Membrane Design Principles for Ion-Selective Electrodialysis: An Analysis for Li/Mg Separation.

Selective electrodialysis (ED) is a promising membrane-based process to separate Li+ from Mg2+, which is the most critical step for Li extraction from brine lakes. This study theoretically compares the ED-based Li/Mg separation performance of different monovalent selective cation exchange membranes (CEMs) and nanofiltration (NF) membranes at the coupon scale using a unified mass transport model, i.e., a solution-friction model. We demonstrated that monovalent selective CEMs with a dense surface thin film like a polyamide film are more effective in enhancing the Li/Mg separation performance than those with a loose but highly charged thin film. Polyamide film-coated CEMs when used in ED have a performance similar to that of polyamide-based NF membranes when used in NF. NF membranes, when expected to replace monovalent selective CEMs in ED for Li/Mg separation, will require a thin support layer with low tortuosity and high porosity to reduce the internal concentration polarization. The coupon-scale performance analysis and comparison provide new insights into the design of composite membranes used for ED-based selective ion-ion separation.

The Hidden Role of the Dielectric Effect in Nanofiltration: A Novel Perspective to Unravel New Ion Separation Mechanisms.

Nanofiltration (NF) membranes play a critical role in separation processes, necessitating an in-depth understanding of their selective mechanisms. Existing NF models predominantly include steric and Donnan mechanisms as primary mechanisms. However, these models often fail in elucidating the NF selectivity between ions of similar dimensions and the same valence. To address this gap, an innovative methodology was proposed to unravel new selective mechanisms by quantifying the nominal dielectric effect isolated from steric and Donnan exclusion through fitted pore dielectric constants by regression analysis. We demonstrated that the nominal dielectric effect encompassed unidentified selective mechanisms of significant relevance by establishing the correlation between the fitted pore dielectric constants and these hindrance factors. Our findings revealed that dehydration-induced ion-membrane interaction, rather than ion dehydration, played a pivotal role in ion partitioning within NF membranes. This interaction was closely linked to the nondeformable fraction of hydrated ions. Further delineation of the dielectric effect showed that favorable interactions between ions and membrane functional groups contributed to entropy-driven selectivity, which is a key factor in explaining ion selectivity differences between ions sharing the same size and valence. This study deepens our understanding of NF selectivity and sheds light on the design of highly selective membranes for water and wastewater treatment.

Mixing due to Solution Switch Limits the Performance of Electrosorption for Desalination.

Electrosorption (ES) is a research frontier in electrochemical separation, with proven potential applications in desalination, wastewater treatment, and selective resource extraction. However, due to the limited adsorption capacity of film electrodes, ES requires short circuiting or circuit reversal, accompanied by a solution switch between the feed solution and receiving solution, to sustain desalination over many charge-discharge cycles. In previously reported studies, solution switches have been commonly ignored to simplify experimental procedures, and their impacts on separation performance are thus not well understood. This study aims to provide a quantitative analysis of the impacts of mixing due to a solution switch on the performance of ES-based desalination. A numerical model of ES has been employed to evaluate the adverse effects of the solution switch on the desalination performance in three commonly used operation modes. The analysis reveals that the impacts of mixing due to solution-switch are more severe with a larger concentration difference between the desalinated water and the brine and provides insights into the effectiveness of increasing electrode loading or specific capacity in mitigating the detrimental impacts of mixing. Even with state-of-the-art systems, producing freshwater from seawater or even brackish water with medium-to-high salinity is practically challenging due to the presence of solution switch.

Two-dimensional fractal nanocrystals templating for substantial performance enhancement of polyamide nanofiltration membrane.

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.

Therapist and client perceptions of the working alliance: Codevelopment, linear growth, variability, and client functioning.

Using longitudinal client and therapist working alliance ratings, previous research examined how alliance: average value, linear growth, variability, stability (autocorrelation), and partner responsiveness were associated with client outcome. However, no research simultaneously examined all of these dimensions. Omitting important variables in analyses could lead to overestimation of related effects. Therefore, the purpose of this study was to examine these effects simultaneously. Therapists (N = 45) and clients (N = 236) rated alliance after every session (N = 10,720) and clients completed a measure of psychological distress after every eighth session. We used dynamic structure equation modeling to model longitudinal ratings using the longitudinal actor-partner interaction and location-scale models. Across sessions, there were significant linear growth and significant variability in client and therapist alliance ratings. The variability indicates multiple "V" patterns, which have been associated with alliance ruptures. Both actor effects were significant, showing session-to-session stability for client and therapist alliance. In addition, client-partner effect was significant, indicating higher-than-usual client alliance in a session predicting an increase in therapist alliance in the subsequent session. Growth in neither client-rated nor therapist-rated working alliances was significantly associated with client improvement. Lower variabilities (fewer fluctuations) in both client- and therapist-rated working alliances were associated with better outcomes. Higher therapist-actor and partner effects were associated with client improvement, but client-actor and partner effects were not associated with client improvement. Average working alliances were not associated with client improvement. Implications for practice and research were discussed. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Cascade Cyclization of 1,5-Diynols and (RO)2P(O)SH to Construct Benzo[b]fluorenyl S-Alkyl Phosphorothioates under Catalyst-Free Conditions.

