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Heterogeneous advanced oxidation processes (AOPs) allow for the destruction of aqueous organic pollutants via oxidation by hydroxyl radicals (•OH). However, practical treatment scenarios suffer from the low availability of short-lived •OH in aqueous bulk, due to both mass transfer limitations and quenching by water constituents, such as natural organic matter (NOM). Herein, we overcome these challenges by loading iron oxychloride catalysts within the pores of a ceramic ultrafiltration membrane, resulting in an internal heterogeneous Fenton reaction that can degrade organics in complex water matrices with pH up to 6.2. With •OH confined inside the nanopores (∼ 20 nm), this membrane reactor completely removed various organic pollutants with water fluxes of up to 100 L m-2 h-1 (equivalent to a retention time of 10 s). This membrane, with a pore size that excludes NOM (>300 kDa), selectively exposed smaller organics to •OH within the pores under confinement and showed excellent resiliency to representative water matrices (simulated surface water and sand filtration effluent samples). Moreover, the membrane exhibited sustained AOPs (>24 h) and could be regenerated for multiple cycles. Our results suggest the feasibility of exploiting ultrafiltration membrane-based AOP platforms for organic pollutant degradation in complex water scenarios.

This study demonstrates the proof-of-concept of biogas sparging to control membrane fouling during sludge centrate pre-concentration by forward osmosis (FO). Sludge centrate sparging by biogas reduced membrane fouling (measured by water flux decline) and filtration time by two and eight times, respectively, compared to FO operation without biogas sparging at the same water recovery of 60%. In addition, the water flux was almost fully recovered by physical flushing when biogas sparging was applied. Biogas sparging also resulted in a significant improvement in the enrichment of organic, ammonia, and phosphate to close to the theoretical value based on mass balance calculation. In other words, organic matter and nutrients were retained in the bulk solution for subsequent recovery. Fouling mitigation and nutrient enrichment improvement by biogas sparging could be attributed to carbonate buffering to maintain a near neutral pH for preventing calcium phosphate precipitation on the membrane surface and ammonia volatilisation.

Synthetic polymer membranes are enabling components in key technologies at the water-energy nexus, including desalination and energy conversion, because of their high water/salt selectivity or ionic conductivity. However, many applications at the water-energy nexus require ion selectivity, or separation of specific ionic species from other similar species. Here, the ion selectivity of conventional polymeric membrane materials is assessed and recent progress in enhancing selective transport via tailored free volume elements and ion-membrane interactions is described. In view of the limitations of polymeric membranes, three material classes-porous crystalline materials, 2D materials, and discrete biomimetic channels-are highlighted as possible candidates for ion-selective membranes owing to their molecular-level control over physical and chemical properties. Lastly, research directions and critical challenges for developing bioinspired membranes with molecular recognition are provided.

In recent years, the development of nanopore-based membranes has revitalized the prospect of harvesting salinity gradient (blue) energy. In this study, we systematically analyze the energetic performance of nanopore-based power generation (NPG) at various process scales, beginning with a single nanopore, followed by a multipore membrane coupon, and ending with a full-scale system. We confirm the high power densities attainable by a single nanopore and demonstrate that, at the coupon scale and above, concentration polarization severely hinders the power density of NPG, revealing the common, yet significant, error in linearly extrapolating single-pore performance to multipore membranes. Through our consideration of concentration polarization, we also importantly show that the development of materials with exceptional nanopore properties provides limited enhancement of practical process performance. For a full-scale NPG membrane module, we find an inherent tradeoff between power density and thermodynamic energy efficiency, whereby achieving a high power density sacrifices the energy efficiency. Furthermore, we derive a simple expression for the theoretical maximum energy efficiency of NPG, showing it is solely related to the membrane selectivity (i.e., S2/2). Through this relation, it is apparent that the energy efficiency of NPG is limited to only 50% (for a completely selective membrane, i.e., S = 1), reinforcing our optimistic full-scale simulations which result in a (practical) maximum energy efficiency of 42%. Finally, we assess the net extractable energy of a full-scale NPG system which mixes river water and seawater by including the energy losses from pretreatment and pumping, revealing that the NPG process-both in its current state of development and in the case of highly optimistic performance with minimized external energy losses-is not viable for power generation.

Gypsum scaling via crystallization is a major obstacle limiting the applications of membrane-based technologies and heat exchangers in engineered systems. Herein, we perform the first comparative investigation on the impacts of natural organic matter (Suwannee River humic acid, SRHA) and colloidal particles on the gypsum crystallization process in terms of induction time and crystal morphology. Results show that the presence of SRHA significantly increases the induction time of gypsum crystallization. Specifically, at a solution saturation index of 4.92, the induction time increases 6.5-fold in the presence of 6 mg/L SRHA, compared to the case without SRHA. SRHA also alters the morphology of the formed calcium sulfate crystals, resulting in a polygon-like shape, differing from the characteristic needle-like shape of gypsum in the absence of additives. These changes in crystal morphology are attributed to the adsorption of SRHA on the gypsum crystal surface, blocking the active sites for gypsum growth. In contrast, in the presence of colloidal particles, the observed induction time of gypsum crystallization either decreases or increases, depending on the competitive interplay between the enhancement effect in the nucleation step and the inhibition effect in the subsequent crystal growth step. Furthermore, the formed gypsum crystals in the presence of colloidal particles exhibit a needle-like morphology similar to the crystals formed in the absence of any additives. Our study provides fundamental understanding of gypsum crystallization in feedwaters containing natural organic matter and colloidal particles, highlighting the importance of feedwater composition in gypsum scaling.

Global depletion of natural resources provides an impetus for developing low-cost, environmentally benign technologies for the recovery of valuable resources from wastewater. In this study, we present an autonomous photo-electrochemical osmotic system (PECOS) that can recover a wide range of metals from simulated metal-laden wastewater with sunlight illumination while generating electricity. The PECOS comprises a draw solution chamber with a nickel nanoparticle-functionalized titanium nanowire (Ni-TiNA) photoanode, a feed solution chamber containing synthetic wastewater with an immersed carbon fiber cathode, and a forward osmosis (FO) membrane mounted between the chambers as a separator. Using a Na2-EDTA anolyte as a draw solution at neutral pH, we demonstrate that a sunlit PECOS achieves copper recovery at a rate of 51 g h-1 per m-2 of membrane area from simulated copper-laden wastewater while simultaneously producing a maximum power density of 228 mW m-2. Moreover, because of the osmotic pressure difference generated by the photo-electrochemical reactions, the PECOS reduces the wastewater volume by extracting fresh water through the FO membrane at a water flux of 0.84 L m-2 h-1. We further demonstrate the feasibility of the PECOS in recovering diverse metals from a simulated metal-laden industrial wastewater under sunlight irradiation. Our proof-of-concept PECOS prototype provides a sustainable technological solution that leverages sunlight in an electrochemical osmotic system to recover multiple resources from wastewater.

