High Ion Selectivity Research Articles

Construction of low-vacancy hexagonal Prussian blue analogues for efficient rubidium recovery

Prussian blue analogues (PBAs) are considered a promising adsorbent for rubidium recovery due to their high ion exchange capacity and selectivity. However, the development of PBAs-based rubidium adsorbents with excellent stability and adsorption capacity is still hindered by the inevitable CN ligand vacancies. Herein, a synthetic strategy is proposed to slow down crystal nucleation and promote the self-repair of crystal defects by incorporating N-doped porous carbon (NPC) as a solid modifier during the synthesis process. As a result, the vacancy content of Zn-PBA-NPC is significantly decreased and large size twinned crystals are produced, which remarkably improves the thermal and acid-base stability. Benefiting from the high content of K+ in the low-vacancy Zn-PBA-NPC, it achieves a high adsorption amount of 199.1 mg/g and rapid adsorption kinetics of just 5 min for Rb+. In addition, it shows good selectivity in the presence of other alkali metal ions. This work not only prepares a high-performance adsorbent for efficient recovery of Rb+, but also facilitates insights into the design and construction of low-vacancy PBAs.

Segmental-porosity regulation of nanochannel membranes with anomalously improved ion selectivity for enhanced osmotic power generation

Nanochannel-based osmotic energy conversion can directly convert salinity gradient energy between solutions with different ion concentrations into electric energy. In the energy conversion process, the high-concentration side of the nanochannel membrane has high ion permeability but low ion selectivity, whereas the low-concentration side exhibits opposite properties, which is the inherent limitation of osmotic power. However, the relationship between ion selectivity and permeability is unclear, which hinders the improvement of the output power density. This paper reports a segmental-porosity regulation method to break through the inherent constraints of the ion selectivity–permeability trade-off. The nanochannel membrane was divided into three regions along the ion transport direction as upstream, midstream, and downstream. The porosities of these three regions were separately regulated to optimize the structures for ion selectivity–permeability matching. When a high porosity was adopted for the downstream region and a small and mediate porosity combination was used for the upstream and midstream regions, the highest output power density was achieved, which was 78.44% higher than that of a straight nanochannel with homogeneous porosity under a 100-fold concentration ratio. The outstanding osmotic power generation performance of the optimized segmental structure was attributed to the alleviated ion concentration polarization and unexpectedly improved ion selectivity. Finally, the process and underlying mechanisms of segmental-porosity regulation are also proposed. This paper reports a novel methodology for designing the structure and porosity of nanochannel membranes to enhance osmotic power generation.

Highly Anion-Conductive Viologen-Based Two-Dimensional Polymer Membranes as Nanopower Generators.

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6-20 nm), as well as low charge density (<4.5 mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55 W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Enhanced Mg2+/Li+ separation performance of polyelectrolyte multilayers nanofiltration membranes modified by trimethylamine N-oxide zwitterions

Polyelectrolyte multilayer nanofiltration (NF) membranes have garnered attention for their potential in Mg2⁺/Li⁺ separation applications, particularly due to their positively charged nature and the versatility offered by the layer-by-layer (LbL) self-assembly technique. However, these membranes often face significant challenges in balancing high ion selectivity with adequate water permeability. Addressing these limitations, this study introduces a novel approach by grafting a zwitterionic material, trimethylamine N-oxide (TMAO), onto polyacrylamide hydrochloride (PAH), creating a new cationic polyelectrolyte (TPAH). By cyclically depositing sodium polystyrene sulfonate (PSS) and TPAH onto a polyethersulfone (PES) substrate, we have successfully fabricated a high-performance NF membrane (i.e., (PSS/TPAH)n) that demonstrates enhanced Mg2⁺/Li⁺ selectivity with high water permeability. TMAO features shorter distances between its positive and negative charge groups and smaller dipoles compared to other zwitterions. These characteristics enhance its ability to resistance to salt effects and transfer charge from amine oxide to water molecule. Furthermore, the grafting of TMAO enhanced the hydrophilicity of TPAH and regulated the charge distribution of the polyelectrolyte. Compared to the control membrane (PSS/PAH)n, the optimized membrane (PSS/TPAH)n showed reduced rejection of LiCl from 60.9 ± 2.7 % to 35.9 ± 1.5 %, while that of MgCl2 increased from 94.3 ± 1.6 % to 96.1 ± 0.7 %. Additionally, water permeability improved from 9.2 ± 0.9 LMH/bar to 16.1 ± 0.5 LMH/bar. Notably, the membranes exhibited an improved selectivity for Mg2+/Li+ ions in synthetic saline, reaching a maximum of 30.5 ± 1.5, highlighting its potential for practical separation applications. Density functional theory simulations indicate that TMAO not only enhances Donnan effect and intensify ion dehydration of polyelectrolyte multilayers NF membranes but also increases their hydrophilicity. In general, these polyelectrolyte multilayers NF membranes exhibit considerable promise for multiple applications, such as seawater pretreatment, groundwater softening and lithium extraction.

