Cation Selectivity Research Articles

Recent Advances in Artificial Anion Channels and Their Selectivity.

Nature performs critical physiological functions using a series of structurally and functionally diverse membrane proteins embedded in cell membranes, in which native ion protein channels modify the electrical potential inside and outside the cell membrane through charged ion movements. Consequently, the cell responds to external stimuli, playing an essential role in various life activities, such as nerve excitation conduction, neurotransmitter release, muscle movement, and control of cell differentiation. Supramolecular artificial channels, which mimic native protein channels in structure and function, adopt unimolecular or self-assembled structures, such as crown ethers, cyclodextrins, cucurbiturils, column arenes, cyclic peptide nanotubes, and metal-organic artificial channels, in channel construction strategies. Owing to the various driving forces involved, artificial synthetic ion channels can be divided into artificial cation and anion channels in terms of ion selectivity. Cation selectivity usually originates from ion coordination, whereas anion selectivity is related to hydrogen bonding, ion pairing, and anion-dipole interactions. Several studies have been conducted on artificial cation channels, and several reviews have summarized them in detail; however, the research on anions is still in the initial stages, and related reviews have rarely been reported. Hence, this article primarily focuses on the recent research on anion channels.

Ionic selectivity of nanopores: Comparison among cases under the hydrostatic pressure, electric field, and concentration gradient

The ionic selectivity of nanopores is crucial for the energy conversion based on nanoporous membranes. It can be significantly affected by various parameters of nanopores and the applied fields driving ions through porous membranes. Here, with finite element simulations, the selective transport of ions through nanopores is systematically investigated under three common fields, i.e. the electric field (V), hydrostatic pressure (p), and concentration gradient (c). For negatively charged nanopores, through the quantitative comparison of the cation selectivity (t+) under the three fields, the cation selectivity of nanopores follows the order of t+V > t+c > t+p. This is due to the transport characteristics of cations and anions through the nanopores. Because of the strong transport of counterions in electric double layers under electric fields and concentration gradients, the nanopore exhibits a relatively higher selectivity to counterions. We also explored the modulation of t+ on the properties of nanopores and solutions. Under all three fields, t+ is directly proportional to the pore length and surface charge density, and inversely correlated to the pore diameter and salt concentration. Under both the electric field and hydrostatic pressure, t+ has almost no dependence on the applied field strength or ion species, which can affect t+ in the case of the concentration gradient. Our results provide detailed insights into the comparison and regulation of ionic selectivity of nanopores under three fields which can be useful for the design of high-performance devices for energy conversion based on nanoporous membranes.

A Clay-Based Quasi-Solid-State electrolyte with high cation selective channels for High-Performance aqueous Zinc-Ion batteries

A clay-based quasi-solid-state electrolyte was prepared using dimethyl sulfoxide (DMSO) intercalated kaolinite as the raw material to suppress the adverse effects of free water molecules on aqueous zinc-ion batteries (AZIBs). Based on the inherent water absorption and retention properties of clay kaolinite, as well as the interlayer modification, this clay-based quasi-solid-state electrolyte not only achieved a low water content but also exhibited a strong water binding effect, which restricted the HER and side reactions involving water participation. Furthermore, the intercalation of DMSO increased the number of negative charges on the surface of kaolinite, resulting in the formation of a continuous spatial electrostatic field area around the kaolinite particles, which played a role in cation selectivity. The ionic transference number of the quasi-solid-state electrolyte reached 0.91. Additionally, the intercalation of DMSO broadened the interlayer ionic transport channels of kaolinite, further enhancing the transport efficiency of Zn2+ in the quasi-solid-state electrolyte, achieving uniform deposition of Zn2+ on the surface of the Zn anode, and suppressing dendrite growth to maintain a stable quasi-solid-state electrolyte/Zn anode interface. Zn||MnO2 battery assembled with this electrolyte demonstrated a discharge specific capacity of 301 mAh/g at a current density of 60 mA g−1. The Zn||MnO2 battery could be stably cycled for 1000 cycles at a current density of 150 mA g−1, and after 1000 cycles, the battery still maintained a discharge specific capacity of 248.2 mAh/g with a capacity retention rate of 84.8 %, showing excellent capacity performance and cycle stability. The Zn||MnO2 pouch battery could still provide stable power under heavy pressure, bending, and continuous tapping and had the potential for use in flexible batteries.

