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Membrane filtration has been widely adopted in various water treatment applications, but its use in selective solute separation for resource extraction and recovery is an emerging research area. When a membrane process is applied for solute-solute separation to extract solutes as the product, the performance metrics and process optimization strategies should differ from a membrane process for water production because of separation goals are fundamentally different. In this analysis, we used lithium (Li) magnesium (Mg) separation as a representative solute-solute separation to illustrate the deficiency of existing performance evaluation framework developed for water-solute separation using nanofiltration (NF). We performed coupon and module scale analyses of mass transfer to elucidate how membrane properties and operating conditions affect the performance of Li/Mg separation in NF. Notably, we identified an important operational tradeoff between Li/Mg selectivity and Li recovery, which is critical for process optimization. We also established a new framework for evaluating membrane performance based on the success criteria of Li purity and recovery. This analysis lays the theoretical foundation for performance evaluation and process optimization for NF-based selective solute separation.

Desalination technologies using salt-rejecting membranes are a highly efficient tool to provide fresh water and augment existing water supplies. In recent years, numerous studies have worked to advance a variety of membrane processes with different membrane types and driving forces, but direct quantitative comparisons of these different technologies have led to confusing and contradictory conclusions in the literature. In this Review, we critically assess different membrane-based desalination technologies and provide a universal framework for comparing various driving forces and membrane types. To accomplish this, we first quantify the thermodynamic driving forces resulting from pressure, concentration, and temperature gradients. We then examine the resistances experienced by water molecules as they traverse liquid- and air-filled membranes. Last, we quantify water fluxes in each process for differing desalination scenarios. We conclude by synthesizing results from the literature and our quantitative analyses to compare desalination processes, identifying specific scenarios where each process has fundamental advantages.

Developing engineered surfaces with scaling resistance is an effective means to inhibit surface-mediated mineral scaling in various industries including desalination. However, contrasting results have been reported on the relationship between scaling potential and surface hydrophilicity. In this study, we combine a theoretical analysis with experimental investigation to clarify the effect of surface wetting property on heterogeneous gypsum (CaSO

Fabrication of nanofiltration (NF) membranes using interfacial polymerization (IP) continues to receive tremendous interest in research and development due to the broad applications of NF in water ...

Seawater desalination has become an important tool to attain global water security and sustainability. Among the available technologies, reverse osmosis (RO) has become the golden standard for seawater desalination due to its unparalleled energy efficiency. While RO is already efficient after development for half a century, there remains room for over 50% further reduction in energy consumption that can translate into tens of terawatt hours of potential annual energy saving. However, this significant energy saving cannot be achieved under the conventional paradigm of on-ground RO. In this analysis, we assess the idea of operating RO with open modules several hundred meters below the ocean surface (i.e., the mesopelagic zone). This new process, namely mesopelagic open reverse osmosis (MORO), can potentially push the energy consumption of seawater desalination to its theoretical limit. We first describe the concept of MORO, and then examine both the theoretical potential of energy saving and the practical challenges facing the implementation of MORO. Our analysis provides a theoretical framework for the future development of MORO for more sustainable desalination.

Enhancing the water permeance while maintaining the solute rejection of a nanofiltration (NF) membrane can potentially result in significant cost-reduction for NF-a membrane process that excels in several unique environmental applications of growing interests. In this work, we demonstrate for the first time that intercalation of surfactant self-assemblies in the polyelectrolyte multilayer (PEM) can lead to significant performance enhancement of salt-rejecting dense NF membranes fabricated using layer-by-layer assembly of polyelectrolytes. Specifically, the intercalation of sodium dodecyl sulfate (SDS) bilayers in a PEM comprising poly(diallyldimethylammonium chloride) (PDADMAC) and poly (sodium 4-styrenesulfonate) (PSS) resulted in a decrease in PEM thickness, increase in pore size, and a smoother and more hydrophilic surface. The water permeance of the resulting PEM NF membrane increased by 100% without compromising the rejection of Na2SO4. Experiments with a quartz crystal microbalance also provide direct evidence that the intercalation of the surfactants substantially reduces the subsequent adsorption of the polyelectrolytes of a similar charge. Based on its mechanism of performance enhancement, surfactant intercalation may become a universally applicable and highly cost-effective approach for dramatically enhancing the performance of PEM NF membranes.

