need due to the pressing global water shortage. However, the existing municipal wastewater treatment plants (WWTPs) with the conventional activated sludge process as a core is not a sustainable engineering solution towards future water sustainability. To tackle such an emerging water-wastewater nexus, a ferrous-assisted aerobic granular sludge membrane bioreactor and reverse osmosis (AGSMBR-RO) process was developed for municipal wastewater reclamation. Results show that about 99.9%, 99.7% and nearly 100% of dissolved organic carbon (DOC), ammonium-N and total phosphorus (TP), respectively, could be removed in the ferrous-assisted AGSMBR-RO process, while the product water could meet the typical NEWater quality of Singapore with respect to the parameters analysed in this study. Moreover, it was found that an addition of 6 mg/L of ferrous could improve the stability of aerobic granular sludge (AGS) through the coagulation and flocculation of suspended flocs as well as phosphorus removal. These in turn led to reduced membrane fouling in both AGSMBR and RO units. Consequently, the proposed process is a promising alternative for municipal wastewater reclamation.

Metallicity-Dependent Ultrafast Water Transport in Carbon Nanotubes.

Carbon nanotubes (CNTs) with hydrophobic and atomically smooth inner channels are promising for building ultrahigh-flux nanofluidic platforms for energy harvesting, health monitoring, and water purification. Conventional wisdom is that nanoconfinement effects determine water transport in CNTs. Here, using full-atomistic molecular dynamics simulations, it is shown that water transport behavior in CNTs strongly correlates with the electronic properties of single-walled CNTs (metallic (met) vs semiconducting (s/c)), which is as dominant as the effect of nanoconfinement. Three pairs of CNTs (i.e., (8,8)met , 10.85 Å vs (9,7)s/c , 10.88 Å; (9,8)s/c , 11.53 Å vs (10,7)met , 11.59 Å; and (9,9)met , 12.20 Å vs (10,8)s/c , 12.23 Å) are used to investigate the roles of diameter and metallicity. Specifically, the (9,8)s/c can restrict the hydrogen-bonding-mediated structuring of water and give the highest reduction in carbon-water interaction energy, providing an extraordinarily high water flux, around 250 times that of the commercial reverse osmosis membranes and approximately fourfold higher than the flux of the state-of-the-art boron nitrate nanotubes. Further, the high performance of (9,8)s/c is also reproducible when embedded in lipid bilayers as synthetic high-water flux porins. Given the increasing availability of high-purity CNTs, these findings provide valuable guides for realizing novel CNT-enhanced nanofluidic systems.

Pre-deposited dynamic membrane filtration - A review.

A dynamic membrane (DM) is a layer of particles deposited via permeation drag onto a conventional membrane, such that the deposited particles act as a secondary membrane that minimizes fouling of the primary membrane to lower transmembrane pressures (TMP) and enable higher permeate fluxes. Since the first DM was created in 1966 at the Oak Ridge National Laboratory, numerous studies have reported synthesis of DMs using various materials and explored their abilities to perform reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF) and microfiltration (MF). DMs are classified into two categories, namely, (i) self-formed, whereby the feed constituents form the DM; and (ii) pre-deposited, whereby the DM is formed by a layer of particles other than the feed prior to introduction of the feed. This paper endeavors to present a comprehensive review of the state-of-the-art on the latter. Key materials used as DMs, their formation and various factors influencing it, regeneration of DMs and modifications to DM systems for performance enhancement are discussed. The role of DMs in preventing fouling in the primary membrane (PM) is explained. The applications of DMs in four major areas, namely, salt and organic solute rejection, treatment of industrial effluents, treatment of water and wastewater, and oily-wastewater treatment are reviewed. Furthermore, technical and economic advantages of DMs over conventional processes are considered, and challenges in current DM research are discussed. Finally, directions for future research are suggested.

N, P and S co-doped carbon materials derived from polyphosphazene for enhanced selective U(VI) adsorption.

Herein, the precursor polyphosphazene was synthesized by the polymerization of hexachlorocyclotriphosphazene (HCCP) and bis(4-hydroxyphenyl) sulfone (BPS). The adsorbent which was codoped with N, P and S (amidate-CS) was developed from the precursor by using the carbonization method. The images of Scanning electron microscope (SEM) and Transmission electron microscope (TEM) indicate that the amidate-CS possessed porous graphene-like carbon lamellar structure. The excellent behaviors with respect to kinetics (120 min for equilibrium) and thermodynamics (maximum removal of 290 mg/g when pH was at 6.0) revealed the outstanding performance of amidate-CS in removing U(VI), which is due to the functional groups and strong covalent bonds between heteroatoms and uranyl ions. The adsorption of amidate-CS followed the pseudo-second-order kinetic and Langmuir adsorption model. The thermodynamic parameters indicate that the process was spontaneous and endothermic. The adsorption and desorption efficiency of amidate-CS had a slight decrease after five cycles, indicating excellent regeneration performance. Overall, the amidate-CS is a prospective candidate for highly selective U(VI) removing.

Oil droplet behavior on model nanofiltration membrane surfaces under conditions of hydrodynamic shear and salinity.

