Ion Selectivity Research Articles

A review of direct recycling methods for spent lithium-ion batteries

The increasing demand for lithium-ion batteries (LIBs) in new energy storage systems and electric vehicles implies a surge in both the shipment and scrapping of LIBs. LIBs contain a lot of harmful substances, and improper disposal can cause severe environment damage. Developing efficient recycling technology has become the key to the sustainable growth of the LIBs industry. At present, the extraction of high-value materials from spent LIBs using pyrometallurgical and hydrometallurgical processes is most usual. However, they consume a lot of energy and lead to secondary environmental pollution, which is not consistent with the idea of creating a green circular economy. Direct recycling has been suggested as a possible alternative method of dealing with the spent LIBs under non-destructive conditions in the further. Compared with traditional metallurgical technologies, direct regeneration significantly reduces the consumption of energy and chemical reagents, and has a high selectivity for certain metal ions, which is environmentally friendly. However, direct cycling is still in its infancy with many scientific and technological barriers. In this review, we first consider the necessity of recycling spent LIBs, and then summarize the failure mechanisms of degraded cathode materials in order to choose a corresponding regeneration method. The direct cycling technologies, including hydrothermal, solid-state, eutectic medium and electrochemical regeneration are introduced separately from the perspective of the experimental process, operating parameters, regeneration principles, advantages, and effects. Furthermore, the current problems and potential future research on the direct cycling of spent LIBs are also discussed.

Enhanced luminescent properties of poly(sodium acrylate)-based composite and its selective interaction towards copper ions

This study investigates the luminescent properties and metal ion interactions of europium when combined with a polymer chain of poly (sodium acrylate) (PSA) and a phenanthroline (Phen) molecule, which acts as an efficient antenna. The study of interactions between lanthanide ions and various compounds in different matrices is crucial, providing valuable insights into the molecular environment, and enabling a deeper understanding of processes affecting their luminescence. In this study, we investigated the luminescent properties of the Eu(PSA)Phen complex and its remarkable capacity for selective interaction with Cu2+ ions in an aqueous solution. From this selective interaction, we conducted a series of detailed studies that provided valuable insights into the mechanisms of luminescence suppression, information about the europium chemical environment, and other related aspects. The luminescence of Eu(PSA)Phen is significantly quenched by Cu2+ ions, driven by both static and dynamic mechanisms. The presence of the PSA polymer chain and Phen molecules within the composite exerts a profound influence on energy transfer processes, enabling selective responses to Cu2+ ions, even in the presence of competing cations. Additionally, we observed a preferential interaction of the PSA molecule in the Eu(PSA)Phen composite with Cu2+ ions over the N groups of phenanthroline. These findings underscore the compound potential as a versatile tool in various fields, ranging from material science to biosensing, where rapid and selective metal ion detection is of paramount importance.

Investigation on the Enhanced Ion Impermeability of Bipolar Corrosion Resistant Coating Prepared with Mg/Al-HT

Hydrotalcite (HT), which contains a large amount of easily exchanged hydroxyl groups, and has attracted great attention in the field of corrosion protection. Taking this aspect into consideration, this study has prepared bipolar corrosion resistant coating with modified magnesium-aluminum synthetic hydrotalcite (Mg/Al-HT) , which restrains both the anion and cation migration in the coating. It is achieved by applying sodium dodecyl benzene sulfonate (SDBS) and cetyltrimethyl ammonium bromide (CTAB) to modify Mg/Al-HT and blending with phenolic epoxy resin. The chemical composition and morphology of the modified Mg/Al-HT are analyzed using SEM, FT-IR, and Raman spectroscopy. The ion selectivity of the prepared coating is evaluated with membrane potential test. Observation of the macroscopic pictures revealed that no corrosion products were observed on the surface of the bipolar coating after 60 days of immersion in 3.5 wt.% NaCl solution. The corresponding interfacial impedance behavior is investigated. The typical impedance modulus @0.01 Hz remains constant at about 109 Ω·cm2 after 60 days of exposure in 3.5 wt.% NaCl solution, which is 102-103 times higher than that of the conventional coating. The mechanism of the enhanced ion impermeability is discussed in the paper.