Membrane distillation (MD) has been garnering increasing attention in research and development, since it has been proposed as a promising technology for desalinating hypersaline brine from various ...

Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes., Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Here, the authors demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization.

The growing needs for sustainable nutrient management and pollution control have motivated the development of novel technologies for nutrient recovery from wastewater. However, most of the existing technologies require extensive use of chemicals and intensive consumption of energy to achieve substantial recovery of nutrients. Herein, we present a hybrid electrochemical sequence integrating two relatively novel electrochemical processes, bipolar membrane electrodialysis (BMED) and membrane capacitive deionization (MCDI), for simultaneous removal of phosphorus and nitrogen. Specifically, the BMED process is employed to alkalify the wastewater to facilitate struvite precipitation and the MCDI process is used to further reduce the ammonia concentration in the effluent and concentrate the excess ammonia to a small stream. The electrochemical sequence is demonstrated to remove ∼89% of phosphorus and ∼77% of ammonia, recovering ∼81% of wastewater as a high-quality effluent that can be discharged or reused. This electrochemical treatment train minimizes chemical use and has competitive energy consumption as compared to electrochemical processes for nutrient recovery from wastewater.

While reverse osmosis (RO) is the leading technology to address the global challenge of water scarcity through desalination and potable reuse of wastewater, current RO membranes fall short in rejecting certain harmful constituents from seawater (e.g., boron) and wastewater [e.g., N -nitrosodimethylamine (NDMA)]. In this study, we develop an ultraselective polyamide (PA) membrane by enhancing interfacial polymerization with amphiphilic metal-organic framework (MOF) nanoflakes. These MOF nanoflakes horizontally align at the water/hexane interface to accelerate the transport of diamine monomers across the interface and retain gas bubbles and heat of the reaction in the interfacial reaction zone. These mechanisms synergistically lead to the formation of a crumpled and ultrathin PA nanofilm with an intrinsic thickness of ~5 nm and a high cross-linking degree of ~98%. The resulting PA membrane delivers exceptional desalination performance that is beyond the existing upper bound of permselectivity and exhibited very high rejection (>90%) of boron and NDMA unmatched by state-of-the-art RO membranes.

The development of membranes capable of precise solute-solute separation is still in its burgeoning stage without a standardized protocol for evaluating selectivity. Three types of membrane processes with different driving forces, including pressure-driven filtration, concentration difference-driven diffusion, and electric field-driven ion migration, have been applied in this study to characterize solute-solute selectivity of a commercial nanofiltration membrane. Our results demonstrated that selectivity values measured using different methods, or even different conditions with the same method, are generally not comparable. The cross-method incomparability is true for both apparent selectivity, defined as the ratio between concentration-normalized fluxes, and the more intrinsic selectivity, defined as the ratio between the permeabilities of solutes through the active separation layer. The difference in selectivity measured using different methods possibly stems from the fundamental differences in the driving force of ion transport, the effect of water transport, and the interaction between cations and anions. We further demonstrated the difference in selectivity measured using feed solutions containing single-salt species and that containing mixed salts. A consistent protocol with standardized testing conditions to facilitate fair performance comparison between studies is proposed.