HYPOTHESES: Oil droplet stability and electrical charge, and membrane's affinity for oil govern droplet attachment to a membrane surface. Moderate droplet-surface affinity encourages surface coalescence and removal of droplets to help maintain the membrane relatively oil-free. EXPERIMENTS: Droplet attachment onto model nanofiltration membranes was studied, in situ and in real time, using the Direct Observation Through the Membrane method. Optically transparent nanofiltration membranes were designed by forming polyelectrolyte multilayer films, with either positively or negatively charged surfaces, on Anopore ultrafilters. Crossflow across the membrane surface employed hexadecane-in-water emulsions stabilized by an anionic surfactant (sodium dodecylsulfate) in model sea water or aqueous solutions containing NaCl or MgSO4. FINDINGS: Moderate affinity between oil and the polyelectrolyte-coated surface promotes crossflow controlled coalescence to remove droplets larger than a critical size, ddropcrit, in the crossflow shear. The torque balance on a sessile oil droplet in a linear shear field overpredicted ddropcrit pointing to a need for more accurate estimates of lift and drag forces on a droplet. In the presence of divalent cations, lower electrostatic repulsion between droplets facilitated droplet-droplet adhesion and led to rapid coalescence that resulted in membrane fouling. The most significant fouling appeared in tests with positively charged and less oleophobic coatings.

Multifunctional Piezoelectric Heterostructure of BaTiO3@Graphene: Decomplexation of Cu-EDTA and Recovery of Cu.

About 3.93 billion tons of wastewater containing heavy metal complexes are discharged (e.g., from the electroplating industry) every year in China alone. It is challenging to appropriately treat such wastewaters. Here, a multifunctional composite nanowires BaTiO3@graphene was designed based on Comsol simulations and made into 3D millimeter-sphere in order to facilitate practical application. Results indicate 100% of Cu-EDTA was decomplexed in situ via piezoelectric potential by BaTiO3@graphene. Notably, the addition of graphene sharply increased the surface potential (from 19.8 ± 0.97 to 96.8 ± 1.48 mV) of BaTiO3@graphene by its flexoelectric effect then effectively promoted piezoelectric electrons to be separated and transferred, which favors the piezoelectric catalysis. Moreover, the released Cu(II) from Cu-EDTA decomplexation were recovered simultaneously via the interaction on graphene groups. This method efficiently recovered Cu(II) to avoid the consumption of massive chemical reagents and the generation of secondary hazardous solid waste containing heavy metal ions, compared with the conventional oxidative decomplexation/precipitation strategy for heavy metal complexes removal. Piezoelectric catalysis paves a new possibility for advanced oxidation in wastewater treatment.

Membrane-based separation for oily wastewater: A practical perspective.

The large volumes of oily wastewater generated by various industries, such as oil and gas, food and beverage, and metal processing, need to be de-oiled prior to being discharged into the environment. Compared to conventional technologies such as dissolved air flotation (DAF), coagulation or solvent extraction, membrane filtration can treat oily wastewater of a much broader compositional range and still ensure high oil removals. In the present review, various aspects related to the practical implementation of membranes for the treatment of oily wastewater are summarized. First, sources and composition of oily wastewater, regulations that stipulate the extent of treatment needed before discharge, and the conventional technologies that enable such treatment are appraised. Second, commercially available membranes, membrane modules, operation modes and hybrids are overviewed, and their economics are discussed. Third, challenges associated with membrane filtration are examined, along with means to quantify and mitigate membrane fouling. Finally, perspectives on state-of-the-art techniques to facilitate better monitoring and control of such systems are briefly discussed.

Influence of Alkali and Alkaline-Earth Metals on the Cleavage of Glycosidic Bond in Biomass Pyrolysis: A DFT Study Using Cellobiose as a Model Compound.

Fast pyrolysis is a promising technology for the production of renewable fuels and chemicals from lignocellulosic biomass. The product distribution (bio-oil, char) and the composition of bio-oil are significantly influenced by the presence of naturally occurring alkali and alkaline-earth metals (AAEMs). In this paper, we investigate, at the molecular level, the influence of Na(I), K(I), Ca(II), and Mg(II) ions on glycosidic bond breaking reactions using density functional theory. Glycosidic bond breaking reactions are categorized as direct C-O breaking mechanisms, namely, transglycosylation, glycosylation, and ring contraction and the two-step pathways, which include the mannose pathway, dehydration, and ring opening. Our calculations show that in the absence of metal, transglycosylation and dehydration pathways (activation barriers ∼55 kcal.mol-1) are kinetically most facile. The linkage type (α- or ß-1,4) has an insignificant effect on kinetics of glycosidic bond cleavage. Mg(II) ions have a pronounced effect on lowering the activation barriers of glycosylation, ring contraction, and the mannose pathway, requiring activation enthalpies of 32-52 kcal.mol-1. Conversely, Mg(II) and Ca(II) ions inhibit the dehydration pathway. Na(I) and K(I) ions do not significantly influence the activation barriers of glycosidic bond cleavage reactions, as the reduction is only about 5-10 kcal.mol-1. Thus, AAEM ions exhibit different catalytic effects on glycosidic bond breaking reactions.