High Ion Research Articles

Graphene oxide nanosheets reinforced quaternized poly(2,6-dimethyl-1,4-phenylene oxide) composite membranes with enhanced hydroxide ions conduction at subzero temperature

The realization of high hydroxide ion conductivity on the premise of enough alkaline stability is basic of the practical application of anion exchange membranes (AEMs). In this research, we propose a facile way to enhance the hydroxide ion conductivity at subzero temperature through constructing multilayered microstructures of AEMs. Graphene oxide (GO) nanosheets and 3,6-diazaspiro[5.5]undecane bromide (DSUBr) are alternately deposited on the surface of a quaternized poly(2,6-dimethyl-1,4-phenylene oxide) (QPPO) membrane with the layer by layer self-assembly process. Multilayered and compact microstructures are retained even if the prepared QPPO/(GO/DSUOH)5 membranes are immersed in 2 M KOH solution for 300 h. The hydroxide ions conduction resistance is reduced, deriving from the well-ordered dispersion of components. For example, the QPPO/2-(GO/DSUOH)5 membrane exhibits the hydroxide ion conductivities of 0.922 mS/cm at −25 °C and 58.5 mS/cm at 80 °C. Furthermore, the prepared AEMs possess the enhanced hydroxide ion conductivity owing to the fine dimension and component stabilities. After the ten-cycle hydroxide ion conductivity stability test, the retention rates of hydroxide ion conductivity are 99.4 % at −25 °C and 105 % at 30 °C. Additionally, the residual hydroxide ion conductivity reaches 61.6 mS/cm at 80 °C in 2 M KOH solution for 624 h. A single fuel cell equipped with the QPPO/2-(GO/DSUOH)5 membrane exhibits the maximum power densities of 80.8 mW/cm2 at 30 °C and 351.6 mW/cm2 at 60 °C.

Evolution of the Secondary Electron Spectrum during Cosmic-Ray Discharge in the Universe

We recently found that streaming cosmic rays (CRs) induce a resistive electric field that can accelerate secondary electrons produced by CR ionization. In this work, we study the evolution of the energy spectrum of secondary electrons by numerically solving the one-dimensional Boltzmann equation and Ohm’s law. We show that the accelerated secondary electrons further ionize a gas, that is, an electron avalanche occurs, resulting in increased ionization and excitation of the gas. Although the resistive electric field becomes weaker than the one before the CR discharge, the weak resistive electric field weakly accelerates the secondary electrons. The quasi-steady state is almost independent of the initial resistive electric field but depends on the electron fraction in the gas. The resistive electric field in the quasi-steady state is larger for the higher electron fraction, which makes the number of secondary electrons that can ionize the gas larger, resulting in a higher ionization rate. The CR discharge could explain the high ionization rate that is observed in some molecular clouds.

Voltammetry of the ferric/ferrous redox couple at platinum microelectrodes in aqueous hydrochloric acid

In this paper, the Fe3+/Fe2+ redox system was investigated in 0.5 M HCl solutions, using steady-state voltammetry at a Pt microelectrode. Measurements were performed in solutions containing each ion alone or in mixtures containing both ions. The reduction of Fe3+ to Fe2+ provided a single sigmoidal wave, regardless of the ion concentration. For the oxidation process of Fe2+ to Fe3+, a wave split was observed at relatively high ion concentrations (i.e., ≥ about 10 mM). This feature, not observed or not considered in previous studies, was rationalized by considering that the Fe2+ oxidation process occurs over the potential region where passivating Pt oxides form on the electrode surface. Standard rate constant (k0′), and transfer coefficient (α) of the electrode process were evaluated using the method based on the quartile potentials ΔE1/4=E1/4-E1/2 and ΔE3/4=E1/2-E3/4, which can be obtained from the experimental steady-state voltammograms. k0′ and α values varied in the range 1.4 x10-3 cm s−1 – 3.1 x 10-2 cm s−1, and 0.44 – 0.64, respectively, depending on the specific status of the electrode surface, in turn depending on the care adopted in cleaning the electrode surface from the Pt oxides. From the quartile potentials approach, the formal potential of the redox system, equal to 0.495 (±0.005) V, vs. Ag/AgCl (KCl saturated) could also be evaluated. This value resulted in good agreement with 0.494 (±0.002) V, formal potential obtained from the cathodic-anodic voltammograms recorded in the mixtures of the two ions at equal concentration. Chronoamperometry was employed to determine the diffusion coefficients on the two ions by fitting the experimental current against time profiles and the theoretical equation that holds for microdisk electrodes. The values found where 4.67 x 10-6 cm2 s−1 and 5.61 x 10-6 cm2 s−1 for Fe3+ and Fe2+ ions, respectively.