A fundamental study elucidates the mechanisms underlying selective ion transport through desalination membranes., State-of-the-art desalination membranes exhibit high water-salt selectivity, but their ability to discriminate between ions is limited. Elucidating the fundamental mechanisms underlying ion transport and selectivity in subnanometer pores is therefore imperative for the development of ion-selective membranes. Here, we compare the overall energy barrier for salt transport and energy barriers for individual ion transport, showing that cations and anions traverse the membrane pore in an independent manner. Supported by density functional theory simulations, we demonstrate that electrostatic interactions between permeating counterion and fixed charges on the membrane substantially hinder intrapore diffusion. Furthermore, using quartz crystal microbalance, we break down the contributions of partitioning at the pore mouth and intrapore diffusion to the overall energy barrier for salt transport. Overall, our results indicate that intrapore diffusion governs salt transport through subnanometer pores due to ion-pore wall interactions, providing the scientific base for the design of membranes with high ion-ion selectivity.

A highly-efficient, autonomous electrochemical-osmotic system (EOS) is developed for simultaneous recovery of electric energy, water, and metals from wastewater. We demonstrate that the system can generate a maximum electric power density of 10.5 W m-2 using a spontaneous Fe/Cu2+ galvanic cell, while simultaneously achieving copper recovery from wastewater. With an osmotic pressure difference generated by the deployed electrochemical reactions, water is osmotically extracted from the feed solution with the EOS at a water flux of 5.1 L m-2 h-1. A scaled-up EOS realizes a power density of 105.8 W per m-3 of treated water to light an LED over 24 h while also enhancing water extraction and metal recovery. The modularized EOS obtains ultrahigh (>97.5%) Faradaic efficiencies under variable operating conditions, showing excellent system stability. The EOS is also versatile: it can recover Au, Ag, and Hg from wastewaters with simultaneous electricity and water coproduction. Our study demonstrates a promising pathway for realizing multiresource recycling from wastewater by coupling electrochemical and osmosis-driven processes.

Reactive membranes based on hydroxyl radical generation are hindered by the need for chemical dosing and complicated module and material design. Herein, we utilize an electrochemical approach featuring in situ generation of reactive (radical) chlorine species (RCS) through anodization of chloride ions for membrane self-cleaning. A hybridized carbon nanotube (CNT)-functionalized ceramic membrane (h-CNT/CM), possessing high hydrophilicity, permeability, and conductivity, was fabricated. Using carbamazepine (CBZ) as a probe, we confirmed the presence of RCS in the electrified h-CNT/CM. The rapid and complete degradation of CBZ in a single-pass ultrafiltration indicates a high localized RCS concentration within the three-dimensional porous CNT interwoven layer. We further demonstrate that the electrogeneration of RCS is a critical prestep for free chlorine (HClO and ClO-) formation. The self-cleaning efficiency of the membrane after fouling with a model organic foulant (alginate) was assessed using an electrified cross-flow membrane filtration system. The fouled h-CNT/CM exhibits a near complete water flux recovery following a short (1 min) self-cleaning with an applied voltage of 3 or 4 V and feed solutions of 100 or 10 mM sodium chloride, respectively. Considering the superior performance of the RCS-mediated self-cleaning compared to conventional membrane chemical cleaning using sodium hypochlorite, our results exemplify an effective strategy for in situ electrogeneration of RCS to achieve a highly efficient membrane self-cleaning.

Inner pores of carbon nanotubes combine extremely fast water transport and ion selectivity that could potentially be useful for high-performance water desalination and separation applications. We used dye-quenching halide assays and stopped-flow spectrometry to determine intrinsic permeability of three small monovalent halide anions (chloride, bromide, iodide) and one pseudohalide anion (thiocyanate) through narrow 0.8 nm diameter carbon nanotube porins (CNTPs). These measurements revealed unexpectedly strong differential ion selectivity with permeabilities of different ions varying by up to 2 orders of magnitude. Removal of the negative charge from the nanotube entrance increased anion permeability by only a relatively small factor, indicating that electrostatic repulsion was not a major determinant of CNTP selectivity. First principle molecular dynamics simulations revealed that the origin of this strong differential ion selectivity is partial dehydration of anions upon entry into the narrow CNTP channels.

Organic fouling and inorganic scaling are the main hurdles for efficient operation of reverse osmosis (RO) technology in a wide range of applications. This study demonstrates dual-functionality surface modification of thin-film composite (TFC) RO membranes to simultaneously impart anti-scaling and anti-fouling properties. Two different grafting approaches were adapted to functionalize the membrane surface with sulfonic groups: (i) non-specific grafting of vinyl sulfonic acid (VSA) via redox radical initiation polymerization and (ii) covalent bonding of hydroxylamide-O-sulfonic acid (HOSA) to the native carboxylic groups of the polyamide layer via carbodiimide mediated reaction. Both approaches to graft sulfonic groups were effective in increasing surface wettability and negative charge density of the TFC-RO membranes without significant alteration of water and salt permeabilities. Importantly, we verified through surface elemental analysis that covalently bound HOSA effectively covers the native carboxylic groups of the PA layer. Both the VSA and HOSA membranes exhibited lower flux decline during silica scaling and organic (alginate) fouling relative to the control unmodified membrane, demonstrating the unique versatility of sulfonic groups to endow the TFC-RO membranes with dual functionality to resist scaling and fouling. In particular, the HOSA membrane showed excellent physical cleaning efficiencies with water flux recoveries of 92.5 ± 1.0% and 88.4 ± 6.4% for silica scaling and alginate fouling, respectively. Additional results from silica nucleation experiments and atomic force measurements provided insights into the mechanisms of improved resistance to silica scaling and organic fouling imparted by the surface-functionalized sulfonic groups. Our study highlights the promise of controlled functionalization of sulfonic groups on the polyamide layer of TFC membranes to enhance the applications of RO technology in treatment and reuse of waters with high scaling and fouling potential.