An efficient and practical cascade cyclization of 1,5-diynols with (RO)2P(O)SH as the acid promoter and nucleophile under mild conditions was developed. A variety of highly substituted benzo[b]fluorenyl-containing S-alkyl phosphorothioates were successfully constructed in moderate to excellent yields. Furthermore, this protocol exhibited good functional group tolerance, a broad substrate scope, and potential practical applications, with water as the only byproduct. The reaction proceeded with allenyl thiophosphate as a key intermediate, followed by a Schmittel-type cyclization process to produce the target product.

Multipass Nanofiltration for Lithium Separation with High Selectivity and Recovery.

Nanofiltration (NF) is a promising and sustainable process to extract Li+ from brine lakes with high Mg2+/Li+ mass ratios. However, a trade-off between Li/Mg selectivity and Li recovery exists at the process scale, and the Li/Mg selectivity of commercially and lab-made NF membranes in a single-pass NF process is insufficient to achieve the industrially required Li purity. To overcome this challenge, we propose a multipass NF process with brine recirculation to achieve high selectivity without sacrificing Li recovery. We experimentally demonstrate that Li/Mg selectivity of a three-pass NF process with a commercial NF membrane can exceed 1000, despite the compromised Li recovery as a result of co-existing cations. Our theoretical analysis further predicts that a four-pass NF process with brine recirculation can simultaneously achieve an ultrahigh Li/Mg selectivity of over 4500 and a Li recovery of over 95%. This proposed process could potentially facilitate efficient NF-based solute-solute separations of all kinds and contribute to the development of novel membrane-based separation technologies.

Membrane Design Criteria and Practical Viability of Pressure-Driven Distillation.

Pressure-driven distillation (PD) is a novel desalination technology based on hydraulic pressure driving force and vapor transport across a hydrophobic porous membrane. In theory, PD offers near-perfect rejection for nonvolatile solutes, chlorine resistance, and the ability to decouple water and solute transport. Despite its advantages, pore wetting and the development of a reverse transmembrane temperature difference are potential critical concerns in PD, with the former compromising the salt rejection and the latter reducing or even eliminating the driving force for vapor transport. We herein present an analysis to evaluate the practical viability and membrane design principles of PD with a focus on the dependence of flux and salt rejection (SR) on membrane properties. By modeling the mass transfer in a PD process under different conditions, we arrive at two important conclusions. First, a practically detrimental reverse transmembrane temperature difference does not develop in PD under all relevant circumstances and is thus not a practical concern. Second, for a PD process to achieve an acceptable SR, the membrane pores should be at the nanometer scale with a highly uniform pore size distribution. This analysis demonstrates the practical viability of PD and provides the principles for designing robust and high-performance PD membranes.

Exploring the Knowledge Attained by Machine Learning on Ion Transport across Polyamide Membranes Using Explainable Artificial Intelligence.

Recent studies have increasingly applied machine learning (ML) to aid in performance and material design associated with membrane separation. However, whether the knowledge attained by ML with a limited number of available data is enough to capture and validate the fundamental principles of membrane science remains elusive. Herein, we applied explainable artificial intelligence (XAI) to thoroughly investigate the knowledge learned by ML on the mechanisms of ion transport across polyamide reverse osmosis (RO) and nanofiltration (NF) membranes by leveraging 1,585 data from 26 membrane types. The Shapley additive explanation method based on cooperative game theory was used to unveil the influences of various ion and membrane properties on the model predictions. XAI shows that the ML can capture the important roles of size exclusion and electrostatic interaction in regulating membrane separation properly. XAI also identifies that the mechanisms governing ion transport possess different relative importance to cation and anion rejections during RO and NF filtration. Overall, we provide a framework to evaluate the knowledge underlying the ML model prediction and demonstrate that ML is able to learn fundamental mechanisms of ion transport across polyamide membranes, highlighting the importance of elucidating model interpretability for more reliable and explainable ML applications to membrane selection and design.

Nanocomposite Hydrogel Engineered Janus Membrane for Membrane Distillation with Robust Fouling, Wetting, and Scaling Resistance.