In Situ-Grown Ultrathin Catalyst Layers for Improving both Proton Exchange Membrane Fuel Cell and Anion Exchange Membrane Fuel Cell Performances.

The mass transport and ion conductivity in the catalyst layer are important for fuel cell performances. Here, we report an in situ-grown ultrathin catalyst layer (UTCL) to reduce the oxygen mass transport and a surface ionomer-coated gas diffusion layer method to reduce the ion conducting resistance. A significantly reduced catalyst layer thickness (ca. 1 μm) is achieved, and coupled with the ionomer introduction method, the ultrathin catalyst layer is in good contact with the membrane, resulting in high ion conductivity and high Pt utilization. This ultrathin catalyst layer is suitable for both proton exchange membrane fuel cells and anion exchange membrane fuel cells, giving peak power densities of 2.24 and 1.11 W cm-2, respectively, which represent an increase of more than 30% compared with the membrane electrode assembly (MEA) fabricated by using traditional Pt/C power catalysts. Electrochemical impedance spectra and limiting current tests demonstrate the reduced charge transfer, mass transfer, and ohmic resistances in the ultrathin catalyst layer membrane electrode assembly, resulting in the promoted fuel cell performances.

Engineering multiple heterogeneous Co/CoSe/MoSe2 embedded in carbon nanofibers with Co/Mo–Se–C bonding towards high performance sodium ion capacitors

MoSe2, as a representative two-dimensional transition selenide with a broad interlayer distance of 0.65 nm and a high theoretical capacity of 422 mAh g−1, is considered an optimal anode material for sodium-ion batteries (SIBs). However, its unsatisfactory electrical conduction and structural instability often lead to severe capacity decay during cycling, hindering its large-scale application in SIBs. To overcome these challenges, coupling heterostructures has been identified as an effective solution. The establishment of multiple heterointerfaces can minimize interface diffusion resistance, significantly enhancing ion and electron delivery dynamics compared to a single component. In this work, multiple heterogeneous Co/CoSe/MoSe2 uniformly distributed in carbon nanofibers (CNF) via Co/Mo–Se–C bonding are successfully synthesized using electrospinning and subsequent calcination. Importantly, the Co/CoSe and Co/MoSe2 heterointerfaces can greatly accelerate charge transfer and improve Na + adsorption capability compared to the CoSe/MoSe2 heterostructure, as corroborated by theoretical calculations. Given the high rate performance of Co/CoSe/MoSe2@CNF as an anode in SIBs (267.9 mAh g−1 at 5 A g−1), a rocking-chair sodium-ion capacitor (SIC) incorporating a Co/CoSe/MoSe2@CNF anode and a Na3V2(PO4)3 cathode is proposed, delivering high energy densities of 199.1 Wh kg−1 at 180 W kg−1 and 126.8 Wh kg−1 at 3280 W kg−1.

Engineering interleaved large and small Na4MnV(PO4)3@NC microspheres cathode towards high performance sodium ion batteries

The booming consumption of energy storage devices spontaneously accelerates the urgent development of robust cathode materials for sodium-ion batteries (SIBs). In view of this, the sodium superionic conductor Na4MnV(PO4)3 (NMVP), with considerable energy density of 425 Wh kg−1, has become the focus in SIB research. Despite this, the performance of NMVP is substantially compromised by Jahn-Teller distortion of Mn3+ ions in conjunction with inherently limited electronic conductivity. In order to address this limitation, this study introduces a series of N-doped carbon (NC) coated NMVP materials with interleaved large and small microsphere morphology. Of particular note, the optimized NMVP-NC2 shows the most excellent performance, maintaining a capacity of 65.7 mAh g−1 at 5C over 500 cycles. A full cell configuration employing an NMVP-NC2 cathode and a commercial hard carbon (HC) anode manifests commendable circular stability with a capacity of 80.7 mAh g−1 underneath 100 cycles at 1C, with an impressive 95.3 % capacity preservation. This distinctive architecture imparts the materials with a high tap density and a relatively low surface area, which is beneficial to the industrial employment. In addition, density functional theory (DFT) calculations indicate that the NC regulation significantly narrows the NMVP's bandgap and facilitates electron transfer, thereby accelerating electron/ion transport kinetics. The NC coating approach combined with large-scale spray drying tactic in this work offers a clear strategy to industrialize NMVP cathode towards high-performance SIBs.

Universal Copolymerization of Crosslinked Polyether Electrolytes for All-Solid-State Lithium-Metal Batteries.