Thin-film composite (TFC) polyamide reverse osmosis (RO) membranes are prone to biofouling due to their inherent physicochemical surface properties. In order to address the biofouling problem, we have developed novel surface coatings functionalized with biocidal silver nanoparticles (AgNPs) and antifouling polymer brushes via polyelectrolyte layer-by-layer (LBL) self-assembly. The novel surface coating was prepared with polyelectrolyte LBL films containing poly(acrylic acid) (PAA) and poly(ethylene imine) (PEI), with the latter being either pure PEI or silver nanoparticles coated with PEI (Ag–PEI). The coatings were further functionalized by grafting of polymer brushes, using either hydrophilic poly(sulfobetaine) or low surface energy poly(dimethylsiloxane) (PDMS). The presence of both LBL films and sulfobetaine polymer brushes at the interface significantly increased the hydrophilicity of the membrane surface, while PDMS brushes lowered the membrane surface energy. Overall, all surface modifications resulted in significant reduction of irreversible bacterial cell adhesion. In microbial adhesion tests with E. coli bacteria, a normalized cell adhesion in the range of only 4 to 16% on the modified membrane surfaces was observed. Modified surfaces containing silver nanoparticles also exhibited strong antimicrobial activity. Membranes coated with LBL films of PAA/Ag–PEI achieved over 95% inactivation of bacteria attached to the surface within 1 hour of contact time. Both the antifouling and antimicrobial results suggest the potential of using these novel surface coatings in controlling the fouling of RO membranes.

The robustness of carbon nanomaterials and their potential for ultrahigh permeability has drawn substantial interest for separation processes. However, graphene oxide membranes (GOms) have demonstrated limited viability due to instabilities in their microstructure that lead to failure under cross-flow conditions and applied hydraulic pressure. Here we present a highly stable and ultrapermeable zeolitic imidazolate framework-8 (ZIF-8)-nanocrystal-hybridized GOm that is prepared by ice templating and subsequent in situ crystallization of ZIF-8 at the nanosheet edges. The selective growth of ZIF-8 in the microporous defects enlarges the interlayer spacings while also imparting mechanical integrity to the laminate framework, thus producing a stable microstructure capable of maintaining a water permeability of 60 l m−2 h−1 bar−1 (30-fold higher than GOm) for 180 h. Furthermore, the mitigation of microporous defects via ZIF-8 growth increased the permselectivity of methyl blue molecules sixfold. Low-field nuclear magnetic resonance was employed to characterize the porous structure of our membranes and confirm the tailored growth of ZIF-8. Our technique for tuning the membrane microstructure opens opportunities for developing next-generation nanofiltration membranes. Highly stable and ultrapermeable membranes can be fabricated by the hybridization of zeolitic imidazolate framework-8 and graphene oxide.

Understanding ion solvation in liquid water is critical in optimizing materials for a wide variety of emerging technologies, including water desalination and purification. In this work, we report a systematic investigation and comparison of solvated K+ and NH4+ using first-principles molecular dynamics simulations. Our simulations reveal a strong analogy in the solvation properties of the two ions, including the size of the solvation shell as well as the solvation strength. On the other hand, we find that the local water structure in the ion solvation is significantly different; specifically, NH4+ yields a smaller number of water molecules and a more ordered water structure in the first solvation shell due to the formation of hydrogen bonds between the ion and water molecules. Finally, our simulations indicate that a comparable solvation strength of the two ions is a result of an interplay between the nature of ion-water interaction and number of water molecules that can be accommodated in the ion solvation shell.

Reverse Osmosis (RO) is a membrane-based technology for water desalination. Of paramount importance is the understanding of ion selectivity in mixtures of salts, i.e., to what extent the membrane retains one ion more than another in a multicomponent salt solution. We apply continuum transport theory to describe a large set of data for the ion selectivity of RO membranes treating brackish groundwater with more than 10 different monovalent and divalent ions. The model is based on the Donnan steric partitioning pore model extended to include ions of multiple charge states, such as bicarbonate/carbonic acid, ammonia/ammonium, and hydroxyl/hydronium ions and the acid-base reactions between them and with the membrane charge. By adjusting for each ion the ratio of ion size over pore size, we can fit the model to the data. We note that the fitted ion sizes do not always follow a logical order based on the ionic or hydrated size of the ions and that rejection of divalent cations is overestimated in some cases. We discuss possible theoretical improvements to address these discrepancies. Our results highlight the potential of continuum transport theory to describe in detail multicomponent ion transport in RO membranes. The development of a detailed and validated physics-based model is an important step toward achieving improved operation and design of RO-based desalination systems.

Polyelectrolyte multilayer membranes (PEMs) produced by the sequential, layer-by-layer deposition of polyelectrolytes on porous supports have been shown to significantly reject ions in dilute saline solutions. However, polyelectrolyte thin films are susceptible to swelling or detachment from the substrate in higher salinities and extreme pH conditions, such that their performance is highly dependent on feed water composition. In this study, we introduce tethered electrolyte active-layer membranes (TEAMs), whereby charged block copolymers are covalently grafted-from a porous support, in aim of reducing the stimuli response of layered polyelectrolyte membranes under variable solution conditions. Cellulose support layers were modified using surface-initiated atom transfer radical polymerization of neutral precursor polymers, which were then converted into charged blocks after polymerization. An ultrathin layer of a single negative or positive block with a degree of polymerization (DP) ≥ 770 exhibited ∼15–20 L m-2 h-1 bar-1 pure water permeability, 45–60% rejection of monovalent co-ions, and ∼75% rejection of divalent co-ions. In mixed feed solutions, selectivity of monovalent over divalent co-ions with single-block TEAMs fell within the range of 2–4. Single-block TEAMs slightly shrank under high salt concentration, contrary to the typical substantial swelling of PEMs. As such, this new form of polyelectrolyte membrane may provide greater stability than conventional PEMs and may have potential applications in water softening and salinity reduction of surface waters.

Capacitive deionization (CDI) is an emerging membraneless water desalination technology based on storing ions in charged electrodes by electrosorption. Due to unique selectivity mechanisms, CDI has been investigated towards ion-selective separations such as water softening, nutrient recovery, and production of irrigation water. Especially promising is the use of activated microporous carbon electrodes due to their low cost and wide availability at commercial scales. We show here, both theoretically and experimentally, that sulfonated activated carbon electrodes enable the first demonstration of perfect divalent cation selectivity in CDI, where we define "perfect" as significant removal of the divalent cation with zero removal of the competing monovalent cation. For example, for a feedwater of 15 mM NaCl and 3 mM CaCl

Enhancing the chemical and physical properties of the polyamide active layer of thin-film composite (TFC) membranes by surface coating is a goal long-pursued. Atomic layer deposition (ALD) has been proposed as an innovative approach to deposit chemically robust metal oxides onto membrane surfaces due to its unique capability to control coating conformality and thickness with atomic scale precision. This study examined the potential to coat the surface of TFC reverse osmosis (RO) and nanofiltration (NF) membranes via ALD of TiO2. Our results suggest that the optimal ALD conditions, the film growth kinetics, and the depth of deposition are different for RO and NF membranes due to the different diffusive transport of ALD precursors through the membrane pores. The TiO2 coating mainly located at the surface of the RO membrane; in contrast, the TiO2 coating extended to the depth of the NF membrane. The TiO2 coating degraded membrane water permeability and salt rejection beyond 10 cycles of ALD, the condition commonly employed in previous ALD-based membrane modification studies. Instead, this study showed that with fewer than 10 cycles, the TiO2 coating of RO membrane increased the membrane surface charge without negatively impacting water permeability and salt rejection. For the NF membranes, the coating of TiO2 inside their pores led to the tuning of pore sizes and increased the rejection of selected solutes.

