Continuous electrochemical water splitting from natural water sources via forward osmosis.

Electrochemical water splitting stores energy as equivalents of hydrogen and oxygen and presents a potential route to the scalable storage of renewable energy. Widespread implementation of such energy storage, however, will be facilitated by abundant and accessible sources of water. We describe herein a means of utilizing impure water sources (e.g., saltwater) for electrochemical water splitting by leveraging forward osmosis. A concentration gradient induces the flow of water from an impure water source into a more concentrated designed electrolyte. This concentration gradient may subsequently be maintained by water splitting, where rates of water influx (i.e., forward osmosis) and effective outflux (i.e., water splitting) are balanced. This approach of coupling forward osmosis to water splitting allows for the use of impure and natural sources without pretreatment and with minimal losses in energy efficiency.

Innovative stimuli-responsive membrane MSF brine rejection dilution by tertiary treated sewage effluent.

In this study, treated wastewater and Multi-Stage Flash (MSF) brine were integrated into the Forward Osmosis (FO) system using pressure stimuli-responsive Nanofiltration (PSRNF) membranes to dilute magnesium, calcium, and sulfate MSF plant brine reject. The deposition of magnesium sulfate and calcium sulfate in the heat exchanger is one of the main issues affecting the performance and efficiency of MSF thermal desalination plants. Reducing the concentration of the divalent ions can minimize scale formation and deposition to a level that allows the MSF plant to operate at high top brine temperature (TBT) and without scale problems. The PSRNF membranes were chosen in the FO process because of their high water permeability, rejection of divalent and monovalent ions, small structure parameter (S), and inexpensiveness compared to commercial FO membranes. Three PSRNF membranes were tested in the FO process with the feed solution facing the active membrane layer to avoid active layer delamination. Although the PSRNF membrane exhibited negligible water flux at 0 bar, it increased when a 2-4 bar was applied to the feed solution. The wastewater temperature was set at 25 °C while 40 °C was the brine operational temperature to mimic the field situation. A maximum average water flux of 39.5 L/m2h was recorded at 4 bar feed pressure when the PSRNF membrane was used for the brine dilution, achieving up to 42% divalent ions dilution at 0.02 kWh/m3 specific power consumption. The average water flux in the PRSNF membrane was 35% higher than that in the commercial TFC FO membrane. Notably, the PSRNF membrane is ten times cheaper than commercial FO membranes. Notably, the PSRNF membrane is ten times cheaper than commercial FO membranes, achieving substantial cost reductions and pioneering advancements in FO purification technology.

Metal-phenolic network as precursor complex coating for forward osmosis membrane with enhanced antifouling property.

In this study, a multi-functional layer was developed based on the commercially available cellulose triacetate (CTA) forward osmosis (FO) membrane to improve its antifouling property. Tannic acid/ferric ion (TA/Fe3+) complexes were firstly coated as a precursor layer on the membrane surface via self-assembly. Afterwards, the tannic acid/diethylenetriamine (TA/DETA) hydrophilic functional layer was further coated, following Ag/polyvinylpyrrolidone (PVP) anti-bacterial layer was formed in situ through the reducibility of TA to obtain TA/Fe3+-TA/DETA-Ag/PVP-modified membrane. The optimized precursor layer was acquired by adjusting the buffer solution pH to 8, TA/Fe3+ ratio to 4 and the number of self-assembled layers to 5. The permeability testing results illustrated that the functional layer had an insignificant effect on the membrane transport parameters. The TA/Fe3+-TA/DETA-Ag/PVP-modified membrane simultaneously exhibited excellent physical and chemical stability. The coated membrane also demonstrated enhanced anti-bacterial properties, achieving 98.63 and 97.30% inhibition against Staphylococcus aureus and Escherichia coli, respectively. Furthermore, the dynamic fouling experiment showed a 12% higher water flux decrease for the TA/Fe3+-TA/DETA-Ag/PVP CTA membrane compared to the nascent CTA membrane, which proved its excellent antifouling performance. This work provides a feasible strategy to heighten the antifouling property of the CTA FO membrane.