Solid polymer electrolytes (SPEs) are pivotal in advancing the practical implementation of all-solid-state batteries. Poly(1,3-dioxane) (PDOL)-based electrolytes have attracted significant attention due to the pseudo-high conductivity achieved through sophisticated in situ polymerization methods; however, such PDOL-based electrolytes present challenges of crystallization over time and monomers residual during processing. In this study, integrating LiTFSI and LiDFOB as a universal copolymerization strategy for developing high-performance PDOL electrolytes with a wide range of epoxy crosslinkers is proposed. It is discovered that this approach leverages the protective effects of TFSI anions on the boron active center and catalyzes polymer chain growth via crosslinking. The homogenously crosslinked (benzene-centered) PDOL electrolyte exhibits remarkable thermo-mechanical stability (up to 100°C), high ion migration number (tLi+ = 0.42), a wide electrochemical window (≈5.0V vs Li+/Li), and high ionic conductivity (4.5×10-4 S cm-1). Notably, the crosslinked PDOL electrolyte is in the all-solid-state with minimal monomer/oligomer residual, exhibiting no crystallization during relaxation, delivering a robust performance in all-solid-state lithium metal batteries.

Structural Principles of Ion-Conducting Mineral-like Crystals with Tetrahedral, Octahedral, and Mixed Frameworks

Materials with high ion mobility are widely used in many fields of modern science and technology. Over the last 40 years, they have thoroughly changed our world. The paper characterizes the structural features of minerals and their synthetic analogs possessing this property. Special attention is paid to the ionic conductors with tetrahedral (zincite- and wurtzite-like), octahedral (ilmenite-like), and mixed (NASICON-like) frameworks. It is emphasized that the main conditions for fast ionic transport are related to the size and positions occupied by a mobile ion, their activation energy, the presence and diameter of conduction channels running inside the structure, isomorphic impurities, and other structural peculiarities. The results of the studies of solid electrolytes are dispersed in different editions, and the overview of new ideas related to their crystal structures was the focus of this paper.

Amphiphilic Polymer Electrolyte Blocking Lattice Oxygen Evolution from High‐Voltage Nickel‐rich Cathodes for Ultra‐Thermal Stabile Batteries

AbstractNi‐rich cathodes have been intensively adopted in Li‐ion batteries to pursuit high energy density, which still suffering irreversible degradation at high voltage. Some unstable lattice O2− species in Ni‐rich cathodes would be oxidized to singlet oxygen 1O2 and released at high volt, which lead to irreversible phase transfer from the layered rhombohedral (R) phase to a spinel‐like (S) phase. To overcome the issue, the amphiphilic copolymers (UMA‐Fx) electrolyte were prepared by linking hydrophobic C−F side chains with hydrophilic subunits, which could self‐assemble on Ni‐rich cathode surface and convert to stable cathode–electrolyte interphase layer. Thereafter, the oxygen releasing of polymer coated cathode was obviously depressed and substituted by the Co oxidation (Co3+→Co4+) at high volt (>4.2 V), which could suppressed irreversible phase transfer and improve cycling stability. Moreover, the amphiphilic polymer electrolyte was also stable with Li anode and had high ion conductivity. Therefore, the NCM811//UMA‐F6//Li pouch cell exhibited outstanding energy density (362.97 Wh/kg) and durability (cycled 200 times at 4.7 V), which could be stalely cycled even at 120°C without short circuits or explosions.

Exsolved NiRu bimetallic nanoparticles induced by Ru doping in LaBaMn1.6Ni0.3Ru0.1O5+δ as a coking resistant anode catalyst layer for direct-methane solid oxide fuel cells

Due to its abundant resources and advantages in transportation and storage, methane fueled solid oxide fuel cells (SOFCs) are highly needed. In this work, an exceptional internal reforming catalyst comprising in-situ exsolved NiRu bimetallic nanoparticles and oxygen-deficient layered double perovskite LaBaMn1.6Ni0.3Ru0.1O5+δ (r-LBMNR) was prepared. Compared to the cell with LaBaMn1.6Ni0.4O5+δ (r-LBMN) catalyst, the cell with a Ru-doping r-LBMNR catalyst layer, exhibits superior peak power output of 336 mW cm−2 and better durability with a less decay rate of 0.014% per hour in CH4 fuel. The enhanced electrochemical performance can be attributed to the high oxygen ion and electron conductivities of the catalyst and the coupling of Ni and Ru sites with the oxygen-deficient r-LBMNR matrix This coupling activates CH4 and H2O, promotes the oxidation of C atoms in CH4 molecules, and enables reversible hydrogen spillover, ultimately leading to the production syngas of CO(g) and H2(g).