Facile design of a crown ether-functionalized polymeric membrane for highly efficient lithium and magnesium separation during electrodialysis

Efficient separation of magnesium and lithium is essential for the extraction of lithium resources from salt-lake brines. However, the current membrane separation technologies are challenged by the membrane permeability-selectivity trade-off. Herein, we demonstrated a facile and practical approach to fabricate crown ether-functionalized polymeric membranes with excellent Li+/Mg2+ separation performance by incorporating 12-crown-4 rings into the cellulose triacetate polymer network. The tightly and regularly arranged polymer chains anchored the crown ether rings firmly in the membrane structure, thereby facilitating the formation of stable and highly selective cation transport channels inside the membrane. As a result, the prepared membrane achieved an ultrahigh Li+/Mg2+ separation factor of ∼872 and Li+ flux of 22.6 μmol m−2 s−1, which was much superior to that of commercial CIMS and reported membrane separation technologies. The good long-term stability of the fabricated membrane is promising for achieving efficient magnesium-lithium separation in large-scale industrial applications.

Cation selectivity during flow electrode capacitive deionization

Efficient separation of specific ions from aqueous media is crucial for advanced water treatment and resource recovery. Flow electrode capacitive deionization (FCDI) offers potential for selective ion removal through continuous operation. This study evaluates the performance of selective cation separation using a commercial activated carbon slurry in a multi-ion solution of monovalent (Li+, Na+, K+) and bivalent (Ca2+, Mg2+) cations. We assess ion removal and cation selectivity under different operational parameters, such as applied potential, slurry flow rate, and feed water flow rate. Our data show that bivalent cations, namely Ca2+ and Mg2+, are preferentially removal due to their higher charge-to-size ratio, aligning with hydrated ion sizes. The highest separation rate was observed for Ca2+ (5.7 μg cm−2 min−1), and the lowest for Li+ (0.2 μg cm−2 min−1). At the highest applied voltage (1.2 V), charge efficiencies reached 70 %, with an energy consumption of 41 Wh mol−1 for nearly complete cation removal. Optimal conditions were identified with a slurry flow rate of 6 mL min−1, feed water flow rate of 2 mL min−1, activated carbon content of 10 mass%, 1 mass% carbon black, and a cell voltage of 1.2 V. These findings highlight the importance of optimizing operational parameters to enhance ion removal.

Pilot-scale capacitive deionization for water softening: Performance, energy consumption, and ion selectivity

Capacitive deionization (CDI) has emerged as an efficient process for hardness control than traditional water-softening technologies. However, few systematic studies have been conducted on water softening using pilot-scale CDI systems. For industrial applications, it is essential to investigate deionization performance, energy consumption, and selectivity for divalent cations through pilot-scale studies. In this study, we examined the deionization performance and energy consumption of a pilot-scale CDI process for effective water softening. The key operational variables analyzed were the applied voltage (200–300 V (i.e., 1.0–1.5 V per pair)), feed concentration (550–1250 mg/L), recovery ratio (50–80 %), flow rate (3–5 L/min), and adsorption/desorption time (80–180 s). Within this range, a high voltage, low feed concentration, low recovery ratio, high flow rate, and long adsorption/desorption times are advantageous for the total dissolved solids (TDS) removal ratio. In terms of energy efficiency, expressed as TDS removal per unit energy consumption, a low voltage, low feed concentration, low recovery ratio, fast flow rate, and long adsorption/desorption time are beneficial. Additionally, we investigated the selective removal of Ca2+ over Na+ under various operating conditions, as well as its impact on enhancing energy efficiency. The pilot CDI system achieved a Ca/Na selectivity coefficient of approximately 2.4 and it was analyzed to achieve up to 45 % energy-saving efficiency compared to nonselective systems (i.e., selectivity coefficient = 1). The results of this study are expected to provide valuable data for the application of CDI to water softening and hardness control processes.