Imparting Outstanding Dispersibility to Nanoscaled 2D COFs for Constructing Organic Solvent Forward Osmosis Membranes.

In the context of thin-film nanocomposite membranes with interlayer (TFNi), nanoparticles are deposited uniformly onto the support prior to the formation of the polyamide (PA) layer. The successful implementation of this approach relies on the ability of nanoparticles to meet strict requirements regarding their sizes, dispersibility, and compatibility. Nevertheless, the synthesis of covalent organic frameworks (COFs) that are well-dispersed, uniformly morphological, and exhibit improved affinity to the PA network, while preventing agglomeration, remains a significant challenge. In this work, a simple and efficient method is presented for the synthesis of well-dispersed, uniformly morphological, and amine-functionalized 2D imine-linked COFs regardless of the ligand composition, group type, or framework pore size, by utilizing a polyethyleneimine (PEI) shielded covalent self-assembly strategy. Subsequently, the as-prepared COFs are incorporated into TFNi for the recycling of pharmaceutical synthetic organic solvents. After optimization, the membrane exhibits a high rejection rate and a favorable solvent flux, making it a reliable method for efficient organic recovery and the concentration of active pharmaceutical ingredient (API) from the mother liquor through an organic solvent forward osmosis (OSFO) process. Notably, this study represents the first investigation of the impact of COF nanoparticles in TFNi on OSFO performance.

Desalination, Water Re-use, and Halophyte Cultivation in Salinized Regions: A Highly Productive Groundwater Treatment System.

Groundwater salinization is a problem affecting access to water in many world regions. Though desalination by conventional reverse osmosis (RO) can upgrade groundwater quality for drinking, its disadvantages include unmanaged brine discharge and accelerated groundwater depletion. Here, we propose a new approach combining RO, forward osmosis (FO), and halophyte cultivation, in which FO optimally adjusts the concentration of the RO reject brine for irrigation of Salicornia or Sarcocornia. The FO also re-uses wastewater, thus, reducing groundwater extraction and the wastewater effluent volume. To suit different groundwater salinities in the range 1-8 g/L, three practical designs are proposed and analyzed. Results include specific groundwater consumption (SGC), specific energy consumption (SEC), wastewater volume reduction, peak RO pressure, permeate water quality, efficiency of water resource utilization, and halophyte yield. Compared to conventional brackish water RO, the results show superior performance in almost all aspects. For example, SGC is reduced from 1.25 to 0.9 m3 per m3 of drinking water output and SEC is reduced from 0.79 to 0.70 kW h/m3 by a FO-RO-FO system treating groundwater of salinity 8 g/L. This system can produce 1.1 m3 of high-quality drinking water and up to 4.9 kg of edible halophyte per m3 of groundwater withdrawn.

Smart Organic-Inorganic Polyoxomolybdates in Forward Osmosis for Antiviral-Drug Wastewater Treatment and Drug Reclamation.

The demand to effectively treat medical wastewater has escalated with the much greater use of antiviral drugs since the COVID-19 pandemic. Forward osmosis (FO) has great potential in wastewater treatment only when appropriate draw solutes are available. Here, we synthesize a series of smart organic-inorganic polyoxomolybdates (POMs), namely, (NH4)6[Mo7O24], (PrNH3)6[Mo7O24], (iPrNH3)6[Mo7O24], and (BuNH3)6[Mo7O24], for FO to treat antiviral-drug wastewater. Influential factors of separation performance have been systematically studied by tailoring the structure, organic characteristics, and cation chain length of POMs. POMs at 0.4 M produce water fluxes ranging from 14.0 to 16.4 LMH with negligible solute losses, at least 116% higher than those of NaCl, NH4HCO3, and other draw solutes. (NH4)6[Mo7O24] creates a water flux of 11.2 LMH, increased by more than 200% compared to that of NaCl and NH4HCO3 in long-term antiviral-drug wastewater reclamation. Remarkably, the drugs treated with NH4HCO3 and NaCl are either contaminated or denatured, while those with (NH4)6[Mo7O24] remain intact. Moreover, these POMs are recovered by sunlight-assisted acidification owing to their light and pH dual sensitivity and reusability for FO. POMs prove their suitability as draw solutes and demonstrate their superiority over the commonly studied draw solutes in wastewater treatment.