Membrane distillation (MD) is considered to be rather promising for high-salinity wastewater reclamation. However, its practical viability is seriously challenged by membrane wetting, fouling, and scaling issues arising from the complex components of hypersaline wastewater. It remains extremely difficult to overcome all three challenges at the same time. Herein, a nanocomposite hydrogel engineered Janus membrane has been facilely constructed for desired wetting/fouling/scaling-free properties, where a cellulose nanocrystal (CNC) composite hydrogel layer is formed in situ atop a microporous hydrophobic polytetrafluoroethylene (PTFE) substrate intermediated by an adhesive layer. By the synergies of the elevated membrane liquid entry pressure, inhibited surfactant diffusion, and highly hydratable surface imparted by the hydrogel/CNC (HC) layer, the resultant HC-PTFE membrane exhibits robust resistance to surfactant-induced wetting and oil fouling during 120 h of MD operation. Meanwhile, owing to the dense and hydroxyl-abundant surface, it is capable of mitigating gypsum scaling and scaling-induced wetting, resulting in a high normalized flux and low distillate conductivity at a concentration factor of 5.2. Importantly, the HC-PTFE membrane enables direct desalination of real hypersaline wastewater containing broad-spectrum foulants with stable vapor flux and robust salt rejection (99.90%) during long-term operation, demonstrating its great potential for wastewater management in industrial scenarios.

Understanding Selectivity in Solute-Solute Separation: Definitions, Measurements, and Comparability.

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.

Negative Pressure Membrane Distillation for Excellent Gypsum Scaling Resistance and Flux Enhancement.

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.

Which Surface Is More Scaling Resistant? A Closer Look at Nucleation Theories for Heterogeneous Gypsum Nucleation in Aqueous Solutions.

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 (CaSO4·2H2O) formation on surfaces immersed in aqueous solutions. Theoretical prediction derived from classical nucleation theory (CNT) indicates that an increase of surface hydrophobicity reduces scaling potential, which contrasts our experimental results that more hydrophilic surfaces are less prone to gypsum scaling. We further consider the possibility of nonclassical pathway of gypsum nucleation, which proceeds by the aggregation of precursor clusters of CaSO4. Accordingly, we investigate the affinity of CaSO4 to substrate surfaces of varied wetting properties via calculating the total free energy of interaction, with the results perfectly predicting experimental observations of surface scaling propensity. This indicates that the interactions between precursor clusters of CaSO4 and substrate surfaces might play an important role in regulating heterogeneous gypsum formation. Our findings provide evidence that CNT might not be applicable to describing gypsum scaling in aqueous solutions. The fundamental insights we reveal on gypsum scaling mechanisms have the potential to guide rational design of scaling-resistant engineered surfaces.

Contact Thermal Resistance between Silver Nanowires with Poly(vinylpyrrolidone) Interlayers.

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.

Mechanism of Permselectivity Enhancement in Polyelectrolyte-Dense Nanofiltration Membranes via Surfactant-Assembly Intercalation.

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.

Janus Membrane with a Dense Hydrophilic Surface Layer for Robust Fouling and Wetting Resistance in Membrane Distillation: New Insights into Wetting Resistance.

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.

Bipolar Membrane Electrodialysis for Ammonia Recovery from Synthetic Urine: Experiments, Modeling, and Performance Analysis.

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.

Differentiating Solutes with Precise Nanofiltration for Next Generation Environmental Separations: A Review.

Selective removal or enrichment of targeted solutes including micropollutants, valuable elements, and mineral scalants from complex aqueous matrices is both challenging and pivotal to the success of water purification and resource recovery from unconventional water resources. Membrane separation with precision at the subnanometer or even subangstrom scale is of paramount importance to address those challenges via enabling "fit-for-purpose" water and wastewater treatment. So far, researchers have attempted to develop novel membrane materials with precise and tailored selectivity by tuning membrane structure and chemistry. In this critical review, we first present the environmental challenges and opportunities that necessitate improved solute-solute selectivity in membrane separation. We then discuss the mechanisms and desired membrane properties required for better membrane selectivity. On the basis of the most recent progress reported in the literature, we examine the key principles of material design and fabrication, which create membranes with enhanced and more targeted selectivity. We highlight the important roles of surface engineering, nanotechnology, and molecular-level design in improving membrane selectivity. Finally, we discuss the challenges and prospects of highly selective NF membranes for practical environmental applications, identifying knowledge gaps that will guide future research to promote environmental sustainability through more precise and tunable membrane separation.

Energy Efficiency of Desalination: Fundamental Insights from Intuitive Interpretation.

Desalination has become an essential toolset to combat the worsening water stress resulting from population and industrial growth and exacerbated by climate change. Various technologies have been developed to desalinate feedwater with a wide spectrum of salinity. While energy consumption is an important consideration in many desalination studies, it is challenging to make (intuitive) sense of energy efficiency due to the different mechanisms of various desalination processes and the very different separations achieved. This perspective aims to provide an intuitive, thermodynamics-based interpretation of energy efficiency by illustrating how energy consumption breaks down into minimum energy of separation and the irreversible energy dissipation. The energy efficiencies of different desalination processes are summarized and rationalized based on their working mechanisms. Notably, a new concept called the minimum mean voltage is proposed as a convenient tool to evaluate the energy efficiency of electrochemical desalination processes. Lastly, the intrinsic trade-off between energy efficiency and desalination rate and the relevance of energy efficiency in different desalination applications are discussed.

Distinct Behaviors between Gypsum and Silica Scaling in Membrane Distillation.

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.