Highly Anion‐Conductive Viologen‐Based Two‐Dimensional Polymer Membranes as Nanopower Generators

AbstractTwo‐dimensional polymers (2DPs) and their layer‐stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (&lt;3 nm), much smaller than the duple Debye length in the diluted electrolyte (6–20 nm), as well as low charge density (&lt;4.5 mC m−2). Here, we introduce a π‐conjugated viologen‐based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m−2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m−2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl−, contributing to an outstanding power density of ~55 W m−2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N‐containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl− ion transport pathway. This work demonstrates the great promise of large‐area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Composite Ion-Exchange Membranes with High Specific Ion Selectivity for Efficient Electro-Membrane Processes

The advancement of ion-exchange membranes (IEMs) with heightened permselectivity for specific ions is pivotal for improving electro-membrane processes. Achieving targeted ion selectivity necessitates precise control over membrane surface characteristics, including electrostatic forces, ion transport channel size, and hydrophobicity. Utilization of diverse nanostructured materials, particularly metal-organic frameworks (MOFs), offers a pathway to modify these surface properties. MOFs, known for their structural diversity, adjustable pore sizes, and customizable frameworks, are widely applied in separation, catalysis, electrochemical, and biomedical fields. This study presents novel composite membranes, enhanced with various nanostructured materials including MOFs, demonstrating improved specific ion selectivity, robust physical strength, and superior electrochemical properties compared to standard commercial membranes. Notably, these membranes exhibit augmented performance in water-splitting electrodialysis for LiOH production, attributed to enhanced proton-blocking and monovalent ion permeability. This work was supported by the National Research Foundation of Korea (NRF) grants funded by the Korea government (MEST) (NRF-2022M3C1A3081178 and NRF-2022M3H4A4097521).

A high-performance watermelon skin ion-solvating membrane for electrochemical CO2 reduction

Ion-solvating membranes have been gaining increasing attention as core components of electrochemical energy conversion and storage devices. However, the development of ion-solvating membranes with low ion resistance and high ion selectivity still poses challenges. In order to propose an effective strategy for high-performance ion-solvating membranes, this study conducted a comprehensive investigation on watermelon skin membranes through a combination of experimental research and molecular dynamics simulation. The micropores and continuous hydrogen-bonding networks constructed by the synergistic effect of cellulose fiber and pectin enable the hypodermis of watermelon skin membranes to have a high ion conductivity of 282.3 mS cm−1 (room temperature, saturated with 1 M KOH). The negatively charged groups and hydroxyl groups on the microporous channels increase the formate penetration resistance of watermelon skin membranes in contrast to commercially available membranes, and this is crucial for CO2 electroreduction. Therefore, the confinement of proton donors and negatively charged groups within three-dimensional microporous polymers gives inspiration for the design of high-performance ion-solvating membranes.

Electrochemical technology to drive spent lithium-ion batteries (LIBs) recycling: recent progress, and prospects

The widespread use of lithium-ion batteries (LIBs) in recent years has led to a marked increase in the quantity of spent batteries, resulting in critical global technical challenges in terms of resource scarcity and environmental impact. Therefore, efficient and eco-friendly recycling methods for these batteries are needed. The recycling methods for spent LIBs include hydrometallurgy, pyrometallurgy, solid-phase regeneration, and electrochemical methods. Compared to other recycling methods, electrochemical methods offer high ion selectivity and environmental friendliness. Assembling research on the recycling and reutilization of spent LIBs, with a focus on the various electrochemical techniques that can enhance these processes, is essential. A thorough analysis of the characteristics and evolution of these methods remains crucial to advancing the field of electrochemical technology in battery recycling. This review first discussed the necessity of recycling spent LIBs from multiple perspectives and briefly introduced the main pyrometallurgical and hydrometallurgical recycling technologies, analyzing their advantages and disadvantages. Moreover, we comprehensively summarized the current applications of electrochemical technology in the recycling of spent LIBs, including pretreatment, leaching, element separation, and regeneration. Then, we analyzed the characteristics and advantages of different electrochemical techniques in the LIB recycling process and discussed the obstacles encountered in the application of electrochemical technology and their solutions. Finally, a comparison between electrochemical technology and traditional recycling processes was provided, highlighting the potential advantages of electrochemical technology in reducing recycling costs and minimizing waste emissions.

Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr‐MOF‐Based Heterogeneous Membrane with Trilayered Continuous Porous Structure

AbstractDesigning a nanofluidic membrane with high selectivity and fast ion transport property is the key towards high‐performance osmotic energy conversion. However, most of reported membranes can produce power density less than commercial benchmark (5 W/m2), due to the imbalance between ion selectivity and permeability. Here, we report a novel nanoarchitectured design of a heterogeneous membrane with an ultrathin and dense zirconium‐based UiO‐66‐NH2 metal–organic framework (MOF) layer and a highly aligned and interconnected branched alumina nanochannel membrane. The design leads to a continuous trilayered pore structure of large geometry gradient in the sequence from angstrom‐scale to nano‐scale to sub‐microscale, which enables the enhanced directional ion transport, and the angstrom‐sized (~6.6–7 Å) UiO‐66‐NH2 windows render the membrane with high ion selectivity. Consequently, the novel heterogeneous membrane can achieve a high‐performance power of ~8 W/m2 by mixing synthetic seawater and river water. The power density can be largely upgraded to an ultrahigh ~17.1 W/m2 along with ~48.5 % conversion efficiency at a 50‐fold KCl gradient. This work not only presents a new membrane design approach but also showcases the great potential of employing the zirconium‐based MOF channels as ion‐channel‐mimetic membranes for highly efficient blue energy harvesting.

Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr-MOF-Based Heterogeneous Membrane with Trilayered Continuous Porous Structure.

Designing a nanofluidic membrane with high selectivity and fast ion transport property is the key towards high-performance osmotic energy conversion. However, most of reported membranes can produce power density less than commercial benchmark (5 W/m2), due to the imbalance between ion selectivity and permeability. Here, we report a novel nanoarchitectured design of a heterogeneous membrane with an ultrathin and dense zirconium-based UiO-66-NH2 metal-organic framework (MOF) layer and a highly aligned and interconnected branched alumina nanochannel membrane. The design leads to a continuous trilayered pore structure of large geometry gradient in the sequence from angstrom-scale to nano-scale to sub-microscale, which enables the enhanced directional ion transport, and the angstrom-sized (~6.6-7 Å) UiO-66-NH2 windows render the membrane with high ion selectivity. Consequently, the novel heterogeneous membrane can achieve a high-performance power of ~8 W/m2 by mixing synthetic seawater and river water. The power density can be largely upgraded to an ultrahigh ~17.1 W/m2 along with ~48.5 % conversion efficiency at a 50-fold KCl gradient. This work not only presents a new membrane design approach but also showcases the great potential of employing the zirconium-based MOF channels as ion-channel-mimetic membranes for highly efficient blue energy harvesting.

Zwitterionic channels within covalent organic frameworks facilitate proton-selective transport for flow battery membrane

Flow batteries demand for ion conductive membranes (ICMs) with high ion selectivity to achieve efficient energy conversion. Herein, we engineered a cysteine-modified covalent organic framework (Cys-COF) by a Thiol-ene click reaction. As a promising proton carrier, the incorporation of the Cys-COF with sulfonated poly(ether ketone) (SPEEK) yields advanced ICMs for vanadium flow batteries (VFBs). The zwitterionic cysteine groups anchored on the nanochannel walls simultaneously narrowed the pore size and ameliorated the protophilicity of Cys-COF, resulting in improved vanadium permeating resistance and proton conductivity. As a result, the optimal membrane demonstrated synchronized improvements in coulombic efficiency (95.01 %–98.84 %), voltage efficiency (95.15 %–77.84 %) and energy efficiency (90.41 %–76.94 %) with the current densities ranging from 40 to 200 mA cm−2. Regarding stability test, it achieved exceptional energy efficiency (∼84.3 %) over 1100 cycles and 550 h at the constant current density of 120 mA cm−2, outperforming pure polymer membrane and Nafion 212.