Internal Concentration Polarization in the Polyamide Active Layer of Thin-Film Composite Membranes.

A free-standing polyamide (PA) film is fabricated via in situ release from a thin-film composite (TFC) membrane achieved through the removal of the polysulfone support. The structure parameter S of the PA film is measured to be 24.2 ± 12.6 µm, which is about 87-fold of its film thickness. A significant decline in water flux of the PA film from an ideal forward osmosis membrane is observed. We find that the decline is predominantly influenced by the internal concentration polarization (ICP) of the PA film based on our experimental measurements and theoretical calculations. We propose that the asymmetric hollow structures of the PA layer with dense crusts and cavities may be the underlying cause of the occurrence of the ICP. More importantly, the structure parameter of the PA film can be reduced and its ICP effect can be mitigated by tuning its structures with fewer and shorter cavities. Our results for the first time provide experimental evidence to prove that the PA layer of the TFC membrane has the ICP effect, which could potentially provide fundamental insights into the influence of structural properties of PA on the membrane separation performance.

Microalgal biofouling formation on tubular cellulose-ester membranes during dewatering by forward osmosis.

This work assesses the biofouling formation of a microalgal consortium, cultivated in wastewater, on dialysis tubular membranes with no supporting layer, in both batch and continuous FO dewatering modes. The biological adhesion strength was compared with the predictions from the Baier and Vogler biocompatibility theories, employing critical surface tension (γc) and water adhesion tension (τ0), respectively, as measurable parameters of surface wettability. The results indicate that most of the tested membranes presented amphiphilic surface characteristics (τ0=22 to 45 mJ.m-2, θW ≈ 65˚) with a minimal biological adhesion tendency, which is compatible with the Vogler criteria. However, the membrane exposed the longest time to the microalgal culture presented more hydrophobic characteristics and poor wettability. The existing thermodynamic models succeeded in predicting cell-cell and cell-surface interactions as a competitive phenomenon. Nevertheless, the XDLVO model was used to determine changes in the cell-to-surface attraction dynamics. This assessment of microalgal foulant-membrane interfacial interactions helps to enhance understanding of the fouling mechanisms present on a novel FO membrane surface.

Optimization and prediction of lead removal from aqueous solution using FO-MD hybrid process: Statistical and artificial intelligence analysis.

Heavy metals (HMs) has become one of the most serious pollutants that are harmful to the environment and ecology. This paper focused on the removal of lead contaminant from wastewater by forward osmosis-membrane distillation (FO-MD) hybrid process using seawater as draw solution. Modeling, optimization, and prediction of FO performance are developed using complementary approach based on response surface methodology (RSM) and an artificial neural network (ANN). FO process optimization using RSM revealed that under initial lead concentration of 60 mg/L, feed velocity of 11.57 cm/s and draw velocity of 7.66 cm/s, FO process achieved highest water flux of 6.75 LMH, lowest reverse salt flux of 2.78 gMH and highest lead removal efficiency of 87.07%. Fitness of all models was evaluated based on determination coefficient (R2) and mean square error (MSE). Results showed highest R2 value up to 0.9906 and lowest RMSE value up to 0.0102. ANN modeling generates the highest prediction accuracy for water flux and reverse salt flux, while RSM produces the highest prediction accuracy for lead removal efficiency. Subsequently, FO optimal conditions are applied on FO-MD hybrid process using seawater as draw solution and evaluate their performance to simultaneously remove lead contaminant and desalination of seawater. Results displays that FO-MD process shows a highly efficient solution to produce fresh water with almost free heavy metals and very low conductivity.