Coal-derived boron and phosphorus co-doped activated carbon with expanded interlayer space for high performance sodium ion capacitor anode

Aiming at the key problem of Na+ insertion difficulty and low charge transfer efficiency of activated carbon materials. It is an effective strategy to increase the lattice spacing and defect concentration by doping to reduce the ion diffusion resistance and improve the kinetics. Hence, anthracitic coal is used to prepare activated carbon (AC) and B,P-doped activated carbon (B,P-AC) as the cathode and anode materials for high-performance all-carbon SICs, respectively. AC cathode material has high specific surface area and reasonable micropore structure, which shows excellent capacitance performance. B,P-AC anode material has the advantages of extremely high specific surface area (1856.1 m2/g), expanded interlayer spacing (0.40 nm) and uniform distribution of B and P heteroatoms. Hence, B,P-AC anode achieves a highly reversible Na+ storage capacity of 243 mAh/g at a current density of 0.05 A/g. Density functional theory (DFT) calculations further verify that B,P-AC has stronger Na+ storage performance. The final assembled B,P-AC//AC SIC offers a high energy density of 109.78 Wh kg−1 and a high-power density of 10.03 kW kg−1. The high-performance coal-derived activated carbon of this work provides a variety of options for industrial production of electrode materials for sodium ion capacitors.

Single proton anti-freezing hydrogel electrolyte with enhanced ion migration number enabling high-performance supercapacitor

Compared with traditional binary ion electrolytes, single-ion electrolytes have higher ion migration number and can avoid concentration polarization. In this work, single proton hydrogel electrolytes were prepared by one-step free radical polymerization of acrylamide and 2-acrylaminoamido-2-methyl-1-propane sulfonic acid in ethylene glycol (EG)/water binary solvent. The electrolyte possesses good mechanical strength and excellent anti-freezing ability. A high conductivity of 1.28 mS cm−1 at −40 °C is achieved by adjusting monomer ratio and EG content. The proton hopping along the ion channel formed by the anionic polymer chain and the Grotthuss transport are responsible for the high conductivity. An extremely high ion migration number of 0.87 is obtained. The fixed anionic group endows the hydrogel electrolyte with good anticorrosion ability. The hydrogel electrolyte assembled supercapacitor (SC) exhibits excellent electrochemical performance in a wide temperature range from −40 °C to 60 °C and can be stored at −30 °C for 10 months without capacitance attenuation. The capacitance retention rate of the SC is as high as 92% after 15,000 cycles at both room temperature and − 40 °C. The single proton hydrogel electrolyte provides a new route for the further development of storage device based proton transport.

Static and dynamic properties investigation of modified polyethersulfone membrane for direct methanol fuel cell applications

The present study's main focus is understanding the impact of modification, especially through phosphoric acid and acetic acid, on polyethersulfone (PES) membranes for direct methanol fuel cell application, as sulfonation is the preferred modification method. The cross-linking introduces the sulfonate, phosphonate, and carboxylate group in the polymer matrix, while the membrane's semi-crystalline nature and homogeneous surface are confirmed through instrumental analysis. The high ion exchange capacity and water retention capacity of the phosphoric acid cross-linked PES membrane (PPES-2) reveal its potentiality. The impact of different hydration levels and temperatures on proton conductivity indicates that based on the operating conditions, the cross-linked membrane can be used, such as at high temperatures and 50 % hydration level, the PPES-2 membrane shows high proton conductivity as well as has low methanol crossover due to the presence of hydroxyl group. At the same time, the acetic acid-treated PES (CPES-2) membrane shows high proton conductivity at 50 % hydration level and low temperature. The same is confirmed through molecular dynamic simulation by understanding their dynamic and static properties. The PPES-2 membrane shows maximum power density (0.34 Wcm−2). In conclusion, the study indicates that PES modification can be done through phosphorylation and carboxylation, apart from sulfonation.

Structure, anti-inflammatory and anti-bacterial activities of novel pentacyclic triterpenoids and other constituents from the leaves of Pittosporum elevaticostatum

The investigation of the leaves of Pittosporum elevaticostatum Chang et Yan led to the isolation of fifteen pentacyclic triterpenoids (1–15), including five previously undescribed ones (1–5), and nine others (16–24). The structures of compounds 1–5 were elucidated based on comprehensive spectroscopic techniques, including one dimension (1D) and 2D nuclear magnetic resonance (NMR), high resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and other methods. Compounds 2 and 13 demonstrated significant inhibitory activity against Listeria monocytogenes (L. monocytogenes) with minimum inhibitory concentration (MIC) values of 32 μM. Scanning electron microscopy (SEM) observations revealed insights into the antibacterial mechanism, indicating that compounds 2 and 13 either prevent biofilm formation of dispersed the preformed cell membranes. Additionally, compounds 1, 5, 7, and 12 exhibited anti-inflammatory activity on lipopolysaccharide (LPS)-stimulated BV-2 microglial cells with IC50 values ranging from 11.27 to 17.80 μM.