Molecular cloning, functional characterization and differential expression of two novel GABAAR-like subunits from red swamp crayfish Procambarus clarkii.

In this work, we cloned and functionally expressed two novel GABAA receptor subunits from Procambarus clarkii crayfish. These two new subunits, PcGABAA-α and PcGABAA-β2, revealed significant sequence homology with the PcGABAA-β subunit, previously identified in our laboratory. In addition, PcGABAA-α subunit also shared a significant degree of identity with the Drosophila melanogaster genes DmGRD (GABA and glycine-like receptor subunits of Drosophila) as well as PcGABAA-β2 subunit with DmLCCH3 (ligand-gated chloride channel homolog 3). Electrophysiological recordings showed that the expression in HEK cells of the novel subunits, either alone or in combination, failed to form functional homo- or heteromeric receptors. However, the co-expression of PcGABAA-α with PcGABAA-β evoked sodium- or chloride-dependent currents that accurately reproduced the time course of the GABA-evoked currents in the X-organ neurons from crayfish, suggesting that these GABA subunits combine to form two types of GABA receptors, one with cationic selectivity filter and the other preferentially permeates anions. On the other hand, PcGABAA-β2 and PcGABAA-β co-expression generated a chloride current that does not show desensitization. Muscimol reproduced the time course of GABA-evoked currents in all functional receptors, and picrotoxin blocked these currents; bicuculline did not block any of the recorded currents. Reverse transcription polymerae chain reaction (RT-PCR) amplifications and FISH revealed that PcGABAA-α and PcGABAA-β2 are predominantly expressed in the crayfish nervous system. Altogether, these findings provide the first evidence of a neural GABA-gated cationic channel in the crayfish, increasing our understanding of the role of these new GABAA receptor subunits in native heteromeric receptors.

In Situ Synthesized HOF Ion Rectification Membrane with Ultrahigh Permselectivity for Nanofluidic Osmotic Energy Harvesting

AbstractThe utilization of salt concentration gradients as a renewable energy source represents a pivotal solution to the energy crisis. However, it is a persistent challenge to fabricate high‐performance ion permeable membranes with excellent ion permselectivity. In this work, hydrogen‐bonded organic framework (HOF) is in situ growth on anodic aluminum oxide (AAO) via chemical‐binding and solution‐processing strategy. The hydrogen bonding and π–π interactions forming the porous structure and the internal unprotonated carboxyl groups endow the HOF with superior cation selectivity and ion permeability. Furthermore, benefiting from the remarkable asymmetry of the prepared nanofluidic membrane arising from structure and charge of AAO and HOF, the HOF/AAO presents outstanding ion current rectification (ICR) characteristic, which can eliminate the ion concentration polarization (ICP) and power loss. Therefore, an impressive output power density with 500‐fold NaCl gradient is achieved as 75.2 W m−2 using the as‐prepared HOF/AAO, which is superior to most of reported membranes (7.0–40.0 W m−2). To show the critical role of HOF, 2D and 3D MOF with the same monomers are also synthesized, achieving decreased power densities of 36.2 and 58.3 W m−2 respectively. The present work provides a novel strategy to develop high‐performance nanofluidic ICR membranes for osmotic energy harvesting.

Mechanisms of mechanotransduction and physiological roles of PIEZO channels.

Mechanical force is an essential physical element that contributes to the formation and function of life. The discovery of the evolutionarily conserved PIEZO family, including PIEZO1 and PIEZO2 in mammals, as bona fide mechanically activated cation channels has transformed our understanding of how mechanical forces are sensed and transduced into biological activities. In this Review, I discuss recent structure-function studies that have illustrated how PIEZO1 and PIEZO2 adopt their unique structural design and curvature-based gating dynamics, enabling their function as dedicated mechanotransduction channels with high mechanosensitivity and selective cation conductivity. I also discuss our current understanding of the physiological and pathophysiological roles mediated by PIEZO channels, including PIEZO1-dependent regulation of development and functional homeostasis and PIEZO2-dominated mechanosensation of touch, tactile pain, proprioception and interoception of mechanical states of internal organs. Despite the remarkable progress in PIEZO research, this Review also highlights outstanding questions in the field.