Techno-economic assessment of a novel algal-membrane system versus conventional wastewater treatment and advanced potable reuse processes: Part II.

This study developed a comprehensive techno-economic assessment (TEA) framework to evaluate an innovative algae resource recovery and near zero-liquid discharge potable reuse system (i.e., the main system) in comparison with a conventional potable water reuse system (i.e., the benchmark system). The TEA study aims to estimate the levelized costs of water of individual units and integrated processes including secondary wastewater treatment, advanced water purification for potable reuse, and sludge treatment. This would provide decision-makers valuable information regarding the capital and operational costs of the innovative main system versus a typical potable water reuse treatment train, along with possible routes of cost optimization and improvements for the design of full-scale facilities. The main system consists of (i) a novel algal-based wastewater treatment coupled with a dual forward osmosis and seawater reverse osmosis (Algal FO-SWRO) membranes system for potable water reuse and hydrothermal liquefaction (HTL) to produce bioenergy and subsequent nutrients extraction from the harvested algal biomass. The benchmark system includes (ii) an advanced water purification facility (AWPF) that consists of a conventional activated sludge biological treatment (CAS), microfiltration (MF), brackish water reverse osmosis (BWRO), ultraviolet/advanced oxidation process (UV-AOP), and granular activated carbon (GAC), with anaerobic digestion for sludge treatment. Capital expenditures (CAPEX) and operational expenditures (OPEX) were calculated for each unit of both systems (i.e., sub-systems). Based on a 76% overall water recovery designed for the benchmark system, the water cost was estimated at $2.03/m3. The highest costs in the benchmark system were found on the CAS and the anaerobic digester, with the UV-AOP combined with GAC for hydrogen peroxide (H2O2) quenching as the driving factor in the increased costs of the system. The cost of the main system, based on an overall 88% water recovery, was estimated to be $1.97/m3, with costs mostly driven by the FO and SWRO membranes. With further cost reduction and optimization for FO membranes such as membrane cost, water recovery, and flux, the main system can provide a much more economically viable alternative in its application than a typical benchmark system.

Effect of Polyethylene Glycol Additive on the Structure and Performance of Fabric-Reinforced Thin Film Composite.

Fabric-reinforced thin film composite (TFC) membranes exhibit outstanding mechanical durability over free-standing membranes for commercial applications. In this study, polyethylene glycol (PEG) was incorporated to modify the polysulfone (PSU) supported fabric-reinforced TFC membrane for forward osmosis (FO). The effects of PEG content and molecular weight on the structure, material property and FO performance of the membrane were investigated comprehensively, and the corresponding mechanisms were revealed. The membrane prepared by using 400 g/mol PEG exhibited better FO performances than those of membranes with 1000 and 2000 g/mol PEG, and 20 wt.% was demonstrated to be the optimal PEG content in the casting solution. The permselectivity of the membrane was further improved by reducing the PSU concentration. The optimal TFC-FO membrane had a water flux (Jw) of 25.0 LMH using deionized (DI) water feed and 1 M NaCl draw solution, and the specific reverse salt flux (Js/Jw) was as low as 0.12 g/L. The degree of internal concentration polarization (ICP) was significantly mitigated. The membrane behaved superior to the commercially available fabric-reinforced membranes. This work provides a simple and low-cost approach in the development TFC-FO membrane and shows great potential in the large-scale production for practical applications.

Wastewater Primary Treatment Using Forward Osmosis Introduces Inhibition to Achieve Stable Mainstream Partial Nitrification.