The safe and economical management of shale gas flowback and produced water (FPW) with the goal of zero-liquid discharge (ZLD) is of paramount significance to the sustainable development of the energy industry. This challenge is still widely impending, due to severe limitations related to the complexity of FPW streams and high costs associated with their treatment. A long-term feasible solution is represented by solar-driven interfacial evaporation (SIE), a low-cost and environmentally friendly desalination technology. Technical and economic analyses show that even in the Sichuan Basin, where solar intensity is low and the volume of FPW is large, 4000 m2 of solar still would be sufficient to accomplish ZLD with a capital cost lower than $ 1 m−3, significantly cheaper than traditional membrane-based and thermal-based technologies (with costs above $ 15 m−3). Beneficial products, including condensate water and crystalline salts, may also be effectively recovered in this process, although design improvements are needed in this area. This study also discusses possible solutions to address the passage of volatile organic compounds into the effluent and to achieve the smart recovery of strategic resources, such as lithium and rare earth elements. The major current challenges of solar-driven evaporation for the beneficial management of FPW are scaling and fouling, cost-effective latent heat recovery, the scalability of the systems, and efficient water production and salts harvesting. These issues require ad hoc research efforts, analyses, and pilot testing.

Membrane distillation (MD) has potential to become a competitive technology for managing hypersaline brine but not until the critical challenge of mineral scaling is addressed. The state-of-the-art approach for mitigating mineral scaling in MD involves the use of superhydrophobic membranes that are difficult to fabricate and are commercially unavailable. This study explores a novel operational strategy, namely, negative pressure direct contact membrane distillation (NP-DCMD) that can minimize mineral scaling with commercially available hydrophobic membranes and at the same time enhance the water vapor flux substantially. By applying a negative gauge pressure on the feed stream, NP-DCMD achieved prolonged resistance to CaSO4 scaling and a dramatic vapor flux enhancement up to 62%. The exceptional scaling resistance is attributable to the formation of a concave liquid–gas under a negative pressure that changes the position of the water–air interface to hinder interfacial nucleation and crystal growth. The substantial flux enhancement is caused by the reduced molecular diffusion resistance within the pores and the enhanced heat transfer kinetics across the boundary layer in NP-DCMD. Achieving substantial performance improvement in both the scaling resistance and vapor flux with commercial membranes, NP-DCMD is a significant innovation with vast potential for practical adoption due to its simplicity and effectiveness.

Recovering nitrogen from source-separated urine is an important part of the sustainable nitrogen management. A novel bipolar membrane electrodialysis with membrane contactor (BMED-MC) process is demonstrated here for efficient recovery of ammonia from synthetic source-separated urine (∼3772 mg N L-1). In a BMED-MC process, electrically driven water dissociation in a bipolar membrane simultaneously increases the pH of the urine stream and produces an acid stream for ammonia stripping. With the increased pH of urine, ammonia transports across the gas-permeable membrane in the membrane contactor and is recovered by the acid stream as ammonium sulfate that can be directly used as fertilizer. Our results obtained using batch experiments demonstrate that the BMED-MC process can achieve 90% recovery. The average ammonia flux and the specific energy consumption can be regulated by varying the current density. At a current density of 20 mA cm-2, the energy required to achieve a 67.5% ammonia recovery in a 7 h batch mode is 92.8 MJ kg-1 N for a bench-scale system with one membrane stack and can approach 25.8 MJ kg-1 N for large-scale systems with multiple membrane stacks, with an average ammonia flux of 2.2 mol m-2 h-1. Modeling results show that a continuous BMED-MC process can achieve a 90% ammonia recovery with a lower energy consumption (i.e., 12.5 MJ kg-1 N). BMED-MC shows significant potential for ammonia recovery from source-separated urine as it is relatively energy-efficient and requires no external acid solution.

Although membrane distillation (MD) has been identified as a promising technology to treat hypersaline wastewaters, its practical applications face two prominent challenges: membrane wetting and fouling. Herein, we report a facile and scalable approach for fabricating a Janus MD membrane comprising a dense polyvinyl alcohol (PVA) surface layer and a hydrophobic polyvinylidene fluoride (PVDF) membrane substrate. By testing the Janus membrane in direct contact MD experiments using feeds containing a sodium dodecyl sulfate (SDS) surfactant or/and mineral oil, we demonstrated that the dense Janus membrane can simultaneously resist wetting and fouling. This method represents the simplest approach to date for fabricating MD membranes with simultaneous wetting and fouling resistance. Importantly, we also unveil the mechanism of wetting resistance by measuring the breakthrough pressure and surfactant permeation (through the PVA layer) and found that wetting resistance imparted by a dense hydrophilic layer is attributable to capillary pressure. This new insight will potentially change the paradigm of fabricating wetting-resistant membranes and enable robust applications of MD and other membrane contactor processes facing challenges of pore wetting or/and membrane fouling.