Rational Design of A-Site Cation for High Performance Lead-Free Perovskite X-Ray Detectors.

Design of hypotoxic lead-free perovskites, e.g. Bismuth(Bi)-based perovskites, is much beneficial for commercialization of perovskite X-ray detectors due to their strong radiation absorption. Nevertheless, the design principles governing the selection of A-site cations for achieving high-performance X-ray detectors remain elusive. Here, seven molecules (methylamine MA, amine NH3, dimethylbiguanide DGA, phenylethylamine PEA, 4-fluorophenethylamine p-FPEA, 1,3-propanediamine PDA, and 1,4-butanediamine BDA) and calculated their dipole moments and interaction strength with metal halide (BiI3) are selected. The first-principles calculations and related spectroscopy measurements confirm that organic molecules (DGA) with large dipole moments can have strong interactions with perovskite octahedron and improve the carrier transport between the organic and inorganic clusters. Consequently, zero-dimensional single crystal (SC) (DGA)BiI5∙H2O is synthesized. The (DGA)BiI5∙H2O SCs demonstrate an exceptional carrier mobility-lifetime product of 6.55×10-3cm2V-1, resulting in the high sensitivity of 5879.4µCGyair -1cm-2, featuring a low detection limit (4.7nGyairs-1) and remarkable X-ray irradiation stability even after 100 days of aging at a high electric field (100Vmm-1). Furthermore, the (DGA)BiI5∙H2O SCs for imaging, achieving a notable spatial resolution of 5.5lpmm-1 are applied. This investigation establishes a pathway for systematically screening A-site cations to design low-dimensional SCs for high-performance X-ray detection.

Elucidating the Role of Alkali Metal Carbonates in Impact on Oxygen Vacancies for Efficient and Stable Perovskite Solar Cells.

Effectively suppressing nonradiative recombination at the SnO2/perovskite interface is imperative for perovskite solar cells. Although the capabilities of alkali salts at the SnO2/perovskite interface have been acknowledged, the effects and optimal selection of alkali metal cations remain poorly understood. Herein, a novel approach for obtaining the optimal alkali metal cation (A-cation) at the interface is investigated by comparatively analyzing different alkali carbonates (A2CO3; Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3). Theoretical calculations demonstrate that A2CO3 coordinates with undercoordinated Sn and O on the surface, effectively mitigating oxygen vacancy (VO) defects with increasing A-cation size, whereas Cs2CO3 exhibits diminished preferability owing to enhanced steric hindrance. The experimental results highlight the crucial role of Rb2CO3 in actively passivating VO defects, forming a robust bond with SnO2, and facilitating Rb+ diffusion into the perovskite layer, thereby enhancing charge extraction, alleviating deep-level trap states and structural distortion in the perovskite film, and significantly suppressing nonradiative recombination. X-ray absorption spectroscopy analyses further reveal the effect of Rb2CO3 on the local structure of the perovskite film. Consequently, a Rb2CO3-treated device with aperture area of 0.14 cm2 achieves a notable efficiency of 22.10%, showing improved stability compared to the 20.11% achieved for the control device.

Mapping Surface-Defect and Ions Migration in Mixed-Cation Perovskite Crystals.

Single crystal perovskites have garnered significant attention as potential replacements for existing absorber layer materials. Despite the extensive investigations on their photoinduced charge-carriers dynamics, most of the time-resolved techniques focus on bulk properties, neglecting surface characteristic which plays a crucial role for their optoelectronic performance. Herein, 4D ultrafast scanning electron microscopy (4D-USEM) is utilized to probing the photogenerated carrier transport at the first few nanometers, alongside density functional theory (DFT) to track both defect centers and ions migration. Two compositions of mixed cation are investigated: FA0.6MA0.4PbI3 and FA0.4MA0.6PbI3, interestingly, the former displays a longer lifetime compared to the latter due the presence of a higher surface-defect centers. DFT calculations fully support that revealing samples with higher FA content have a lower energy barrier for iodide ions to migrate from the bulk to top layer, assisting in passivating surface vacancies, and a higher energy diffusion barrier to escape from surface to vacuum, resulting in fewer vacancies and longer-lived hole-electron pairs. These findings manifest the influence of cation selection on charge carrier transport and formation of defects, and emphasize the importance of understanding ion migrations role in controlling surface vacancies to assist engineering high-performance optoelectronic devices based on single crystal perovskites.