Achieving stable long-term mainstream nitrite oxidizing bacteria (NOB) suppression is the bottleneck for the novel partial nitrification (PN) process toward energy- and carbon-efficient wastewater treatment. However, long-term PN stability remains a challenge due to NOB adaptation. This study proposed and demonstrated a novel strategy for achieving NOB suppression by the primary treatment of mainstream wastewater with a forward osmosis (FO) membrane process, which facilitated two external NOB inhibition factors (salinity and free nitrous acid, FNA). To evaluate the proposed strategy, a lab-scale sequencing batch reactor was operated for 200 days. A stable PN operation was achieved with a nitrite accumulation ratio of 97.7 ± 2.8%. NOB were suppressed under the combined inhibition effect of NaCl (7.9 ± 0.2 g/L, as introduced by the FO direct filtration) and FNA (0.11 ± 0.02 mg of HNO2-N/L, formed as a result of the increased NH4+-N concentration after the FO process). The two inhibition factors worked in synergy to achieve a more stable PN operation. The microbial analysis showed that the elevated salinity and accumulation of FNA reshaped the microbial community and selectively eliminated NOB. Finally, an economic and feasibility analysis was conducted, which suggests that the integration of an FO unit into PN/A is a feasible and economically viable wastewater treatment process.

EDTA-Na2 as a recoverable draw solute for water extraction in forward osmosis.

Regeneration and reuse of draw solute (DS) is a key challenge in the application of forward osmosis (FO) technologies. Herein, EDTA-Na2 was studied as a recoverable DS for water extraction by taking advantages of its pH-responsive property. The FO system using EDTA DS achieved a higher water flux of 2.22 ± 0.06 L m-2 h-1 and a significantly lower reverse salt flux (RSF) of 0.06 ± 0.01 g m-2 h-1, compared to that with NaCl DS having either the same DS concentration or the same Na+ concentration. The suitable pH range for the application of EDTA DS was between 4.0 and 10.5. A simple recovery method via combined pH adjustment and microfiltration was employed to recover EDTA DS and could achieve the recovery efficiency (at pH 2) of 96.26 ± 0.48%, 97.13 ± 1.03% and 98.56 ± 1.40% by using H2SO4, H3PO4 and HCl, respectively. The lowest acid cost for DS recovery was estimated from 0.0012 ± 0.0001 to 0.0162 ± 0.0003 $ g-1 by using H2SO4. The recovered EDTA DS could be reused in the subsequent FO operation and the overall recovery efficiency was 94.4% for four reuse cycles. These results have demonstrated the feasible of EDTA-Na2 DS and a potentially cost-effective recovery approach, and encouraged further exploration of using EDTA-based compounds as a draw solute for FO applications.

Fabrication and characterization of high-performance forward-osmosis membrane by introducing manganese oxide incited graphene quantum dots.

Forward osmosis (FO) is the futuristic membrane desalination technology as it transcends the disadvantages of other pressure-driven techniques. But, there still remain critical challenges like fabrication of highly permeable membrane with ideal structures maintaining high rejection rates that need to be addressed for implementation as a practical technology. In this work, novel thin-film composite (TFC) membranes were fabricated by means of incorporating manganese oxide (MnO2) incited graphene quantum dots (GQDs) nanocomposite into a cellulose acetate (CA) suspension followed by phase inversion (PI) for enhanced FO performance. The surface morphology and chemical structure of fabricated membranes were studied using various characterization techniques like XRD, FT-IR, SEM-EDS, Mapping, AFM, and TGA. The structural parameters, water flux, reverse salt flux and salt rejection was estimated on the basis of data obtained from four varying initial draw solution concentrations. At high nanocomposites stacking, the hydrophilicity of the casting blend increase, and subsequently, the PI exchange rate additionally increases, which brings about noticeable difference in the surface morphology. The membrane with 0.5 wt% nanocomposite exhibited superior FO separation performance with osmotic water flux of 18.89, 34.49, 41.76 and 42.34 in L.m-2.h-1 with variable concentrations of NaCl salt solution (0.25M, 0.5M, 1M, and 2M), respectively. Also, the porosity of the membrane was increased to 47.23% with 96.87% salt rejection. The results indicate that the hydrophilicity of the nanocomposite drives them to the interface among CA and water during PI process leading to solid hydrogen bonding to achieve high water permeability.