Ultrathin Ionic Diodes with Electrostatically Heterogeneous Hybrid Interfaces of Nanoporous SiO2 Nanofilms and Polymer Layer-by-Layer Multilayers.

Nanofluidic ionic diodes have attracted much attention due to their unique functions as unidirectional ion transportation ability and promising applications from molecular sensing, and energy harvesting to emerging neuromorphic devices. However, it remains a challenge to fabricate diode-like nanofluidic systems with ultrathin film thickness <100nm. Herein the formation of ultrathin ionic diodes from hybrid nanoassemblies of nanoporous (NP) SiO2 nanofilms and polyelectrolyte layer-by-layer (LbL) multilayers is described. Ultrathin ionic diodes are prepared by integrating polyelectrolyte multilayers onto photo-oxidized NP SiO2 nanofilms obtained from silsesquioxane-containing block copolymer thin films as a template. The obtained ultrathin ionic diodes exhibit ion current rectification (ICR) properties with high ICR factor = ≈20 under low ionic strength and asymmetric pH conditions. It is concluded that this ICR behavior arises from effective ion accumulation and depletion at the interface of NP SiO2 nanofilms and LbL multilayers attributed to high ion selectivity by combining the experimental data and theoretical calculations using finite element methods. These results demonstrate that the hybrid nano assemblies of NP SiO2 nanofilms and polyelectrolyte LbL multilayers have potential applications for (bio)sensing materials and integrated ionic circuits for seamless connection of human-machine interfaces.

Selectivity filter mutations shift ion permeation mechanism in potassium channels.

Potassium (K+) channels combine high conductance with high ion selectivity. To explain this efficiency, two molecular mechanisms have been proposed. The "direct knock-on" mechanism is defined by water-free K+ permeation and formation of direct ion-ion contacts in the highly conserved selectivity filter (SF). The "soft knock-on" mechanism involves co-permeation of water and separation of K+ by water molecules. With the aim to distinguish between these mechanisms, crystal structures of the KcsA channel with mutations in two SF residues-G77 and T75-were published, where the arrangements of K+ ions and water display canonical soft knock-on configurations. These data were interpreted as evidence of the soft knock-on mechanism in wild-type channels. Here, we test this interpretation using molecular dynamics simulations of KcsA and its mutants. We show that while a strictly water-free direct knock-on permeation is observed in the wild type, conformational changes induced by these mutations lead to distinct ion permeation mechanisms, characterized by co-permeation of K+ and water. These mechanisms are characterized by reduced conductance and impaired potassium selectivity, supporting the importance of full dehydration of potassium ions for the hallmark high conductance and selectivity of K+ channels. In general, we present a case where mutations introduced at the critical points of the permeation pathway in an ion channel drastically change its permeation mechanism in a nonintuitive manner.

Ion-selective supramolecular membrane with pH-regulated smart nanochannels for lithium extraction

Tunable gating ion-conducting membranes with high water permeability and precise ion selectivity remain urgently demanded in smart nanofiltration for efficient lithium extraction. Herein, inspired by the filtration function of protein channels, we report a smart and high-performance supramolecular membrane constructed via coordination between quaternary ammonium ligands (m-phenylenediamine/polyethyleneimine) and metal ion center (Cu2+). The pore architecture of the supramolecular membrane is dynamic and can be switched by applying pH stimulus, where coordinated interchain expands when exposed to acidic operating conditions and induces concomitantly reinforced electrostatic exclusion due to enhanced local charge density. The tunable gating regularity enables operando modulation of precise ionic separation in situ. The resulting membrane exhibits significantly enhanced water permeance (19.8 L m−2 h−1·bar−1) and simultaneously promoted Li+/Mg2+ selectivity (RMg2+ = 96.4 %), surpassing typical trade-off between permeability and selectivity at pH 3 condition. This study demonstrates the amazing capability of environmental-responsive regulation of membrane pore-channel structure, and provides inspiration for engineering advanced supramolecular membranes for lithium extraction and beyond.

Optimizing Nanofluidic Energy Harvesting in Synthetic Clay-based Membranes by Annealing Treatment.