Three-dimensional hydrogel membranes for boosting osmotic energy conversion: Spatial confinement and charge regulation induced by zirconium ion crosslinking

Ion-exchange membranes have been widely used to harvest osmotic energy in the past decades. However, conventional ion-exchange membranes suffer from low output power and poor conversion efficiency due to their limited pores and high membrane resistance. Herein, a sodium alginate (SA)/3-sulfopropyl acrylate potassium salt (SPAK) hydrogel membrane which has good cationic selectivity and can effectively harvest osmotic energy is designed, yielding a maximum power density of 16.44 W/m2 under a 50-fold NaCl concentration gradient and 36.85 W/m2 with ion selectivity of 0.73 at 500-fold. Furthermore, by introducing Zr4+, post-crosslinking reaction was employed to prepare tougher hydrogel membranes at room temperature for breaking a trade-off between selectivity and permeability, boosting a maximum power density up to 25.07 W/m2 under a 50-fold NaCl concentration gradient and 121.66 W/m2 with a high cation selectivity of 0.87 at 500-fold. Importantly, the resultant SA/SPAK/Zr4+ membrane reveals excellent osmotic energy harvesting property with the largest thickness of 500 μm, exceeding other reported porous nanofluidic membranes. Theoretical calculations correlate the enhanced power density of SA/SPAK/Zr4+ membranes with the enriched Cl- and smaller pore size after the introduction of Zr4+. This work paves an avenue to design and develop the 3D hydrogel membranes for high-performance osmotic energy generators.

Two serial filters control P2X7 cation selectivity, Ser342 in the central pore and lateral acidic residues at the cytoplasmic interface.

The human P2X7 receptor (hP2X7R) is a homotrimeric cell surface receptor gated by extracellular ATP4- with two transmembrane helices per subunit, TM1 and TM2. A ring of three S342 residues, one from each pore-forming TM2 helix, located halfway across the membrane bilayer, functions to close and open the gate in the apo and ATP4--bound open states, respectively. The hP2X7R is selective for small inorganic cations, but can also conduct larger organic cations such as Tris+. Here, we show by voltage-clamp electrophysiology in Xenopus laevis oocytes that mutation of S342 residues to positively charged lysines decreases the selectivity for Na+ over Tris+, but maintains cation selectivity. Deep in the membrane, laterally below the S342 ring are nine acidic residues arranged as an isosceles triangle consisting of residues E14, D352, and D356 on each side, which do not move significantly during gating. When the E14K mutation is combined with lysine substitutions of D352 and/or D356, cation selectivity is lost and permeation of the small anion Cl- is allowed. Lysine substitutions of S342 together with D352 or E14 plus D356 in the acidic triangle convert the hP2X7R mutant to a fully Cl--selective ATP4--gated receptor. We conclude that the ion selectivity of wild-type hP2X7R is determined by two sequential filters in one single pathway: (i) a primary size filter, S342, in the membrane center and (ii) three cation filters lateral to the channel axis, one per subunit interface, consisting of a total of nine acidic residues at the cytoplasmic interface.

Untangling individual cation roles in rock salt high-entropy oxides

We unravel the distinct role each cation plays in phase evolution, stability, and properties within the Mg1/5Co1/5Ni1/5Cu1/5Zn1/5O high-entropy oxide (HEO) by integrating experimental findings, thermodynamic analyses, and first-principles predictions. Our approach is through sequentially removing one cation at a time from the five-component high-entropy oxide to create five four-component derivatives. Bulk synthesis experiments indicate that Mg, Ni, and Co act as rock salt phase stabilizers whereas only Mg and Ni enthalpically enhance single-phase rock salt stability in thin film growth; synthesis conditions dictate whether Co is a rock salt phase stabilizer or destabilizer. By examining the competing phases and oxidation state preferences using pseudo-binary phase diagrams and first-principles calculations, we resolve the stability differences between bulk and thin film for all compositions. We systematically explore HEO macroscopic property sensitivity to cation selection employing both predicted and measured optical spectra. This study establishes a framework for understanding high-entropy oxide synthesizability and properties on a per-cation basis that is broadly applicable to tailoring functional property design in other high-entropy materials.