Influence of high field strength ions on the crystallization characteristics and properties of slag glass-ceramics

Blast furnace slag glass–ceramics were prepared by melting using rare-earth-containing blast furnace slag (REBFS) as the main raw material and Fe2O3 and Cr2O3 as composite nucleating agents. By adding different TiO2 contents, the study comprehensively revealed the effects of high field strength ions on the glass network structure, crystalline properties, elemental distribution and physicochemical properties. Raman spectroscopy and differential scanning calorimetry revealed that TiO2 acted primarily as a network modifier in the glass network. The appropriate TiO2 content disrupted the glass network, decreasing the crystallization activation energy (EC) of the glass–ceramic. However, excess TiO2 repaired the network structure, thereby increasing the EC. The combined effect of the Cr and Ti substantially improved the crystallization characteristics of the glass-ceramics. Cr2O3 induced the formation of spinel, which promoted the crystallization of the main crystalline augite phase. The self-aggregation of the high field strength Ti4+ ion induced the formation of a titanium- and cerium-containing titanite phase, which also contributed to grain refinement. This titanite phase effectively increased the Vickers hardness and acid and alkali resistances of the glass-ceramics to 9.16 GPa and over 98.5 %, respectively. The excellent physicochemical properties render REBFS glass–ceramics as being promising materials for various construction applications. This research provides theoretical support for comprehensively utilizing blast furnace slag and provides theoretical guidance for preparing slag glass–ceramics possessing desirable physicochemical properties.

High-performance transistors based on monolayer all-inorganic two-dimensional halide perovskite Cs2PbI2Cl2 and its optoelectronic application

The two-dimensional (2D) Ruddlesden−Popper phase all-inorganic halide perovskite Cs2PbI2Cl2 has attracted tremendous attention because of its high carrier mobility, strong light-absorbing ability, and excellent environmental stability, possessing enormous potential for use as a high-performance optoelectronic device. Here, we present two transistor devices based on monolayer (ML) Cs2PbI2Cl2 and reveal their performance and current transport mechanisms through ab initio quantum transport calculations. The n-type 10 nm metal-oxide-semiconductor field-effect transistor shows a high on-state current Ion of 3160 μA/μm, and excellent performance regarding subthreshold swing, intrinsic delay time (τ), and power consumption, which completely match the International Roadmap for Device and Systems (2021 version) targets for high-performance devices and low-power devices in 2028. Moreover, phototransistors based on monolayer Cs2PbI2Cl2 also display a strong response to UV light, with a light-to-dark current ratio reaching a maximum of 104. Meanwhile, a high specific detectivity of 2.45 × 1011 Jones is obtained. The results of our study suggest that ML Cs2PbI2Cl2 is a promising candidate for high-performance transistors.

Dual carbon protected ultrafine SnO2 nanoparticles with Sn–C interface for robust lithium storage

Stannic oxide (SnO2)-based lithium-ion batteries (LIBs) have garnered tremendous attention due to their high theoretical capacity and suitable lithium ion insertion potential. However, their widespread applications have been hindered by severe electrode degradation caused by substantial volume expansion of SnO2. In this study, we embedded amorphous carbon encapsulated ultrafine SnO2 nanoparticles on hollow macroporous carbon (AC@SnO2/HMC) as a superior anode material for LIBs. The unique Sn–C interface and dual carbon protection layers effectively mitigated SnO2 nanoparticle agglomeration and volume expansion, reinforcing the cycling stability. Additionally, the capacitive contribution from amorphous carbon significantly improved the reversible capacity and rate capability. As such, the resulting AC@SnO2/HMC electrode exhibited high capacity (1828 mAh g−1 after 200 cycles at 0.1 A g−1), excellent rate capability (1017.6 mAh g−1 at 1 A g−1), and outstanding cycling performance (792.1 mAh g−1 after 880 cycles at 2 A g−1), surpassing previously reported SnO2-based anodes. Furthermore, the AC@SnO2/HMC-based Li-ion full cell demonstrated a remarkable capacity of 566.3 mAh g−1 at 0.2 A g−1 after 200 cycles. This study offers valuable insights into the development of advanced SnO2-based anodes for LIBs and beyond, highlighting their potential for future advancements in battery technology.

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.