Current technologies for water purification are limited by their contaminant-specific removal capability, requiring multiple processes to meet water quality objectives. Here we show an innovative biomimetic micellar nanocoagulant that imitates the structure of Actinia, a marine predator that uses its tentacles to ensnare food, for the removal of an array of water contaminants with a single treatment step. The Actinia-like micellar nanocoagulant has a core-shell structure and readily disperses in water while maintaining a high stability against aggregation. To achieve effective coagulation, the nanocoagulant everts its configuration, similar to Actinia. The shell hydrolyses into 'flocs' and destabilizes and enmeshes colloidal particles while the core is exposed to water, like the extended tentacles of Actinia, and adsorbs the dissolved contaminants. The technology, with its ability to remove a broad spectrum of contaminants and produce high-quality water, has the potential to be a cost-effective replacement for current water treatment processes.

Membrane modification using zwitterion polymers is an excellent strategy to reduce organic fouling and initial bacterial deposition, and functionalization of the membrane surface with antibacterial material can reduce biofilm formation. In this study, we combined these two approaches to develop an ultrafiltration polyethersulfone (PES) membrane with dual antifouling and antibacterial properties. At the beginning, a zwitterion polyampholyte hydrogel was UV grafted onto PES membrane surface (p-PES membrane). Then, the hydrogel was loaded with graphene oxide (GO) nanosheets using vacuum filtration strategy (GO-p-PES membrane). Raman spectroscopy and scanning electron microscopy (SEM) confirmed the successful incorporation of the GO nanosheets into the zwitterion hydrogel, and contact angle measurements indicated that the membrane hydrophilicity was enhanced. Static adsorption and dynamic filtration experiments demonstrated that the p-PES and GO-p-PES membranes exhibited similar organic fouling propensity. Moreover, the loading of GO induced antibacterial property for the membrane as evidenced by contact killing and antibiofouling filtration experiments. Leaching of GO was very low, with over 98% of the GO remaining on the membrane surface after 7 days. Our findings highlight the potential of this GO-functionalized polyampholyte hydrogel for long-term wastewater treatment.

Discovering electrode materials with exceptional capacitance, an indicator of the ability of a material to hold charge, is critical for developing capacitive deionization devices for water desalina...

Reverse osmosis (RO) has become a premier technology for desalination and water purification. The need for increased selectivity has incentivized research into novel membranes, such as biomimetic membranes that incorporate the perfectly selective biological water channel aquaporin or synthetic water channels like carbon nanotubes. In this study, we consider the performance of composite biomimetic membranes by projecting water permeability, salt rejection, and neutral-solute retention based on the permeabilities of the individual components, particularly the water channel, the amphiphilic bilayer matrix, and potential support layers that include polymeric RO, nanofiltration (NF), and porous ultrafiltration membranes. We find that the support layer will be crucial in the overall performance. Selective, relatively low-permeability supports minimize the negative impact of defects in the biomimetic layer, which are currently the main performance-limiting factor for biomimetic membranes. In particular, RO membranes as support layers would enable99.85% salt rejection at ∼10000-fold greater biomimetic-layer defect area than for porous supports. By fundamentally characterizing neutral-solute permeation through RO and NF membranes, we show that RO membranes as support layers would enable high rejection of organic pollutants based on molecular size, overcoming the rapid permeation of hydrophobic solutes through the biomimetic layer. A biomimetic membrane could also achieve exceptionally high boron rejections of ∼99.7%, even with 1% defect area in the biomimetic layer. We conclude by discussing the implications of our findings for biomimetic membrane design.

Biofouling is a major obstacle for the efficient and reliable operation of membrane-based desalination processes. Innovations in membrane materials and fabrication processes are therefore needed to develop antibiofouling strategies. In this study, we utilize the alignability of an emerging two-dimensional nanomaterial, graphene oxide (GO), to fabricate a desalination membrane with enhanced bacterial resistance. GO nanosheets are dispersed in a polymer solution to form a homogeneous mixture, which undergoes slow solvent evaporation in a magnetic field to create a thin nanocomposite membrane with vertically aligned GO nanosheets. The structural characteristics of the fabricated membranes confirm the enhanced exposure of nanosheet edges on the surface through the vertical alignment of GO. Notably, the addition and alignment of GO do not compromise membrane water permeability and water–salt selectivity. When contacted with bacterial cells, membranes with vertically aligned GO nanosheets exhibit enhanced antim...

We fabricated polyelectrolyte multilayer (PEM) nanofiltration (NF) membranes using a layer-by-layer (LbL) method for effective removal of scale-forming divalent cations (Mg2+, Ca2+, Sr2+, and Ba2+) from feedwaters with different salinities. Two polymers with opposite charges, polycation (poly(diallyldimethylammonium chloride), PDADMAC) and polyanion (poly(sodium 4-styrenesulfonate), PSS), were sequentially deposited on a commercial polyamide NF membrane to form a PEM. Compared to pristine and PSS-terminated membranes, PDADMAC-terminated membranes demonstrated much higher rejection of divalent cations and selectivity for sodium transport over divalent cations (Na+/X2+) due to a combination of both Donnan- and size-exclusion effects. A PDADMAC-terminated membrane with 5.5 bilayers exhibited 97% rejection of Mg2+ with selectivity (Na+/Mg2+) greater than 30. We attribute the order of cation rejection (Mg2+ > Ca2+ > Sr2+ > Ba2+) to the ionic size, which governs both the hydration radius and hydration energy of the cations. The ionic strength (salinity) of the feed solution had a significant influence on both water flux and cation rejection of PEM membranes. In feed solutions with high ionic strength, abundant NaCl salt screened the charge of the polyelectrolytes and led to swelling of the multilayers, resulting in decreased selectivity (Na+/X2+) and increased water permeability. The fabricated PEM membranes can be potentially applied to the pretreatment of mild-salinity brackish waters to reduce membrane scaling in the main desalination stage.