Ion and Molecular Sieving with Ultrathin Polydopamine Nanomembranes.

In contrast to biological cell membranes, it is still a major challenge for synthetic membranes to efficiently separate ions and small molecules, due to their similar sizes in the sub-nanometer range. Inspired by biological ion channels with their unique channel wall chemistry that facilitates ion sieving by ion-channel interactions, we report here the first free-standing, ultrathin (10-17nm) nanomembranes composed entirely of polydopamine (PDA) as ion and molecular sieves. These nanomembranes are obtained via an easily scalable electropolymerization strategy and provide nanochannels with various amine and phenolic hydroxyl groups that offer a favorable chemical environment for ion-channel electrostatic and hydrogen bond interactions. They exhibit remarkable selectivity for monovalent ions over multivalent ions and larger species with K+/Mg2+ of ≈4.2, K+/[Fe(CN)6]3- of ≈10.3, and K+/Rhodamine B of ≈273.0 in a pressure-driven process, as well as cyclic reversible pH-responsive gating properties. Infrared spectra reveal hydrogen bond formation between hydrated multivalent ions and PDA, which prevents the transport of multivalent ions and facilitates high selectivity. We propose chemically rich, free-standing, and pH-responsive PDA nanomembranes with specific interaction sites as customizable high-performance sieves for a wide range of challenging separation requirements. This article is protected by copyright. All rights reserved.

Robust antibacterial activity of rare-earth ions on planktonic and biofilm bacteria.

Bacterial infections pose a serious threat to human health, with emerging antibiotic resistance, necessitating the development of new antibacterial agents. Cu2+and Ag+are widely recognized antibacterial agents with a low propensity for inducing bacterial resistance; however, their considerable cytotoxicity constrains their clinical applications. Rare-earth ions, owing to their unique electronic layer structure, hold promise as promising alternatives. However, their antibacterial efficacy and biocompatibility relative to conventional antibacterial agents remain underexplored, and the variations in activity across different rare-earth ions remain unclear. Here, we systematically evaluate the antibacterial activity of five rare-earth ions (Yb3+, Gd3+, Sm3+, Tb3+, and La3+) againstStaphylococcus aureusandPseudomonas aeruginosa, benchmarked against well-established antibacterial agents (Cu2+, Ag+) and the antibiotic norfloxacin. Cytotoxicity is also assessed via live/dead staining of fibroblasts after 24 h rare-earth ion exposure. Our findings reveal that rare-earth ions require higher concentrations to match the antibacterial effects of traditional agents but offer the advantage of significantly lower cytotoxicity. In particular, Gd3+demonstrates potent bactericidal efficacy against both planktonic and biofilm bacteria, while maintaining the lowest cytotoxicity toward mammalian cells. Moreover, the tested rare-earth ions also exhibited excellent antifungal activity againstCandida albicans. This study provides a critical empirical framework to guide the selection of rare-earth ions for biomedical applications, offering a strategic direction for the development of novel antimicrobial agents.

Advances in Two-Dimensional Ion-Selective Membranes: Bridging Nanoscale Insights to Industrial-Scale Salinity Gradient Energy Harvesting.

Salinity gradient energy, often referred to as the Gibbs free energy difference between saltwater and freshwater, is recognized as "blue energy" due to its inherent cleanliness, renewability, and continuous availability. Reverse electrodialysis (RED), relying on ion-selective membranes, stands as one of the most prevalent and promising methods for harnessing salinity gradient energy to generate electricity. Nevertheless, conventional RED membranes face challenges such as insufficient ion selectivity and transport rates and the difficulty of achieving the minimum commercial energy density threshold of 5 W/m2. In contrast, two-dimensional nanostructured materials, featuring nanoscale channels and abundant functional groups, offer a breakthrough by facilitating rapid ion transport and heightened selectivity. This comprehensive review delves into the mechanisms of osmotic power generation within a single nanopore and nanochannel, exploring optimal nanopore dimensions and nanochannel lengths. We subsequently examine the current landscape of power generation using two-dimensional nanostructured materials in laboratory-scale settings across various test areas. Furthermore, we address the notable decline in power density observed as test areas expand and propose essential criteria for the industrialization of two-dimensional ion-selective membranes. The review concludes with a forward-looking perspective, outlining future research directions, including scalable membrane fabrication, enhanced environmental adaptability, and integration into multiple industries. This review aims to bridge the gap between previous laboratory-scale investigations of two-dimensional ion-selective membranes in salinity gradient energy conversion and their potential large-scale industrial applications.