Impacts of seasonality and operating conditions on algal-dual osmosis membrane system for potable water reuse: Part 2.

This study investigated the impact of seasonal variation and operating conditions on recovery of potable quality water from municipal wastewater effluent using an integrated algal treatment process with a dual forward osmosis (FO)-reverse osmosis (RO) membrane system. Pilot study of the algal process treating primary effluent validated the technical viability and seasonal performance during warm weather (May to October, 25-55 °C) using an extremophilic algal strain Galdieria sulphuraria, and during cold weather (November to April, 4-17 °C) using polyculture strains of algae and bacteria. Algal effluents from both seasons were used as the feed solution for the laboratory FO-RO study. In addition, pilot-scale FO-RO experiments were conducted to compare the system performance during treatment of algal effluent and secondary effluent from the conventional treatment facility. At 90% water recovery, the FO-RO achieved over 90% overall rejection of major ions and organic matter using the bench-scale system and over 99% rejection of all contaminants in pilot-scale studies. Detailed water quality analysis indicated that the product water from the integrated system met both the primary and secondary drinking water standards. This study demonstrated that the FO-RO system can be engineered as a viable alternative to treat algal effluent and secondary effluent for potable water reuse independent of seasonal variations and operating conditions.

Exploring the limitations of forward osmosis for direct hydroponic fertigation: Impact of ion transfer and fertilizer composition on effective dilution.

There is a need for water reuse technologies and applications to minimize the imminent water crisis, caused by the world population growth, the reduction of freshwater resources and the increasing water pollution. Fertilizer-drawn forward osmosis (FDFO) is a promising process capable of simultaneously extracting fresh water from low-quality sources as feed water (e.g., wastewater or greywater), while diluting fertilizer solutions for direct fertigation, avoiding the demand for freshwater for irrigation. Achieving an adequate level of dilution for direct fertigation is a key element to be evaluated for the implementation of FDFO. This study assessed the performance of the forward osmosis process to dilute fertilizer solutions to be applied directly in hydroponic systems. Experiments were carried out under conditions close to osmotic equilibrium to evaluate the process performance up to the maximum dilution point. Tests were carried out with individual and blended fertilizers (i.e., (NH4)2HPO4 or DAP, and KNO3) used as draw solution (DS) and with deionized water or individual salts (NaCl, MgCl2, Na2SO4, MgSO4) in the feed solution (FS). Water fluxes and reverse salt fluxes indicated that both fertilizer DS composition and concentrations play a fundamental role in the process. Suitable nutrient concentrations to be directly applied without further dilution for N, P and K (119, 40, 264 mg.L-1 respectively) were obtained with deionized water as FS and blended DAP (0.025 M) and KNO3 (0.15 M) as DS. However, important fertilizer losses from DS to FS were observed, being the highest for NO3- (33-70% losses from DS to FS). The presence of salts in FS decreased the water fluxes and the DS dilution due to the osmotic equilibrium caused by a greater loss of nutrients from DS to FS (up to 100%), compared with tests using just deionized water as FS. This study points out the potential limitations of the FDFO process, due to the high solute fluxes and low water fluxes in conditions close to osmotic equilibrium.

Prediction of forward osmosis membrane engineering factors using artificial intelligence approach.