We investigated the relationship between silica scaling and protein fouling in reverse osmosis (RO). Flux decline caused by combined scaling and fouling was compared with those by individual scaling or fouling. Bovine serum albumin (BSA) and lysozyme (LYZ), two proteins with opposite charges at typical feedwater pH, were used as model protein foulants. Our results demonstrate that water flux decline was synergistically enhanced when silica and protein were both present in the feedwater. For example, flux decline after 500 min was far greater in combined silica scaling and BSA fouling experiments (55 ± 6% decline) than those caused by silica (11 ± 2% decline) or BSA (9 ± 1% decline) alone. Similar behavior was observed with silica and LYZ, suggesting that this synergistic effect was independent of protein charge. Membrane characterization by scanning electron microscopy and Fourier transform infrared spectroscopy revealed distinct foulant layers formed by BSA and LYZ in the presence of silica. A combination of dynamic light scattering, transmission electron microscopy , and energy dispersive X-ray spectroscopy analyses further suggested that BSA and LYZ facilitated the formation of aggregates with varied chemical compositions. As a result, BSA and LYZ were likely to play different roles in enhancing flux decline in combined scaling and fouling. Our study suggests that the coexistence of organic foulants, such as proteins, largely alters scaling behavior of silica, and that accurate prediction of RO performance requires careful consideration of foulant-scalant interactions.

Self-cleaning, antifouling ultrafiltration membranes are critically needed to mitigate organic fouling in water and wastewater treatment. In this study, we fabricated a novel polyvinylidene fluoride (PVDF) composite ultrafiltration membrane coated with FeOCl nanocatalysts (FeOCl/PVDF) via a facile, scalable thermal-treatment method, for the synergetic separation and degradation of organic pollutants. The structure, composition, and morphology of the FeOCl/PVDF membrane were extensively characterized. Results showed that the as-prepared FeOCl/PVDF membrane was uniformly covered with FeOCl nanoparticles with an average diameter of 1–5 nm, which greatly enhanced membrane hydrophilicity. The catalytic self-cleaning and antifouling properties of the FeOCl/PVDF membrane were evaluated in the presence of H2O2 at neutral pH. Using a facile H2O2 cleaning process, we showed that the FeOCl/PVDF membrane can achieve an excellent water flux recovery rate of ∼100%, following organic fouling with a model organic foulant...

Biological wastewater treatment is not effective in removal of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs). In this study, we fabricated a photocatalytic reactive membrane by functionalizing polyvinylidene fluoride (PVDF) ultrafiltration (UF) membrane with titanium oxide (TiO2) nanoparticles for the removal of ARB and ARGs from a secondary wastewater effluent. The TiO2-modified PVDF membrane provided complete retention of ARB and effective photocatalytic degradation of ARGs and integrons. Specifically, the total removal efficiency of ARGs (i.e., plasmid-mediated floR, sul1, and sul2) with TiO2-modified PVDF membrane reached ∼98% after exposure to UV irradiation. Photocatalytic degradation of ARGs located in the genome was found to be more efficient than those located in plasmid. Excellent removal of integrons (i.e., intI1, intI2, and intI3) after UV treatment indicated that the horizontal transfer potential of ARGs was effectively controlled by the TiO2 photocatalytic reacti...

Water scarcity, expected to become more widespread in the coming years, demands renewed attention to freshwater protection and management. Critical to this effort are the minimization of freshwater withdrawals and elimination of wastewater discharge, both of which can be achieved via zero liquid discharge (ZLD), an aggressive wastewater management approach. Because of the high energetic cost of thermal desalination, ZLD is particularly challenging for high-salinity wastewaters. In this review, we discuss the potential of high-pressure reverse osmosis (HPRO) (i.e., reverse osmosis operated at a hydraulic pressure greater than ∼100 bar) to efficiently desalinate hypersaline brines. We first discuss the inherent energy efficiency of membrane processes compared to that of conventional thermal processes for brine desalination. We then highlight the opportunity of HPRO to reduce energy requirements for desalination of key high-salinity industrial wastewaters. The current state of membrane materials and processe...

In this study, we demonstrate nanostructured osmosis membranes that employ vapor-phase water transport to simultaneously achieve high rejection of solutes and a high permeability. The membranes consist of a hydrophobic, thermally conductive silica nanoparticle (SiNP) layer with tunable thickness supported by a hydrophilic track-etched membrane. The membrane permeability for water vapor is 1–2 orders of magnitude higher than hydrophobic microporous membranes used for osmotic distillation. This permeability is only mildly lower (~ 3 times) than the equivalent water permeability of typical forward osmosis (FO) membranes. We also demonstrate the high selectivity of the SiNP membrane via urea permeation tests, where this membrane exhibits a 2–3 orders of magnitude lower urea permeability coefficient than a thin-film composite (TFC) FO membrane. Further measurements and theoretical analysis using the dusty-gas model suggest that membranes with a smaller SiNP layer thickness are capable of having comparable water fluxes to TFC FO membranes while maintaining higher selectivity. Our work demonstrates that thin, hydrophobic nanostructured membranes composed of thermally conductive materials have a great potential to significantly extend the applications of osmosis-driven processes to treat challenging water sources.

We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a poly(ether sulfone) support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ∼1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ∼0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (∼90%) while allowing high passage of scale-forming cations (i...

Sustainable provision of safe, clean and adequate water supply is a global challenge. Water treatment and desalination technologies remain chemically and energy intensive, ineffective in removing key trace contaminants, and poorly suited to deployment in decentralized (distributed) water treatment systems globally. Several recent efforts have sought to leverage the reactive and tunable properties of nanomaterials to address these technological shortcomings. This Review assesses the potential applications of nanomaterials in advancing sustainable water treatment systems and proposes ways to evaluate the environmental risks and social acceptance of nanotechnology-enabled water treatment processes. Future areas of research necessary to realize safe deployment of promising nanomaterial applications are also identified. Despite recent technological progress, providing safe, clean and sufficient water sustainably for all remains challenging. This Review assesses the potential applications of nanomaterials in advancing the sustainability of water treatment systems, and their associated barriers.

Conventional asymmetric or thin-film composite forward osmosis (FO) membranes suffer from severe internal concentration polarization, which significantly hinders process performance and practical applications. Here we report the synthesis of the COOH-derived polyoxadiazole copolymer for the fabrication of a self-standing selective thin film without a support layer. The thickness of the membrane was controlled at merely a few micrometers to achieve a high rate of rejection of the Na2SO4 draw solution, while maintaining acceptable water permeability. Because of the symmetric architecture, the membrane exhibited excellent and identical FO performance at both of its sides. The structural parameter of the fabricated membranes was zero because of the absence of internal concentration polarization in the symmetric FO membranes. Our results highlight the potential of support-free membranes for the further development of FO technology.