Efficient Zn-Ion Pouch Cell Assembling Based on Aramid Nanofiber Hydrogel

With the fast advancement of portable and wearable electronics, it is urgent to develop safe, stable and flexible power supply devices. Safe and environmentally friendly aqueous zinc-ion batteries (AZIBs) have a low-cost and are perfect candidates for energy storage device in such applications [1-4]. Giving the general challenges, such as the formation of the dendrites on the Zn anodes and hydrogen evolution and side reactions, extensive and wide research has focused on building stable AZIBs with high performance, but less attention was paid to making Zn ion pouch cells which are flexible and with high capacity In this presentation, we developed an efficient method to assemble Zn-ion pouch cells based on the process of formation of the aramid nanofiber hydrogel. The method involves the dipping precursor solution, solvent exchanging, and in-situ electrodeposition of MnO2. The assembled Zn-ion pouch cells exhibit excellent mechanical performance, flexibility and electrochemical performance, which are ideal for portable and wearable electronics. Based on this method, we successfully assembled 3-layer (cathode/anode/cathode, A/C/A) and 5 layer (A/C/A/C/A) pouch cells with over 100 times higher capacity compared with coin cell. In addition, the pouch cell with aramid nanofiber hydrogel and in-situ electrodeposited MnO2 cathode on carbon nanotube mat demonstrates superior cycling stability [5,6]. More details about our assembling method for flexible and stable pouch cells for AZIBs and experimental measurements related to the cycling and stability characteristics, will be presented at the meeting.[1] Yu, Peng, et al. "Flexible Zn‐ion batteries: recent progresses and challenges." Small 15.7 (2019): 1804760.[2] Li, Yingbo, et al. "Recent advances in flexible zinc‐based rechargeable batteries." Advanced Energy Materials 9.1 (2019): 1802605.[3] Li, Chunyang, et al. "High-rate and high-voltage aqueous rechargeable zinc ammonium hybrid battery from selective cation intercalation cathode." ACS Applied Energy Materials 2.10 (2019): 6984-6989.[4] Yu, Feng, et al. "Aqueous alkaline–acid hybrid electrolyte for zinc-bromine battery with 3V voltage window." Energy Storage Materials 19 (2019): 56-61.[5] Wang, Peng, and Petru Andrei. "High Performance Separator and Hydrogel Based on Aramid Fibers for Zn Ion Batteries." Electrochemical Society Meeting s 242. No. 4. The Electrochemical Society, Inc., 2022.[6] Xu, Lizhi, et al. "Water‐rich biomimetic composites with abiotic self‐organizing nanofiber network." Advanced Materials 30.1 (2018): 1703343.

Rational construction of positively charged polyamide nanofiltration membranes for precision cation separations

Nanofiltration has gained extensive attention in various energetically efficient separations towards a sustainable water–energy nexus. However, state-of-the-art polyamide nanofiltration membranes are constrained by the inherent trade-off between water permeance and solute selectivity, and a remarkable improvement in membrane permselectivity remains a big challenge. Here we conceived a density functional theory (DFT) assisted surface modification approach using triaminoguanidine hydrochloride (TGH) as the functional modifier to fabricate polyamide membranes with extremely high surface electropositivity and well-defined nanopores to overcome this challenge. Experimental data and DFT simulation results show that TGH surface modification can significantly manipulate surface charges and polarity to facilitate water permeation and enhance Donnan exclusion selectivity. Compared with the pristine benchmark membrane, the TGH-modified membrane exhibited a 4-fold increase in water permeance and a 6-fold increase in salt rejection, which successfully breaks the trade-off, excellent monovalent/divalent cation selectivity, and superior operational stability over a wide range of testing pressure, feed pH, and operation time, outperforming state-of-the-art membranes with similar chemistry. Taken together, this study demonstrates a feasible and reliable method combining DFT and experiments to rationally tailor the membrane characteristics at the molecular level, enabling the successful fabrication of effective polyamide nanofiltration membranes with precisely regulated structural and surface properties for water purification and precision ion separations.