Nanofluidic energy harvesting from salinity gradients is studied in 2D nanomaterials-based membranes with promising performance as high ion selectivity and fast ion transport. In addition, moving forward to scalable, feasible systems requires environmentally friendly materials to make the application sustainable. Clay-based membranes are attractive for being environmentally friendly, non-hazardous, and easy to manipulate materials. However, achieving underwater stability for clay-based membranes remains challenging. In this work, the synthetic clay Laponite is used to prepare clay-based membranes with high stability and excellent performance for osmotic energy harvesting. The Laponite membranes (Lap-membranes) are stabilized by low-temperature annealing treatment to effectively reduce the interlayer space, achieving a continuous operation under salinity gradients. Furthermore, the Lap-membranes conserve integrity while soaking in water for more than one month. The output power density improves from ≈4.97W m-2 on the pristine membrane to ≈9.89W m-2 in the membrane treated 12 h at 300°C from a 30-fold concentration gradient. Especially, It is found that the presence of interlayer water to be favorable for ion transport. Different mechanisms are proposed in the Lap-membranes involved for efficient ion selectivity and the states found with varying annealing temperatures. This work demonstrates the potential application of Laponite based nanomaterials for nanofluidic energy harvesting.

Phosphoric acid pre-swelling strategy constructing acid-doped fluoropoly(aryl pyridinium) membranes to enable high-performance vanadium flow batteries

Vanadium flow batteries (VFBs) have promising applications for grid-scale energy storage. Unfortunately, the widespread integration of VFBs into large-scale energy storage applications is hindered by the lack of low-cost ion-conducting membranes (ICMs) with high ion selectivity and excellent stability. Herein, we propose an intrinsically stabilized ether-free fluoropoly(aryl pyridine) (PFNP) and provide a high-performance acid-doped membrane via a phosphoric acid pre-swelling strategy for the battery. Effective acid-doping enables the formation of discrete hydrophilic nano-channels within the PFNP matrix, and the extensive internal hydrogen-bonding network synergistically facilitates charge carrier transport. Simultaneously, the close stacking of PFNP chains and the Donnan effect of protonated piperidinium groups within the membrane effectively prevent vanadium ions permeation. Consequently, this innovative strategy allows the acid-doped membrane to achieve nearly perfect ion selectivity (3.64 × 105 S min cm−3), outperforming the Nafion 212 membrane (3.01 × 104 S min cm−3). Moreover, the fluorinated ether-free structure and non-weak-bondpyridine structure impart excellent mechanical and chemical stability to the acid-doped membrane, ensuring long-term membrane operation. As expected, the VFBs assembled with the acid-doped membrane achieve high energy efficiency (83.1 %) at high current density (200 mA cm−2), offer an ultra-low capacity decay rate of 0.08 % per cycle and retain outstanding stability after 1500 cycles at 120 mA cm−2. This study provides a potential material system for commercial VFB membranes by achieving high performance at low cost.

Have a Cake and Eat it Too: A Nanofluidic Hybrid Membrane with Both High Stability and Ionic Conductivity

AbstractTwo‐dimensional nanofluidic membranes are promising candidates for various applications, such as energy conversion and ionic sensing. However, simultaneously achieving high stability and high ion transport in a nanofluidic membrane remains a great challenge. Herein, a robust and durable aramid nanofiber/carboxylated aramid nanofiber (ANF/cANF) nanofluidic hybrid membrane is designed with high ion conductivity and selectivity via surface grafting engineering and hybridization strategies. Due to the inherent ordered and asymmetric molecular structure, the strong interchain interactions of the ANF and the strong interfacial interactions between the ANF and cANF enable the membrane to exhibit robust structural stability in a wet state. Meanwhile, the enhanced surface charge enabled by the surface functionalization of carboxyl groups on the ANF results in excellent ion transport. As a result, the conductivity of the membrane is 5 and 36 times higher than the ANF membrane and bulk solution, respectively. Importantly, the ionic conductivity and mechanical strength of the membrane remain unchanged even after immersing in water for 90 days, demonstrating favorable underwater application potential. Moreover, the membrane is recyclable and has superior processability, allowing for large‐scale processing. This work provides a new strategy for designing durable and high‐ion‐transporting nanofluidic membranes for ion sensing and energy conversion.

Unlocking Direct Lithium Extraction in Harsh Conditions through Thiol-Functionalized Metal-Organic Framework Subnanofluidic Membranes.