We used layer-by-layer (LbL) self-assembly to fabricate a polyelectrolyte (PE) nanofiltration membrane for salt rejection and to immobilize trypsin on the membrane outer layer for biocatalytic activity. Poly(ethylene imine) (PEI) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) were used as cationic PE while poly(acrylic acid) (PAA) and poly(styrene sulfonate) (PSS) were used as anionic PE. The impact of PE type, number of PE bilayers, and PE concentration on the rejection of inorganic salts (NaCl, MgCl2, Na2SO4, and MgSO4) and protein (bovine serum albumin, BSA) was systematically investigated. A maximum rejection of 12.7%, 45.2%, 85.5%, 94.0%, and 100% of MgCl2, NaCl, MgSO4, Na2SO4, and BSA, respectively, was obtained by the PDADMAC-PSS membrane with four bilayers. Trypsin (TRY) was immobilized on the membrane surface by electrostatic attraction or covalent bonding to produce a biocatalytic membrane and to alleviate protein fouling. Important parameters for enzymatic activity, such as immobilization time, pH, temperature, salt concentration and type, as well as the reuse number and storage time were investigated to expound the mechanism of enzyme activity in the presence of salt and BSA. BSA was used as a model protein for organic fouling experiments, and flux decline rate of the membranes was determined. Our results show that LbL-modified membranes with covalent enzyme immobilization had the lowest protein fouling rate, which we attribute to the biocatalytic activity of the immobilized trypsin.

This study intends to reinvent classical Fenton chemistry by enabling the Fe(II)/Fe(III) redox cycle to occur on a newly developed FeOCl nanosheet catalyst for facile hydroxyl radical (•OH) generation from H2O2 activation. This approach overcomes challenges such as low operating pH and large sludge production that have prevented a wider use of otherwise attractive Fenton chemistry for practical water treatment, in particular, for the destruction of recalcitrant pollutants through nonselective oxidation by •OH. We demonstrate that FeOCl catalysts exhibit the highest performance reported in the literature for •OH production and organic pollutant destruction over a wide pH range. We further elucidate the mechanism of rapid conversion between Fe(III) and Fe(II) in FeOCl crystals based on extensive characterizations. Given the low-cost raw material and simple synthesis and regeneration, FeOCl catalysts represent a critical advance toward application of iron-based advanced oxidation in real practice.

Recent studies have documented the existence of discrete voids in the thin polyamide selective layer of composite reverse osmosis membranes. Here we present compelling evidence that these nanovoids are formed by nanosized gas bubbles generated during the interfacial polymerization process. Different strategies were used to enhance or eliminate these nanobubbles in the thin polyamide film layer to tune its morphology and separation properties. Nanobubbles can endow the membrane with a foamed structure within the polyamide rejection layer that is approximately 100 nm in thickness. Simple nanofoaming methods, such as bicarbonate addition and ultrasound application, can result in a remarkable improvement in both membrane water permeability and salt rejection, thus overcoming the long-standing permeability–selectivity trade-off of desalination membranes.

Neutron radiography, a non-destructive imaging technique, is applied to study water and solute transport through desalination membranes. Specifically, we use neutron radiography to quantify lithium chloride draw solute concentrations across a thin-film composite membrane during forward osmosis permeation. This measurement provides direct visual confirmation of incomplete support layer wetting and reveals significant dilutive external concentration polarization of the draw solution outside of the membrane support layer. These transport-limiting phenomena have been hypothesized in previous work and are not accounted for in the standard thin-film model of forward osmosis permeation, resulting in inaccurate estimations of membrane transport properties. Our work demonstrates neutron radiography as a powerful measurement tool for studying membrane transport and emphasizes the need for direct experimental measurements to refine the forward osmosis transport model.

Low-grade heat from geothermal sources and industrial plants is a significant source of sustainable power that has great potential to be converted to electricity. The two main approaches that have been extensively investigated for converting low-grade heat to electrical energy, organic Rankine cycles and solid-state thermoelectrics, have not produced high power densities or been cost-effective for such applications. Newer, alternative liquid-based technologies are being developed that can be categorized by how the heat is used. Thermoelectrochemical cells (TECs), thermo-osmotic energy conversion (TOEC) systems, and thermally regenerative electrochemical cycles (TRECs) all use low-grade heat directly in a device that generates electricity. Other systems use heat sources to prepare solutions that are used in separate devices to produce electrical power. For example, low-temperature distillation methods can be used to produce solutions with large salinity differences to generate power using membrane-based systems, such as pressure-retarded osmosis (PRO) or reverse electrodialysis (RED); or highly concentrated ammonia solutions can be prepared for use in thermally regenerative batteries (TRBs). Among all these technologies, TRECs, TOEC, and TRBs show the most promise for effectively converting low-grade heat into electrical power mainly due to their high power productions and energy conversion efficiencies.

Waterborne pathogens are a major health threat and must be eliminated to guarantee safe usage of water for potable purposes. For this purpose, a new carbon-based nanomaterial composed of single-walled carbon nanotubes (SWCNTs) and iron oxides was constructed for bacterial inactivation. Owing to its magnetic properties, the SWCNT–iron oxide nanocomposite may serve as a reusable antimicrobial agent. The nanocomposite material exhibited high antimicrobial activity against Escherichia coli. Successful reuse of the nanocomposite material was achieved by washing with calcium chloride and distilled water, which restored its performance for several successive cycles. To investigate the cytotoxicity mechanisms of the nanocomposite material, we exposed it to single-gene knockout mutant strains of E. coli. Mutants bearing shorter lipopolysaccharide (LPS) layers in the outer membrane (ΔrfaC and ΔrfaG) demonstrated an increased sensitivity in comparison to the wildtype strain, exemplified in enhanced removal by the nanocomposite material. This finding suggests that the LPS acts as a protective shield against the nanocomposite material. Inactivation of mutants impaired in specific oxidative stress defense mechanisms (ΔsodA, ΔkatG and ΔsoxS) emphasized that oxidative stress plays a significant role in the inactivation mechanism of the nanocomposite. This study sheds light on the mechanisms of bacterial inactivation by carbon-based nanomaterials and advances their potential implementation for water disinfection.

Exploring non-precious-metal catalysts (NPMCs) for highly-efficient oxygen reduction reactions (ORRs) in fuel cells holds great potential to ease the global energy challenge. Recent developments regarding state-of-the-art Fe–N–C catalysts in terms of precursor development, synthesis innovation, and active site identification are compelling. Here, an efficient and sustainable Fe–N–C catalyst was successfully synthesized by temperature-programmed N2-pyrolysis from a ferrous ethylenediaminetetraacetic acid (EDTA) chelate. The unique structural properties were characterized by a wide existence of FeN4/C species encapsulated by a N–C coat, multiple porous morphologies, and a defective graphitic matrix, all of which greatly enhanced their intrinsic conductivities and prevented the aggregation of active moieties. The best Fe–N–C–800 catalysts promoted the ORR peak potential to −0.21 V with a nearly four-electron transfer pathway, only facilitating ∼14% H2O2 production. Both the Mossbauer fingerprints and X-ray absorption near edge structure (XANES) analysis revealed the origin of the ORR features derived from the structural compositions and corresponding hyperfine interaction. Interestingly, the embedding of oxygen in the Fe–N–C structure was found favorable for boosting durability and methanol endurance, which also hints at a strategy for rationally designing and producing promising ORR electrocatalysts from proper approaches and precursors.

