Ultra-High Metal-Ions Selectivity Induced by Intramolecular Cation-π Interaction for the One-Pot Synthesis of Precise Heterometallic Architecture.

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host-guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than statistical mixture, due to the limited metal-ions selectivity of coordination units. Especially, heterometallic architectures precisely encoding with different metal ions usually fail to obtain in one-pot method when only one type of coordinated motif exists due to its poor metal-ion selectivity. Herein, we proposed an effective intramolecular cation-π (ICπ) strategy and successfully constructed the heterometallic supramolecule Zn2Cu4L34 by one-pot self-assembly of tritopic terpyridyl ligand L3 with Zn(II) and Cu(II), following the clear self-assembly mechanism that only thermodynamic dimers ZnL12 and Cu2L22 were constructed with model ligands L1, L2, Zn(II) and Cu(II) with perfect self-sorting and ultra-high metal-selectivity feature. The successful construction of the heterometallic supramolecule Zn2Cu4L34, encoding the definite sequence of metal ions Zn(II) and Cu(II) in one-pot method, will offer a novel approach to precisely construct heterometallic architectures.

A Novel Sulfonated Polyimide Composite Membrane Containing a Sulfonated Porous Material for All-Vanadium Redox Flow Batteries.

To improve the battery efficiency and cycling stability of sulfonated polyimide (SPI), a polyphosphazene with built-in -SO3H moieties (PP-SO3H), which is a porous covalent organic framework (COF) material, is facilely synthesized by the polymeric combination of hexachlorocyclotriphosphazene (HCCP) and p-diaminobenzenesulfonic acid. Due to its tunable pore size and flexible molecular design, the COF material can address the trade-off between the conductivity and the ion permeability of ion exchange membranes well, thereby improving the ion selectivity of membranes. The experimental results show that the SPI/PP-SO3H composite membrane has an excellent conductivity (up to 114.8 mS cm-1); the ion selectivity of the SPI/2% PP-SO3H membrane is 11.69 × 104 S min cm-3, which is 2.18 times higher than that of the SPI base membrane. PP-SO3H also improves the SPI membrane's mechanical strength, and the effect of PP-SO3H on SPI intermolecular interactions is analyzed by surface electrostatic potential (ESP) theoretical calculations. The Coulombic efficiency (CE) of the SPI/2% PP-SO3H membrane is 98.92%, the energy efficiency (EE) is 84.1% at a current density of 100 mA cm-2, and the self-discharge time of the SPI/2% PP-SO3H membrane is 3.5 times compared with the SPI base membrane. To measure the cycling stability of the composite membrane, the SPI/2% PP-SO3H membrane is cycled in the VRFB for more than 400 cycles, which is more stable than that of the SPI base membrane. These results show that SPI/2% PP-SO3H composite membranes are viable for VRFB applications.

Massively Enhanced Charge Selectivity, Ion Transport, and Osmotic Energy Conversion by Antiswelling Nanoconfined Hydrogels.

Developing a nanofluidic membrane with simultaneously enhanced ion selectivity and permeability for high-performance osmotic energy conversion has largely been unexplored. Here, we tackle this issue by the confinement of highly space-charged hydrogels within an orderedly aligned nanochannel array membrane. The nanoconfinement effect endows the hydrogel-based membrane with excellent antiswelling property. Furthermore, experimental and simulation results demonstrate that such a nanoconfined hydrogel membrane exhibits massively enhanced cation selectivity and ion transport properties. Consequently, an amazingly high power density up to ∼52.1 W/m2 with an unprecedented energy conversion efficiency of 37.5% can be reached by mixing simulated salt-lake water (5 M NaCl) and river water (0.01 M NaCl). Both efficiency indexes surpass those of most of the state-of-the-art nanofluidic membranes. This work offers insights into the design of highly ion-selective membranes to achieve ultrafast ion transport and high-performance osmotic energy harvesting.

Quantitative insights into the mechanism of proton conduction and selectivity for the human voltage-gated proton channel Hv1.

Human voltage-gated proton (hHv1) channels are crucial for regulating essential biological processes such as immune cell respiratory burst, sperm capacitation, and cancer cell migration. Despite the significant concentration difference between protons and other ions in physiological conditions, hHv1 demonstrates remarkable proton selectivity. Our calculations of single-proton, cation, and anion permeation free energy profiles quantitatively demonstrate that the proton selectivity of the wild-type channel originates from its strong proton affinity via the titration of the key residues D112 and D174, although the channel imposes similar kinetic blocking effects for protons compared to other ions. A two-proton knock-on model is proposed to mathematically explain the electrophysiological measurements of the pH-dependent proton conductance in the conductive state. Moreover, it is shown that the anion selectivity of the D112N mutant channel is tied to impaired proton transport and substantial anion leakage.