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.

Synthesis of polyvinylpyrrolidone-protected silver nanoclusters with strong fluorescence for highly sensitive and selective hexavalent chromium ion detection

Synthesis of polyvinylpyrrolidone-protected silver nanoclusters with strong fluorescence for highly sensitive and selective hexavalent chromium ion detection

Self-Adaptive Graphdiyne/Sn Interface for High-Performance Sodium Storage.

Efficiently reconciling the substantial volume strain with maintaining the stabilities of both interfacial protection and three-dimensional (3D) conductive networks is a scientific and technical challenge in developing tin-based anodes for sodium ion storage. To address this issue, a proof-of-concept self-adaptive protection for the Sn anode is designed, taking advantage of the arbitrary substrate growth of graphdiyne. This protective layer, employing a flexible chain doping strategy, combines the benefits of 2D graphdiyne and linear chain structures to achieve 2D mechanical stability, electronic and ion conductions, ion selectivity, adequate elongation, and flexibility. It establishes close contact with the Sn particles and can adapt to dynamic size changes while effectively facilitating both electronic and ion transports. It successfully mitigates the detrimental effects of particle pulverization and coarsening induced by large-volume changes. The as-obtained Sn electrodes demonstrate exceptional stability, enduring 1800 cycles at a high current density of 2.5 A g-1. This strategy promises to address the general issues associated with large-strain electrodes in next-generation of high-energy-density batteries.

Perfect confinement of crown ethers in MOF membrane for complete dehydration and fast transport of monovalent ions.

Fast transport of monovalent ions is imperative in selective monovalent ion separation based on membranes. Here, we report the in situ growth of crown ether@UiO-66 membranes at a mild condition, where dibenzo-18-crown-6 (DB18C6) or dibenzo-15-crown-5 is perfectly confined in the UiO-66 cavity. Crown ether@UiO-66 membranes exhibit enhanced monovalent ion transport rates and mono-/divalent ion selectivity, due to the combination of size sieving and interaction screening effects toward the complete monovalent ion dehydration. Specifically, the DB18C6@UiO-66 membrane shows a permeation rate (e.g., K+) of 1.2 mol per square meter per hour and a mono-/divalent ion selectivity (e.g., K+/Mg2+) of 57. Theoretical calculations and simulations illustrate that, presumably, ions are completely dehydrated while transporting through the DB18C6@UiO-66 cavity with a lower energy barrier than that of the UiO-66 cavity. This work provides a strategy to develop efficient ion separation membranes via integrating size sieving and interaction screening and to illuminate the effect of ion dehydration on fast ion transport.

Green Synthesis of Highly Fluorescent NCQDs: A Comprehensive Study on Synthesis, Characterization, Photophysical Properties, pH Sensing, Heavy Metal Detection, and Solvatochromic Behavior through Hydrothermal Method.

Solvatochromic studies in conjunction with NCQDs and analysis of material at different pH levels provide valuable insights about the process of metal ion sensing. Metal ion sensing holds significant importance in various fields like environment monitoring, biomedical diagnostics and various industrial purpose. The detection of metal ions by mixing the nitrogen-doped quantum dots (NCQDs) in the solvent at different pH levels for the analysis of the photoluminescence spectra is the unique property to achieve selective metal ion detection.In present study, the synthesis of NCQDs was performed by the use of flowers of Tecoma stans. The synthesis of NCQDs to best of our knowledge using flowers of Tecoma stans as natural carbon source via hydrothermal process has been done for the first time. The NCQDs exhibit absorption bands ranging from 190 to 450nm, with the energy band gap varying from 3.55 to 5.42eV when mixed with different solvent such as, 1-4 dioxane, acetone, acetonitrile, ethyl- acetate, ethanol, methanol and toluene. The fluorescence spectra exhibited highly intense range from approximately 390 to 680nm across various solvents. XRD analysis further confirmed the crystalline nature of the particles with an average size of 6.96nm. Different peak positions of the FTIR spectra support functional groups having C-H stretching, C = O (carbonyl) stretching, and C = C stretching vibrations.In the study a notable solvatochromic shift was observed, indicating sensitivity to change in solvent polarity. Additionally, the investigation of the ratio of ground to excited state dipole moment based on solvatochromic shift yielded a value of 3.30. This provide valuable information about optical and electronic properties of NCQDs. Overall, our study sheds light on the unique properties of NCQDs synthesized from Tecoma stans flowers and their potential applications in metal ion sensing, pH probing, and solvent polarity studies.