Diffusion cannot be a major water transport mechanism in osmotic membranes because of the lack of true water concentration gradient within the membrane. Due to the semipermeable property of osmotic membranes, water concentration in the membrane is virtually constant because of the absence of salts. The recently confirmed porous structure of the skin layer of osmotic membranes cannot support the basis to exclude bulk water flow in the membrane as assumed in the classic solution-diffusion model. Herein we demonstrate that the concentration difference of water at the membrane-solution interface manifests itself as a negative hydraulic pressure in the membrane. Hence, the only possible driving force for water movement in osmotic membranes is hydraulic pressure gradient. Osmotically driven membrane processes are characterized with negative pressure within the membrane below the water vapor pressure, inevitably leading to the formation of vapor or small bubbles within the membrane matrix. This phenomenon is expected to markedly reduce the effectiveness of osmotic pressure as a driving force for water transport. Delineation of the breakdown and possible restoration of water continuity under negative pressure is essential for proper understanding of the principles governing water transport in osmotic membranes.

Electrodialysis (ED) is an electro-driven desalination technology that relies on the selective transport of ions through ion exchange membranes. Though several approaches have been developed to model and evaluate the performance of ED, mechanistic ion-transport models, which rigorously solve the fundamental Nernst-Planck equation, remain some of the most reliable and utilized. However, complexity of the involved transport phenomena prevents analytical solutions of such models, and numerical solutions can be prohibitively intensive. Here, we use an equivalent circuit analogue to derive a simple correlation equation that predicts the energetic performance of ED for brackish water desalination. Specifically, our correlation equation predicts the specific energy consumption of ED for a given productivity, set of desalination parameters (i.e., feed salinity, salt removal, water recovery), and system properties. The correlation equation demonstrates robustness in predicting the specific energy consumption across a wide range of operational parameters, showing excellent agreement with a Nernst-Planck ion-transport model and literature-reported experimental data. Furthermore, we use the developed correlation equation to show the dependence of the specific energy consumption on the productivity, highlighting the tradeoff between the thermodynamic energy efficiency and desalination rate of the ED process. Overall, our developed correlation equation provides a convenient alternative to computationally intensive mechanistic models for performance analysis of the ED process.

We studied the efficacy of grafting zwitterionic polymer brushes for the antifouling modification of ultrafiltration (UF) membranes. Poly(vinylidene fluoride) (PVDF) UF membranes were modified by surface initiated atom transfer radical polymerization (SI-ATRP) to graft poly(sulfobetaine methacrylate) (PSBMA) brushes to the membrane surface. Protein adsorption tests and chemical force microscopy show that a large brush layer thickness (greater than 100 nm) is necessary in order to impart effective fouling resistance. In dynamic fouling experiments with bovine serum albumin (BSA) as a model foulant, however, the modified membranes exhibited only a slight increase of flux recovery after fouling compared to pristine PVDF membranes. Despite the thick PSBMA brush layer, this low water flux recovery indicates that internal fouling takes place within the membrane pores. To prevent internal fouling, we grafted PSBMA brushes to both the surface and internal structure of the membranes. Nevertheless, dynamic fouling experiments again showed only a minute improvement in water flux recovery. While a thick brush layer is required for effective fouling resistance, we note that the small pore size of UF membranes imposes a fundamental limit on the brush layer thickness inside the pores. Finally, we discuss the challenges of polymer brush grafting for antifouling UF membrane modification and suggest possible alternative methods to create fouling resistant UF membranes.

We conducted a comparative study to investigate the efficacies of two different types of highly hydrophilic materials (i.e., silica nanoparticles (SiNPs) and zwitterionic polymers) for antifouling surface modification of polyamide thin-film composite (TFC) membranes. Dense layers of SiNPs and zwitterionic polymer brushes were grafted on the membrane surfaces via dip-coating with aminosilane-functionalized SiNPs (i.e., SiNP-TFC membrane) and surface-initiated atom-transfer radical-polymerization of sulfobetaine methacrylate (i.e., PSBMA-TFC membrane), respectively. With the same degree of enhancement of surface hydrophilicity and identical surface roughness, the PSBMA-TFC membrane exhibited significantly higher fouling resistance than the SiNP-TFC membrane in adsorption tests of proteins and bacteria as well as in forward osmosis (FO) dynamic fouling experiments using alginate as a model organic foulant. Chemical force microscopy measurements revealed that membrane-foulant electrostatic attraction aggravates organic fouling of the SiNP-TFC membrane to a certain degree, but the primary fouling mechanism is the complexation of organic foulants with carboxylic groups on the polyamide membrane surface. We attribute the lower fouling resistance of the SiNP-TFC membrane to the high density of surface carboxylic groups that may still be accessible to foulants as well as to membrane-foulant electrostatic interaction. On the contrary, the zwitterionic polymer brushes effectively shield the surface carboxylic groups and provide steric hindrance against foulant adsorption due to significant hydration of the zwitterionic brushes.

Direct contact membrane distillation (DCMD) is a thermal desalination process that is capable of treating high salinity waters using low-grade heat. As a water treatment process, DCMD has several advantages, including the utilization of waste heat (below 100 ℃ ), perfect rejection of nonvolatile solutes, low areal footprint, and high scalability. However, the energy efficiency of DCMD is relatively low compared to other work-based and thermal desalination processes. In this study, we aim to quantify how membrane properties and process conditions affect the exergy or second-law efficiency ( η II ) of a DCMD desalination system with external heat recovery. In particular, we analyze how the membrane permeability coefficient ( B ) and thermal conduction coefficient ( K ) impact MD performance. We show that increasing the B value of a membrane by reducing its thickness, initially leads to an increase in η II before conductive heat loss through the membrane causes η II to fall. For a typical MD membrane with a porosity of 0.90 , material thermal conductivity of 0.20 W m − 1 K − 1 , and a nominal pore diameter of 0.6 μ m , we find that the optimal permeability coefficient is 1.59 × 10 − 6 kg m − 2 s − 1 Pa − 1 ( 572 kg m − 2 h − 1 bar − 1 ). This value corresponds to an optimal membrane thickness of around 95 μ m . Our analysis stresses the importance of effective heat recovery in DCMD. We show that an external heat exchanger with a minimum approach temperature of 5 ℃ reduces energy consumption by 72 % . Finally, we demonstrate that increasing the ratio B / K , rather than just the B value, is key to increasing the exergy efficiency of DCMD desalination. For example, increasing membrane porosity from 0.70 to 0.90 , which yields a 160 % increase in B / K , leads to a 42 % increase in η II from 5.3 % to 7.6 % . The advantages of reducing the bulk pressure ( P ) in the membrane pores are also explored. For a typical membrane, halving P from 1.0 bar to 0.5 ⁢ bar , results in a 21 % increase in η II from 7.0 % to 9.2 % . We conclude by identifying that the maximum exergy efficiency achievable as membrane porosity tends to unity is 10 % for a bulk membrane pressure of 1.0 bar and 12 % for a bulk membrane pressure of 0.5 bar , given perfect heat recovery.