Enhanced Vanadium Redox Flow Battery Performance with New Amphoteric Ion Exchange Membranes.

Vanadium redox flow batteries (VRFBs) depend on the separator membrane for their efficiency and cycle life. Herein, two amphoteric ion exchange membranes are synthesized, based on sulfonic acid group-grafted poly(p-terphenyl piperidinium), for VRFBs. Using ether-free poly(p-terphenyl piperidine) (PTP) as the polymer matrix, and sodium 2-bromoethanesulphonate (ES) and 1,4-butane sultone (BS) as grafting agents, We achieve quaternization of PTP through an environmentally friendly process without alkaline catalysts. PTP-ES and PTP-BS membranes exhibit low area resistance, high H+ permeability, and significantly reduced vanadium ion permeability, leading to exceptional ion selectivity, which is 3.06 × 106 S min cm-3 and 4.34 × 106 S min cm-3, respectively, three orders of magnitude higher than that of Nafion115 (0.27 × 104 S min cm-3). The VRFB with PTP-BS achieves a self-discharge duration of 190 h, compared to 86 h for Nafion 115. Additionally, under current densities of 40-160 mA cm-2, PTP-BS shows coulombic efficiencies of 98.1-99.1% and energy efficiencies of 92.0-82.1%, outperforming Nafion 115. The VRFB with PTP-BS also demonstrates excellent cycle stability and discharge capacity retention over 300 cycles at 100 mA cm-2. Therefore, the amphoteric PTP-BS membrane shows remarkable performance, offering significant potential for VRFB applications.

Ion-Ion Selectivity of Synthetic Membranes with Confined Nanostructures.

Synthetic membranes featuring confined nanostructures have emerged as a prominent category of leading materials that can selectively separate target ions from complex water matrices. Further advancements in these membranes will pressingly rely on the ability to elucidate the inherent connection between transmembrane ion permeation behaviors and the ion-selective nanostructures. In this review, we first abstract state-of-the-art nanostructures with a diversity of spatial confinements in current synthetic membranes. Next, the underlying mechanisms that govern ion permeation under the spatial nanoconfinement are analyzed. We then proceed to assess ion-selective membrane materials with a focus on their structural merits that allow ultrahigh selectivity for a wide range of monovalent and divalent ions. We also highlight recent advancements in experimental methodologies for measuring ionic permeability, hydration numbers, and energy barriers to transport. We conclude by putting forth the future research prospects and challenges in the realm of high-performance ion-selective membranes.

Angstrom-Scale 2D Channels Designed For Osmotic Energy Harvesting.

Confronting the impending exhaustion of traditional energy, it is urgent to devise and deploy sustainable clean energy alternatives. Osmotic energy contained in the salinity gradient of the sea-river interface is an innovative, abundant, clean, and renewable osmotic energy that has garnered considerable attention in recent years. Inspired by the impressively intelligent ion channels in nature, the developed angstrom-scale 2D channels with simple fabrication process, outstanding design flexibility, and substantial charge density exhibit excellent energy conversion performance, opening up a new era for osmotic energy harvesting. However, this attractive research field remains fraught with numerous challenges, particularly due to the complexities associated with the regulation at angstrom scale. In this review, the latest advancements in the design of angstrom-scale 2D channels are primarily outlined for harvesting osmotic energy. Drawing upon the analytical framework of osmotic power generation mechanisms and the insights gleaned from the biomimetic intelligent devices, the design strategies are highlighted for high-performance angstrom channels in terms of structure, functionalization, and application, with a particular emphasis on ion selectivity and ion transport resistance. Finally, current challenges and future prospects are discussed to anticipate the emergence of more anomalous properties and disruptive technologies that can promote large-scale power generation.

Ion Selectivity, Current, and Water Flow Regulation in Ti3C2 MXene Nanopores.

Recent years have seen a growing interest in zero-dimensional (0D) transport phenomena occurring across two-dimensional (2D) materials for their potential applications to nanopore technology such as ion separation and molecular sensing. Herein, we investigate ion transport through 1 nm-wide nanopores in Ti3C2 MXene using molecular dynamics simulations. The high polarity and fish-bone arrangement of the Ti3C2 MXene offer a built-in potential and an atomic-scale distortion to the nanopore, causing an adsorption preference for cations. Our observation of variable cation-specific ion selectivity and Coulomb blockade highlights the complex interplay between adsorption affinity and cation size. The cation-specific ion selectivity can induce both the ion current and electro-osmotic water transmission, which can be regulated by tailoring the ions' preferential pathways through electric field tilting. Our finding underscores the pivotal role of the atomic arrangement of MXenes in 0D ion transport and provides fundamental insight into the application of 2D material in nanopores-based technologies.