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.

Second-order, positive, and unconditional energy dissipative scheme for modified Poisson–Nernst–Planck equations

First-order energy dissipative schemes in time are available in literature for the Poisson–Nernst–Planck (PNP) equations, but second-order ones are still in lack. This work proposes novel second-order discretization in time and finite volume discretization in space for modified PNP equations that incorporate effects arising from ionic steric interactions and dielectric inhomogeneity. A multislope method on unstructured meshes is proposed to reconstruct positive, accurate approximations of mobilities on faces of control volumes. Numerical analysis proves that the proposed numerical schemes are able to unconditionally ensure the existence of positive numerical solutions, original energy dissipation, mass conservation, and preservation of steady states at discrete level. Extensive numerical simulations are conducted to demonstrate numerical accuracy and performance in preserving properties of physical significance. Applications in ion permeation through a 3D nanopore show that the modified PNP model, equipped with the proposed schemes, has promising applications in the investigation of ion selectivity and rectification. The proposed second-order discretization can be extended to design temporal second-order schemes with original energy dissipation for a type of gradient flow problems with entropy.

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.

Toward Selective Transport of Monovalent Metal Ions with High Permeability Based on Crown Ether-Encapsulated Metal-Organic Framework Sub-Nanochannels.

Achieving selective transport of monovalent metal ions with high precision and permeability analogues to biological protein ion channels has long been explored for fundamental research and various applications, such as ion sieving, mineral extraction, and energy harvesting and conversion. However, it still remains a significant challenge to construct artificial nanofluidic devices to realize the trade-off effects between selective ion transportation and high ion permeability. In this work, we report a bioinspired functional micropipet with in situ growth of crown ether-encapsulated metal-organic frameworks (MOFs) inside the tip and realize selective transport of monovalent metal ions. The functional ion-selective micropipet with sub-nanochannels was constructed by the interfacial growth method with the formation of composite MOFs consisting of ZIF-8 and 15-crown-5. The resulting micropipet device exhibited obvious monovalent ion selectivity and high flux of Li+ due to the synergistic effects of size sieving in subnanoconfined space and specific coordination of 15-crown-5 toward Na+. The selectivity of Li+/Na+, Li+/K+, Li+/Ca2+, and Li+/Mg2+ with 15-crown-5@ZIF-8-functionalized micropipet reached 3.9, 5.2, 105.8, and 122.4, respectively, which had an obvious enhancement compared to that with ZIF-8. Notably, the ion flux of Li+ can reach up to 93.8 ± 3.6 mol h-1·m-2 that is much higher than previously reported values. Furthermore, the functional micropipet with 15-crown-5@ZIF-8 sub-nanochannels exhibited stable Li+ selectivity under various conditions, such as different ion concentrations, pH values, and mixed ion solutions. This work not only provides new opportunities for the development of MOF-based nanofluidic devices for selective ion transport but also facilitates the promising practical applications in lithium extraction from salt-like brines, sewage treatment, and other related aspects.

Modification induced by electronic excitation in CoFe2O4 thin films: Structural, morphological, and magnetic properties