Metal-organic framework (MOF) membranes with high ion selectivity are highly desirable for direct lithium-ion (Li+) separation from industrial brines. However, very few MOF membranes can efficiently separate Li+ from brines of high Mg2+/Li+ concentration ratios and keep stable in ultrahigh Mg2+-concentrated brines. This work reports a type of MOF-channel membranes (MOFCMs) by growing UiO-66-(SH)2 into the nanochannels of polymer substrates to improve the efficiency of MOF membranes for challenging Li+ extraction. The resulting membranes demonstrate excellent monovalent metal ion selectivity over divalent metal ions, with Li+/Mg2+ selectivity up to 103 since Mg2+ should overcome a higher energy barrier than Li+ when transported through the MOF pores, as confirmed by molecular dynamics simulations. Under dual-ion diffusion, as the Mg2+/Li+ mole ratio of the feed solution increases from 0.2 to 30, the membrane Li+/Mg2+ selectivity decreases from 1516 to 19, corresponding to the purity of lithium products between 99.9 and 95.0%. Further research on multi-ion diffusion that involves Mg2+ and three monovalent metal ions (K+, Na+, and Li+, referred to as M+) in the feed solutions shows a significant improvement in Li+/Mg2+ separation efficiency. The Li+/Mg2+ selectivity can go up to 1114 when the Mg2+/M+ molar concentration ratio is 1:1, and it remains at 19 when the ratio is 30:1. The membrane selectivity is also stable for 30 days in a highly concentrated solution with a high Mg2+/Li+ concentration ratio. These results indicate the feasibility of the MOFCMs for direct lithium extraction from brines with Mg2+ concentrations up to 3.5 M. This study provides an alternative strategy for designing efficient MOF membranes in extracting valuable minerals in the future.

Crown-Ether Crystal Channel Membranes with Subnanometer Pores for Selective Na+ Transport.

Emulating biological sodium ion channels to achieve high selectivity and rapid Na+ transport is important for water desalination, energy conversion, and separation processes. However, the development of artificial ion channels, especially multichannels, to achieve high ion selectivity, remains a challenge. In this work, we demonstrate the fabrication of ion channel membranes utilizing crown-ether crystals (DA18C6-nitrate crystals), which feature extremely consistent subnanometer pores. The polyethylene terephthalate (PET) membranes were initially subjected to amination, followed by the in situ growth of DA18C6-nitrate crystals to establish ordered multichannels aimed at facilitating selective Na+ conductance. These channels allow rapid Na+ transport while inhibiting the migration of other ions (K+ and Ca2+). The Na+ transport rate was 2.15 mol m-2 h-1, resulting in the Na+/K+ and Na+/Ca2+ selectivity ratios of 6.53 and 12.56, respectively. Due to the immobilization of the crown-ether ring, when the size of the transmembrane ion exceeded that of the crown-ether ring's cavity, the ions had to undergo a dehydration process to pass through the channel. This resulted in the ions encountering a higher energy barrier upon entering the channel, making it more difficult for them to permeate. However, the size of Na+ was compatible with the cavity of the crown-ether ring and was able to displace the hydrated layer effectively, facilitating selective Na+ translocation. In summary, this research offers a promising approach for the future development of functionalized ion channels and efficient membrane materials tailored for high-performance Na+ separation.

Enhancing Surface Charge Density of Graphene Oxide Membranes through Al(OH)4− Anion Incorporation for Osmotic Energy Conversion

Graphene oxide (GO) has been extensively studied for fabricating ion exchange membranes. This material is of interest due to its surface‐governed charge which, combined with the interlayer distance between the GO flakes stack, offers ion selectivity. However, obtaining high‐performing membranes with high ion selectivity and low ionic resistance remains challenging. To address this issue, Al(OH)4− anions are incorporated into graphene oxide membranes to increase their spontaneous negative surface charge. The anions are successfully formed and encapsulated through a reaction with the alumina support under alkaline conditions during the membrane fabrication. A modeling of the system proves the anchoring of the Al(OH)4− anions within the GO matrix. The incorporation of these anions significantly improves the permselectivity and reduces the ionic resistance, reaching approximately 95% and 2 Ω cm2, respectively. The GO‐modified membranes also present mono‐valent selectivity, which can boost reverse electrodialysis power densities.