Ion-Selective Transport Promotion Enabled by Angstrom-Scale Nanochannels in Dendrimer-Assembled Polyamide Nanofilm for Efficient Electrodialysis.

The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m-2 h-1 (K+), reaching excellent mono/multivalent selectivity up to 20.1 (K+/Mg2+) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.

Ion-Selective Metathesis Design of Flow-Electrode Capacitive Deionization for Energy-Saving and Anti-Scaling Softening of Brackish Water.

While flow-electrode capacitive deionization (FCDI) is recognized as an attractive desalination technology, its practical implementation has been hindered by the ease of scaling and energy-intensive nature of the single-cell FCDI system, particularly when treating brackish water with elevated levels of naturally coexisting SO42- and Ca2+. To overcome these obstacles, we propose and design an innovative ion-selective metathesis FCDI (ISM-FCDI) system, consisting of a two-stage tailored cell design. Results indicate that the specific energy consumption per unit volume of water for the ISM-FCDI is lower (by up to ∼50%) than that of a conventional single-stage FCDI due to the parallel circuit structure of the ISM-FCDI. Additionally, the ISM-FCDI benefits from a conspicuous disparity in the selective removal of ions at each stage. The separate storage of Ca2+ and SO42- by the metathesis process in the ISM-FCDI (46.25% Ca2+, 14.25% SO42- in electrode 1 and 4.75% Ca2+, 35.25% SO42- in electrode 2) can effectively prevent scaling. Furthermore, configuration-performance analysis on the ion-selective migration suggests that the properties of the ion exchange membrane, rather than the carbon species, govern the selectivity of ion removal. This work introduces system-level enhancements aimed at enhancing energy conservation and scaling prevention, providing critical optimization of the FCDI for brackish water softening.

Scalability of nanopore osmotic energy conversion.

Artificial nanofluidic networks are emerging systems for blue energy conversion that leverages surface charge-derived permselectivity to induce voltage from diffusive ion transport under salinity difference. Here the pivotal significance of electrostatic inter-channel couplings in multi-nanopore membranes, which impose constraints on porosity and subsequently influence the generation of large osmotic power outputs, is illustrated. Constructive interference is observed between two 20 nm nanopores of 30 nm spacing that renders enhanced permselectivity to osmotic power output via the recovered electroneutrality. On contrary, the interference is revealed as destructive in two-dimensional arrays causing significant deteriorations of the ion selectivity even for the nanopores sparsely distributed at an order of magnitude larger spacing than the Dukhin length. Most importantly, a scaling law is provided for deducing the maximal membrane area and porosity to avoid the selectivity loss via the inter-pore electrostatic coupling. As the electric crosstalk is inevitable in any fluidic network, the present findings can be a useful guide to design nanoporous membranes for scalable osmotic power generations.

Micro- and Nanofluidic pH Sensors Based on Electrodiffusioosmosis.

Recently, various kinds of micro- and nanofluidic functional devices have been proposed, where a large surface-to-volume ratio often plays an important role in nanoscale ion transport phenomena. Ionic current analysis methods for ions, molecules, nanoparticles, and biological cells have attracted significant attention. In this study, focusing on ionic current rectification (ICR) caused by the separation of cation and anion transport in nanochannels, we successfully induce electrodiffusioosmosis with concentration differences between protons separated by nanochannels. The proton concentration in sample solutions is quantitatively evaluated in the range from pH 1.68 to 10.01 with a slope of 243 mV/pH at a galvanostatic current of 3 nA. Herein, three types of micro- and nanochannels are proposed to improve the stability and measurement accuracy of the current-voltage characteristics, and the ICR effects on pH analysis are evaluated. It is found that a nanochannel filled with polyethylene glycol exhibits increased impedance and an improved ICR ratio. The present principle is expected to be applicable to various types of ions.

Electro-osmotic Flow Generation via a Sticky Ion Action.