In this study, we report the emergence of two-dimensional (2D) branching fractal structures (BFS) in the nanoconfinement between the active and the support layer of a thin-film-composite polyamide (TFC-PA) nanofiltration membrane. These BFS are crystal dendrites of NaCl formed when salts are either added to the piperazine solution during the interfacial polymerization process or introduced to the nascently formed TFC-PA membrane before drying. The NaCl dosing concentration and the curing temperature have an impact on the size of the BFS but not on the fractal dimension (∼1.76). The BFS can be removed from the TFC-PA membranes by simply dissolving the crystal dendrites in deionized water, and the resulting TFC-PA membranes have substantially higher water fluxes (three- to fourfold) without compromised solute rejection. The flux enhancement is believed to be attributable to the distributed reduction in physical binding between the PA active layer and the support layer, caused by the exertion of crystallization pressure when the BFS formed. This reduced physical binding leads to an increase in the effective area for water transport, which, in turn, results in higher water flux. The BFS-templating method, which includes the interesting characteristics of 2D crystal dendrites, represents a facile, low-cost, and highly practical method of enhancing the performance of the TFC-PA nanofiltration membrane without having to alter the existing infrastructure of membrane fabrication.

While reverse osmosis (RO) is the leading technology to address the challenge of water scarcity through desalination and potable reuse of wastewater, current RO membranes still fall short in rejecting certain harmful constituents from seawater (e.g., boron) and wastewater (e.g., N-nitrosodimethylamine, or NDMA). In this study, we develop an ultra-selective polyamide (PA) membrane via enhancing interfacial polymerization using amphiphilic metal-organic framework (MOF) nanoflakes. In this process, MOF nanoflakes horizontally aligned at the water/hexane interface to accelerate the transport of diamine monomers across the interface and conserve gas bubbles and heat of reaction near the interface. These mechanisms synergistically led to the formation of a crumpled PA nanofilm with an ultrathin intrinsic thickness of ~ 5 nm and a high cross-linking degree of ~ 97%. The resulting PA membrane delivered excellent desalination performance that is beyond the existing upper-bound of perm-selectivity, and exhibited very high rejection (> 90%) of boron and NDMA unmatched by state-of-the-art RO membranes.

Mineral scaling constrains membrane distillation (MD) and limits its application in treating hypersaline wastewater. Addressing this challenge requires enhanced fundamental understanding of the scaling phenomenon. However, MD scaling with different types of scalants may have distinctive mechanisms and consequences which have not been systematically investigated in the literature. In this work, we compared gypsum and silica scaling in MD and demonstrated that gypsum scaling caused earlier water flux decline and induced membrane wetting that was not observed in silica scaling. Microscopic imaging and elemental mapping revealed contrasting scale morphology and distribution for gypsum and silica, respectively. Notably, while gypsum crystals grew both on the membrane surface and deep in the membrane matrix, silica only formed on the membrane surface in the form of a relatively thin film composed of connected submicrometer silica particles. We attribute the intrusion of gypsum into membrane pores to the crystallization pressure as a result of rapid, oriented crystal growth, which leads to pore deformation and the subsequent membrane wetting. In contrast, the silica scale layer was formed via polymerization of silicic acid and gelation of silica particles, which were less intrusive and had a milder effect on membrane pore structure. This hypothesis was supported by the result of tensile testing, which showed that the MD membrane was significantly weakened by gypsum scaling. The fact that different scaling mechanisms could yield different consequences on membrane performance provides valuable insights for the future development of cost-effective strategies for scaling control.

Membrane distillation (MD) is a thermal desalination process with the capability of harnessing low-grade waste heat to treat hypersaline brine. For this reason, MD has been actively explored as a p...