The interaction of two-dimensional (2D) nanomaterials with biological membranes has important implications for ecotoxicity and human health. In this study, we use a dye-leakage assay to quantitatively assess the disruption of a model phospholipid bilayer membrane (i.e., lipid vesicles) by five emerging 2D nanomaterials: graphene oxide (GO), reduced graphene oxide (rGO), molybdenum disulfide (MoS2), copper oxide (CuO), and iron oxide (α-Fe2O3). Leakage of dye from the vesicle inner solution, which indicates loss of membrane integrity, was observed for GO, rGO, and MoS2 nanosheets but not for CuO and α-Fe2O3, implying that 2D morphology by itself is not sufficient to cause loss of membrane integrity. Mixing GO and rGO with lipid vesicles induced aggregation, whereas enhanced stability (dispersion) was observed with MoS2 nanosheets, suggesting different aggregation mechanisms for the 2D nanomaterials upon interaction with lipid bilayers. No loss of membrane integrity was observed under strong oxidative condi...

Innovation in urban water systems is required to address the increasing demand for clean water due to population growth and aggravated water stress caused by water pollution, aging infrastructure, and climate change. Advances in materials science, modular water treatment technologies, and complex systems analyses, coupled with the drive to minimize the energy and environmental footprints of cities, provide new opportunities to ensure a resilient and safe water supply. We present a vision for enhancing efficiency and resiliency of urban water systems and discuss approaches and research needs for overcoming associated implementation challenges.

Fully aromatic polyamide thin-film composite (TFC) membranes are the industry standard for membrane-based desalination. Due to the extensive application of TFC membranes to treat feed waters of widely varying composition, new methods are needed to modulate the water permeability, water–solute selectivity, and surface charge of the polyamide selective layer. In this study, the quenching of residual acyl-chloride groups in nascent polyamide films is performed using amine, ammonia, and alcohol solutions, including common alcohol solvents such as methanol and ethanol. Membrane transport characterization in reverse osmosis demonstrates that quenching can substantially increase water permeability. For example, quenching in ammonium hydroxide resulted in water permeability of 2.50 L m−2 h−1 bar−1, which was 2.8 times greater than that for water-quenched control membranes, paired with a small decrease in sodium chloride rejection from 99.7% to 99.3%. By using different quenching solutions, quenching resulted in a range of water permeabilities (0.15–2.50 L m−2 h−1 bar−1) and water–salt selectivities (98.4–99.7% salt rejection), with performance falling along a previously proposed permeability–selectivity trade-off. Transport behavior and surface characterization indicate that chemical reactions occur to form amides and esters during quenching. Additionally, quenching decreased the carboxyl group density from 25.5 sites/nm2 for water-quenched control membranes to 11.8 sites/nm2 for membranes quenched in ammonium hydroxide. Taken together, the results demonstrate that acyl-chloride quenching provides a novel route to alter the surface charge in addition to water permeability and water–salt selectivity. Potential ways to further optimize the method are discussed.

Osmotic power harnesses the energy of mixing between high salinity and low salinity streams to generate mechanical energy. The closed-loop osmotic heat engine (OHE) is a low-grade heat powered, membrane-based energy system that couples membrane distillation (MD), a thermally driven membrane process, with pressure retarded osmosis (PRO), an osmotically driven membrane process. The objective of this study was to evaluate the technical and economic feasibility of an OHE to generate electricity. Experimental data and previously established MD and PRO models were used to develop an OHE system model that calculates system efficiency (a ratio between the net energy output and thermal energy input), net power output, and electricity generation costs. Results show that the levelized cost of electricity generation by an OHE at the current state of the technology is $0.48 per kWh, which is not competitive with wholesale conventional U.S. grid electricity costs of $0.04/kWh [1], nor comparable to low-grade heat-powered Organic Rankine Cycle electricity generation costs ($0.08–0.13/kWh). To investigate the robustness of the OHE model, a sensitivity analysis was performed to evaluate the influence of select model inputs on electricity costs. Results indicate that improving PRO membrane power density has the highest potential benefit to reduce OHE electricity generation costs. Development of highly permeable and selective PRO membranes that are mechanically stable at increased hydraulic pressures is critical for maturation of PRO and OHE. Alternative working fluids capable of producing higher osmotic pressures and having lower reverse solute fluxes may aid in increasing OHE performance, but not substantially. Our analysis shows that substantial improvements to system operation and membrane performance could reduce electricity generation cost of large installations close to $0.10 per kWh.

Polyamide thin-film composite (TFC) membranes are the industry standard for membrane-based desalination. Negatively-charged carboxyl groups in the polyamide selective layer play an important role in membrane performance, affecting ion permeation, fouling, and scaling. As such, simple and accurate quantitation of the carboxyl group density is needed. While several methods already exist, each has important drawbacks that limit its application. In this study, we develop a simple bind-and-elute method utilizing silver ion probes, with silver quantitation performed using inductively coupled plasma mass spectrometry. First, the efficacy of the binding, wash, and elution steps is verified, most notably using ion exchange resin with known binding capacity. The method is then used to characterize the carboxyl group density and ionization behavior of six commercial polyamide TFC membranes, with total densities ranging from 7.2 to 37 sites/nm2 and ionization behaviors best described using two acid dissociation constants (pKa values). Comparison with data for polyamide layers isolated using dimethylformamide (DMF) shows a 35%–65% decrease in carboxyl density, suggesting that DMF may dissolve uncrosslinked polyamide oligomers. Lastly, the method is used to characterize the effect of two membrane surface modifications, with the results supporting an alternative physical interpretation of the ionization behavior in which a carboxyl group's pKa is dependent on whether it is located on the surface or buried within the polyamide network. The simplicity, accuracy, and accessibility of the developed method should allow for widespread usage in future studies involving membrane surface charge, as well as studies involving other charged interfaces.