AbstractThe present study focuses on the modification induced by 200 MeV Ag15+ and 100 MeV O7+ ion irradiations on the structural, surface morphological, and magnetic properties of radio frequency sputtered CoFe2O4 (CFO) thin films grown on SiO2/Si (100) substrates. X‐ray diffraction shows amorphization of the CFO thin films when irradiated with Ag ions and varies with fluences. This effect is absent in the case of O ion irradiated CFO films. These results are consistent with the measurements from the Raman spectroscopy, where the intensities of Eg and T2g modes are significantly reduced and further disappear in the high fluence. The surface morphology of the O ion irradiated films is dramatically different from the pristine and Ag ion irradiated films where the surfaces appear in nanopillars‐like patterns. The topography of the O ion irradiated films appears to be like hill and valley structures, the roughness first increases (from 10.11 to 24.39 nm). Then it decreases to 18.93 nm on further increasing ion fluence. The coercivity, remnant magnetization, and saturation magnetization increase upon irradiation at low fluence 5 × 1011 ions/cm2 for both the ion beams and then downturn with the increase of fluence 5 × 1012 ions/cm2. The changes in the magnetic and structural characteristics are ascribed to the defects induced by ion irradiation. These results are understood based on the structural and surface modifications induced by the electronic excitation of Ag and O ions. The study depicts that a controlled selection of ions and beam fluence can tailor the structure, morphology, and magnetic properties of ferrite films.

Dual-network fiber-hydrogel membrane for osmotic energy harvesting

Osmotic energy harvesting was a promising way to alleviate energy crisis with reverse electrodialysis (RED) membrane-based technology. Charged hydrogel combined with other materials was an effective strategy to overcome problems, including restricted functional groups and complicated fabrication, but the effect of the respective charges of the two materials combined on the membrane properties has rarely been studied in depth. Herein, a new method was proposed that charged hydrogel was equipped with charged filter paper to form dual network fiber-hydrogel membrane for osmotic energy harvesting, which had excellent ion selectivity (beyond 0.9 under high concentration gradient), high ion transference number and energy conversion efficiency (beyond 32.5% under wide range concentration gradient), good property of osmotic energy conversion (∼4.84 W/m2 under 50-fold KCl and ∼6.75 W/m2 under simulated sea water and river water). Moreover, the power density was attributed to the surface-space charge synergistic effect from large amounts overlapping of electric double layer (EDL), so that the transmembrane ion transport was enhanced. It might be a valid mode to extensively develop the osmotic energy harvesting.

Borophene Quantum Dots with Strong Photoluminescence for Selective Metal Ion Sensing

Borophene Quantum Dots with Strong Photoluminescence for Selective Metal Ion Sensing

Mechanistic basis of the dynamic response of TWIK1 ionic selectivity to pH

Highly selective for K+ at neutral pH, the TWIK1 channel becomes permeable to Na+ upon acidification. Using molecular dynamics simulations, we identify a network of residues involved in this unique property. Between the open and closed states previously observed by electron microscopy, molecular dynamics simulations show that the channel undergoes conformational changes between pH 7.5–6 involving residues His122, Glu235, Lys246 and Phe109. A complex network of interactions surrounding the selectivity filter at high pH transforms into a simple set of stronger interactions at low pH. In particular, His122 protonated by acidification moves away from Lys246 and engages in a salt bridge with Glu235. In addition, stacking interactions between Phe109 and His122, which stabilize the selectivity filter in its K+-selective state at high pH, disappear upon acidification. This leads to dissociation of the Phe109 aromatic side chain from this network, resulting in the Na+-permeable conformation of the channel.

Large‐Area Graphene‐Based Ion‐Selective Membranes with Micro/Meso‐Pores for Osmotic Energy Harvesting

AbstractRenewable osmotic energy between seawater and river water shows great potential in meeting global energy demand. Reverse electrodialysis (RED) technique using ion‐selective membrane is particularly outstanding for its easy operation. Preparing low‐cost and large‐area ion‐selective membranes with excellent ion transport characteristics is particularly important to promote commercial applications. Herein, large‐area ion‐selective membrane is prepared by scraping slurry of flocculated GO (graphene oxide)/PAAS (sodium polyacrylate) solution and then coated with PVA (polyvinyl alcohol)/SA (sodium alginate) gel layer. The PVA/SA molecules can penetrate into the membrane through the unique micro/meso‐pores, which together increase the ion selectivity, membrane permeability, and stability. This ion‐selective membrane can achieve a power density of 8.65 W m−2 under a 50‐fold salinity gradient (NaCl) simulating the sea/river junction environment (with the testing area of 0.0314 mm2). This work significantly promotes the application of GO in large‐area preparation of low‐cost ion‐selective membrane.