Electrochemical capacitive deionization (CDI) is a promising technology for distributed and energy-efficient water desalination. The development of high-performance, low-cost capacitive electrodes is critical for enhancing CDI performance and scaling up its applications. Here, we report a novel design of highly compact, free-standing nanoporous carbon film electrodes for high-performance CDI. Such porous electrodes are fabricated by slip-roll compressing polypyrrole (PPy)-derived activated microporous carbon particles (PPy-AMC) with a small amount of polymer binder (5 wt%). The unique PPy-AMCs are synthesized from a rigid polymer precursor using a scalable carbonization-activation process, which is adopted in the manufacturing of commercial activated carbons. With small and uniform particle size, large specific surface area and short diffusion length, the PPy-AMC-based compact carbon electrodes offer very high salt adsorption capacity and enable very fast desalination, which significantly outperforms the state-of-the-art porous carbon-based CDI electrodes. This work provides an important strategy to design and fabricate compact yet porous carbon electrodes for efficient water desalinization and can be potentially extended to other applications such as energy storage and conversion.

Failure of membrane distillation (MD) due to pore wetting by amphiphilic molecules has recently received growing interests because it is a critical challenge to overcome for MD to be applicable for treating unconventional feed water. Recent MD studies using feed solutions containing surfactants have elucidated fundamental mechanism of wetting and generated practical solutions for wetting mitigation. However, what remains unclear is the impact of surfactant species on pore wetting kinetics. Based on a recently developed kinetic model for surfactant-induced pore wetting in MD, we hypothesize that the surface excess concentration of a surfactant is the most important surfactant property in affecting the pore wetting kinetics. In this study, we performed controlled MD wetting experiments using seven different types of surfactants and measured their respective breakthrough time as a quantitative metric for wetting kinetics. Our experiments reveal a good linear correlation between the surface excess concentration and breakthrough time for most but one tested surfactant. When surface excess concentration and diffusion coefficient are both considered, the model-simulated breakthrough time matches the experimentally measurement remarkably well for all tested surfactants.

While membrane-based oil-water separation has been widely explored, using conventional membranes to treat oily wastewaters remains practically challenging especially when such wastewaters contain more stable nano-sized oil droplets and are of high oil content, and harsh chemical conditions. Herein, we report a novel protocol of efficiently separating both synthetic and real oil nano-emulsions via specially designed robust zirconia membranes. The best-performing zirconia membrane, fabricated at low sintering temperature, has relatively uniform sub-100 nm pores and is underwater superoleophobic. Such zirconia membranes possess not only outstanding separation performance under long-term operation but robust structural stability at harsh conditions. At different cross-flow velocities, a combined model of intermediate pore blocking and cake filtration dominated membrane fouling behavior. Specifically, at high pH value (especially > pH(IEP)), membrane fouling was effectively mitigated due to a dominant role of electrostatic repulsion interaction at membrane–oil interface. Compared with conventional and commercial ceramic membranes, our zirconia membrane is the first reported in literature that can effectively reject nano-sized oil droplets (∼18 nm) with over 99% rejection. Moreover, the zirconia membrane has also been challenged with real degreasing wastewater with very high oil content (∼4284 mg L–1) and pH (∼12.4) and delivered consistently high separation performance over many operation cycles.

Various nanofillers have been adopted to enhance the thermal conductivity of polymer nanocomposites. While it is widely believed that the contact thermal resistance between adjacent nanofillers can play an important role in limiting thermal conductivity enhancement of composite materials, lack of direct experimental data poses a significant challenge to perceiving the effects of these contacts. This study reports on direct measurements of thermal transport through contacts between silver nanowires (AgNWs) with a poly(vinylpyrrolidone) (PVP) interlayer. The results indicate that a PVP layer as thin as 4 nm can increase the total thermal resistance of the contact by up to an order of magnitude, when compared to bare AgNWs, even with a larger contact area. On the other hand, the thermal boundary resistance for PVP/silver interfaces could be significantly lower than that between polymer-carbon nanotubes (CNTs). Analyses based on these understandings further show why AgNWs could be more effective nanofillers than CNTs.

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.