Currently, forward osmosis (FO) is widely studied for wastewater treatment and reuse. However, there are still challenges which need to be addressed for the application of the FO on a commercial scale. In the meantime, with a strong capability to solve the complicated nonlinear relationships and to examine of the relations between multiple variables, artificial intelligence (AI) technique could be a viable tool to improve FO system performance to make it more applicable. This study aims to develop an AI-based model for supporting early control and making decision in the FO membrane system. The results show that the artificial neural networks model is extremely suitable for prediction of water flux, membrane fouling, and removal efficiencies. The most appropriate input dataset for the model was proposed, in which organic matters, sodium ion, and calcium ion concentrations played a vital role in all predictions. The best model architecture was suggested with an optimal hidden layers (2-4 layers), and neurons (10-15 neurons). The developed models for membrane fouling show strong correlation between experimental and predicted data (with R2 values for prediction of membrane fouling porosity, thickness, roughness, and density were 0.85, 0.97, 0.97, and 0.98, respectively). The prediction of water flux presented a high R2 and low root mean square error (RMSE) of 0.92 and 0.9 L m-2.h-1, respectively. Prediction of the contaminant removal exhibits a relatively high correlation between the observed and predicted data with R2 values of 0.87 and RMSE values of below 2.7%. The developed models are expected to create a breakthrough in the control and enhancement in a novel FO membrane process used for wastewater treatment by providing us with actionable insights to produce fit-for-future systems in the context of sustainable development.

Synthesis of PNIPAAm-g-P4VP Microgel as Draw Agent in Forward Osmosis by RAFT Polymerization and Reverse Suspension Polymerization to Improve Water Flux.

Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m-2∙h-1.

Thermoresponsive Ionic Liquid with Different Cation-Anion Pairs as Draw Solutes in Forward Osmosis.

We synthesized various phosphonium- and ammonium-based ionic liquids (ILs), using benzenesulfonate (BS) and 4-methylbenzenesulfonate (MBS) to establish the criteria for designing an ideal draw solute in a forward osmosis (FO) system. Additionally, the effects of monocationic, dicationic, and anionic species on FO performance were studied. Monocationic compounds ([P4444][BS], [P4444][MBS], [N4444][BS], and [N4444][MBS]) were obtained in one step via anion exchange. Dicationic compounds ([(P4444)2][BS], [(P4444)2][MBS], [(N4444)2][BS], and [(N4444)2][MBS]) were prepared in two steps via a Menshutkin SN2 reaction and anion exchange. We also investigated the suitability of ILs as draw solutes for FO systems. The aqueous [P4444][BS], [N4444][BS], [N4444][MBS], and [(N4444)2][BS] solutions did not exhibit thermoresponsive behavior. However, 20 wt% [P4444][MBS], [(P4444)2][BS], [(P4444)2][MBS], and [(N4444)2][MBS] had critical temperatures of approximately 43, 33, 22, and 60 °C, respectively, enabling their recovery using temperature. An increase in IL hydrophobicity and bulkiness reduces its miscibility with water, demonstrating that it can be used to tune its thermoresponsive properties. Moreover, the FO performance of 20 wt% aqueous [(P4444)2][MBS] solution was tested for water flux and found to be approximately 10.58 LMH with the active layer facing the draw solution mode and 9.40 LMH with the active layer facing the feed solution.

Thermoresponsive Ionic Liquid/Water Mixtures: From Nanostructuring to Phase Separation.

The thermodynamics, structures, and applications of thermoresponsive systems, consisting primarily of water solutions of organic salts, are reviewed. The focus is on organic salts of low melting temperatures, belonging to the ionic liquid (IL) family. The thermo-responsiveness is represented by a temperature driven transition between a homogeneous liquid state and a biphasic state, comprising an IL-rich phase and a solvent-rich phase, divided by a relatively sharp interface. Demixing occurs either with decreasing temperatures, developing from an upper critical solution temperature (UCST), or, less often, with increasing temperatures, arising from a lower critical solution temperature (LCST). In the former case, the enthalpy and entropy of mixing are both positive, and enthalpy prevails at low T. In the latter case, the enthalpy and entropy of mixing are both negative, and entropy drives the demixing with increasing T. Experiments and computer simulations highlight the contiguity of these phase separations with the nanoscale inhomogeneity (nanostructuring), displayed by several ILs and IL solutions. Current applications in extraction, separation, and catalysis are briefly reviewed. Moreover, future applications in forward osmosis desalination, low-enthalpy thermal storage, and water harvesting from the atmosphere are discussed in more detail.