Selective transport of ions through nanometer-sized pores is fundamental to cell biology and central to many technological processes such as water desalination and electrical energy storage. Conventional methods for generating ion selectivity include placement of fixed electrical charges at the inner surface of a nanopore through either point mutations in a protein pore or chemical treatment of a solid-state nanopore surface, with each nanopore type requiring a custom approach. Here, we describe a general method for transforming a nanoscale pore into a highly selective, anion-conducting channel capable of generating a giant electro-osmotic effect. Our molecular dynamics simulations and reverse potential measurements show that exposure of a biological nanopore to high concentrations of guanidinium chloride renders the nanopore surface positively charged due to transient binding of guanidinium cations to the protein surface. A comparison of four biological nanopores reveals the relationship between ion selectivity, nanopore shape, composition of the nanopore surface, and electro-osmotic flow. Guanidinium ions are also found to produce anion selectivity and a giant electro-osmotic flow in solid-state nanopores via the same mechanism. Our sticky-ion approach to generate electro-osmotic flow can have numerous applications in controlling molecular transport at the nanoscale and for detection, identification, and sequencing of individual proteins.

Commercial Nafion Membranes for Harvesting Osmotic Energy from Proton Gradients that Exceed the Commercial Goal of 5.0 W/m2.

Osmotic energy from proton gradients in industrial acidic wastewater can be harvested and converted to electricity through membranes, making it a renewable and sustainable power source. However, the currently designed membranes for harvesting proton gradient energy in acidic wastewater cannot simultaneously achieve excellent chemical/mechanical stability and high power density under a large-scale area and require high cost and complex operations. Here, we demonstrate that commercial Nafion membranes with high chemical/mechanical stability and proton transport selectivity can generate a power density of 5.1 W/m2 for harvesting osmotic energy from proton gradients under a test area of 0.2 mm2, which exceeds the commercial goal of 5.0 W/m2. Even under a test area of 12.5 mm2, a power density of 2.1 W/m2 can be achieved under a strong acid condition. In addition, the heat can greatly promote proton transport, and the power density is increased, i.e., 8.1 W/m2 at 333 K (5.1 W/m2 at 293 K) under a test area of 0.2 mm2. By matching membranes with ion selectivity, our work demonstrates the potential of Nafion membranes for harvesting proton gradient energy in acidic wastewater and provides an approach for large-scale conversion of osmotic energy.

Energy harvesting from acid mine drainage using a highly proton/ion-selective thin polyamide film.

A huge chemical potential difference exists between the acid mine drainage (AMD) and the alkaline neutralization solution, which is wasted in the traditional AMD neutralization process. This study reports, for the first time, the harvest of this chemical potential energy through a controlled neutralization of AMD using H+-conductive films. Polyamide films with controllable thickness achieved much higher H+ conductance than a commercially available cation exchange membrane (CEM). Meanwhile, the optimal polyamide film had an excellent H+/Ca2+ selectivity of 63.7, over two orders of magnitude higher than that of the CEM (0.3). The combined advantages of fast proton transport and high proton/ion selectivity greatly enhanced the power generation of the AMD battery. The power density was 3.1 W m-2, which is over one order of magnitude higher than that of the commercial CEM (0.2 W m-2). Our study provides a new sustainable solution to address the environmental issues of AMD while simultaneously enabling clean energy production.

Dilation of ion selectivity filters in cation channels.

Ion channels establish the voltage gradient across cellular membranes by providing aqueous pathways for ions to selectively diffuse down their concentration gradients. The selectivity of any given channel for its favored ions has conventionally been viewed as a stable property, and in many cation channels, it is determined by an ion-selectivity filter within the external end of the ion-permeation pathway. In several instances, including voltage-activated K+ (Kv) channels, ATP-activated P2X receptor channels, and transient receptor potential (TRP) channels, the ion-permeation pathways have been proposed to dilate in response to persistent activation, dynamically altering ion permeation. Here, we discuss evidence for dynamic ion selectivity, examples where ion selectivity filters exhibit structural plasticity, and opportunities to fill gaps in our current understanding.

Tuning mono-divalent cation water composition by the capacitive ion-exchange mechanism.