MOFs/MXene nano-hierarchical porous structures for efficient ion dynamics

Nature's various hierarchical structures exhibit exceptional performance in enhancing mass transport. However, how to bionic nano-hierarchical structures to enhance ion dynamics and achieve charge regulation is a significant challenge. Herein, a nano-hierarchical porous hybrid membrane inspired by nature was designed by integrating 1D metal-organic frameworks (MOFs) on the 2D MXene substrate utilizing MOF nanoparticles with tailorable positive and negative surface charges. The synergistic effects of the bioinspired nanohierarchical porous structure and surface charge interactions significantly enhance the performance and stability of the nanoconfined membrane, as corroborated by experimental characterizations and theoretical simulations. As a result, the optimized nanohierarchical porous membrane exhibits high a cation selectivity of 0.95, an outstanding power density of 35.04 W m−2, and excellent stability over one month. Synergizing enhanced mass transport and ion dynamics in nano-hierarchically structured materials with tailored charge improves osmotic power generation efficiency and benefits logic circuits with controlled charge transport.

Biomimetic MOFs/GO membranes with enhanced charge density for osmotic power generation

Osmotic power generation is a renewable energy technology that harnesses energy from the natural mixing of freshwater and saltwater, offering a promising solution for sustainable energy. However, it is still a challenge to achieve high energy output without compromising scalability and stability. Herein, inspired by the nano-constrained dynamics of neuronal cell transmembrane transport, an anodic oxidation electrodeposition method is employed to fabricate metal organic frameworks (MOFs) within 2D graphene oxide (GO) layers. The in-situ integration of high-density charges within nanometer pore with 0.34 nm entrance of MOFs facilitates rapid and selective cation transport, which significantly increases the diffusion voltage (363.8 mV, 106 fold concentration gradient). Our device demonstrates a maximum output power of 6.82 μW under a 10 fold concentration gradient at a load resistance of 5000 Ω, possessing an energy conversion efficiency of 48.8% at an effective area of 12.56 mm2, which substantially surpasses the performance reported before. More importantly, the device performs exceptionally well, showing robust and stable performance. This is proven by its ability to power various electronic devices. These findings underscore the potential of biomimetic ion channel membranes in sustainable energy applications, offering a promising avenue for the broader field of energy harvesting technologies.

Unipolar Ionic Diode Nanofluidic Membranes Enabled by Stepped Mesochannels for Enhanced Salinity Gradient Energy Harvesting.

Developing ionic diode membranes featuring asymmetric structures is in high demand for salinity gradient energy harvesting. These membranes offer benefits in mitigating ion concentration polarization, thereby promoting ion permeability. However, most reported works focus on the role of heterogeneous charge-based bipolar ionic diode membranes for ion concentration polarization suppression, with comparatively less attention given to maintaining ion selectivity. Herein, unipolar ionic diode nanofluidic mesoporous silica membranes featuring stepped mesochannels were developed via a micellar sequential oriented interfacial self-assembly strategy as a salinity gradient energy harvester. Due to the asymmetric mesochannels and unipolar structure (both sides carry negative charge), the ionic diode membranes exhibit a strong rectification ratio of ∼15.91 to facilitate unidirectional ion transport while maintaining excellent cation selectivity (cation transfer number of ∼0.85). Besides, the vertically aligned mesochannels significantly reduce ion transport resistance, generating a high ionic flux. Consequently, the unipolar ionic diode nanofluidic membranes demonstrate a power output of 5.88 W/m2 between artificial sea and river water. The unipolar feature gives notable enhancements of 296% and 144% in power output compared to the symmetric membrane and bipolar ionic diode membrane, respectively. This work opens up new routes for designing ionic diode membranes for salinity gradient energy harvesting.