Soil salinization poses a significant challenge to agricultural activities. To address this, the agricultural industry seeks an irrigation water solution that reduces both ionic conductivity and sodium adsorption rate (SAR), thereby diminishing the risks of soil sodification and fostering sustainable crop production. Capacitive deionization (CDI) is an attractive electrochemical technology to advance this search. Recently, a one-dimensional transient CDI model unveiled a capacitive ion-exchange mechanism presenting the potential to adjust the treated water composition by modifying monovalent and divalent cation concentrations, thereby influencing the SAR index. This behavior would be achieved by using electrodes rich in surface functional groups able to efficiently capture divalent cations during conditioning and releasing them during charging while capturing monovalent ions. Beyond the theoretical modelling, the current experimental research demonstrates, for the first time, the effectiveness of the capacitive ion-exchange mechanism in a CDI pilot plant using real water samples spiked with solutions containing specific mono and divalent ions. Electrosorption experiments and computational modeling, specifically Density-Functional Theory (DFT), were used along with the analysis of the surface functional groups present in the electrodes to describe the capacitive ion-exchange phenomenon and validate the steps involved on it, highlighting the conditioning as a critical step. Various operational and flow modes confirm the versatility of CDI technology, achieving separation factors (RMg/Na) of 5-6 in batch, raising production from 0.5 to 0.8 L m-2 h-1 (batch) to 8.0-8.1 L m-2 h-1 when using single pass although reducing RMg/Na to 2. The reliability of the CDI technology in reducing SAR was also successfully tested with different influent compositions, including magnesium and calcium. Finally, the robustness of the capacitive ion-exchange mechanism was validated by a second CDI laboratory 9-cell stack cycled over 350 cycles. Our results confirm the reported theoretical model and expands the conclusions through the experiments in a pilot plant showing direct implications for employing CDI in agricultural applications.

Charge-Gradient Sulfonated Poly(ether ether ketone) Membrane with Enhanced Ion Selectivity for Osmotic Energy Conversion.

Engineered asymmetric heterogeneous ion-selective membranes have become a focal point for their improved efficiency in harnessing osmotic energy from ionic solutions with varying salinity. However, achieving both energy conversion efficiency and excellent chemical stability necessitates effectively mitigating the formation of detrimental interface cracks between two different layers. We develop a charge-gradient sulfonated poly(ether ether ketone) (SPEEK) membrane (CG-SPEEK) on a large-scale using a straightforward coating method. As an osmotic energy generator, CG-SPEEK membrane achieves an impressive output power density of 9.2 W m-2 and exhibits ultrahigh cation selectivity (0.99), with an energy conversion efficiency of 48% at a 50-fold NaCl concentration gradient. The results highlight the ion diode effects of CG-SPEEK, driven by a charge density gradient that accelerates cation transport while suppressing ion concentration polarization. Density functional theory simulations provide further insights, revealing that the energy barrier for Na+ ion transport through CG-SPEEK membrane is lower than that through a homogeneous SPEEK membrane. This work not only enhances our understanding of ion transport dynamics but also establishes the CG-SPEEK membrane as a promising candidate for efficient osmotic energy conversion applications.

The Molecular Mechanism of Ion Selectivity in Nanopores.

Ion channels exhibit strong selectivity for specific ions over others under electrochemical potentials, such as KcsA for K+ over Na+. Based on the thermodynamic analysis, this study is focused on exploring the mechanism of ion selectivity in nanopores. It is well known that ions must lose part of their hydration layer to enter the channel. Therefore, the ion selectivity of a channel is due to the rearrangement of water molecules when entering the nanopore, which may be related to the hydrophobic interactions between ions and channels. In our recent works on hydrophobic interactions, with reference to the critical radius of solute (Rc), it was divided into initial and hydrophobic solvation processes. Additionally, the different dissolved behaviors of solutes in water are expected in various processes, such as dispersed and accumulated distributions in water. Correspondingly, as the ion approaches the nanopore, there seems to exist the "repulsive" or "attractive" forces between them. In the initial process (

Tuning Pore Size in Graphene in the Angstrom Regime for Highly Selective Ion-Ion Separation.

Zero-dimensional pores spanning only a few angstroms in size in two-dimensional materials such as graphene are some of the most promising systems for designing ion-ion selective membranes. However, the key challenge in the field is that so far a crack-free macroscopic graphene membrane for ion-ion separation has not been realized. Further, methods to tune the pores in the Å-regime to achieve a large ion-ion selectivity from the graphene pore have not been realized. Herein, we report an Å-scale pore size tuning tool for single layer graphene, which incorporates a high density of ion-ion selective pores between 3.5 and 8.5 Å while minimizing the nonselective pores above 10 Å. These pores impose a strong confinement for ions, which results in extremely high selectivity from centimeter-scale porous graphene between monovalent and bivalent ions and near complete blockage of ions with the hydration diameter, DH, greater than 9.0 Å. The ion diffusion study reveals the presence of an energy barrier corresponding to partial dehydration of ions with the barrier increasing with DH. We observe a reversal of K+/Li+ selectivity at elevated temperature and attribute this to the relative size of the dehydrated ions. These results underscore the promise of porous two-dimensional materials for solute-solute separation when Å-scale pores can be incorporated in a precise manner.