Crystal Channel Engineering for Rapid Ion Transport: From Nature to Batteries

Ion transport behaviours through cell membranes are commonly identified in biological systems, which are crucial for sustaining life for organisms. Similarly, ion transport is significant for electrochemical ion storage in rechargeable batteries, which has attracted much attention in recent years. Rapid ion transport can be well achieved by crystal channels engineering, such as creating pores or tailoring interlayer spacing down to the nanometre or even sub-nanometre scale. Furthermore, some functional channels, such as ion selective channels and stimulus-responsive channels, are developed for smart ion storage applications. In this review, the typical ion transport phenomena in the biological systems, including ion channels and pumps, are first introduced, and then ion transport mechanisms in solid and liquid crystals are comprehensively reviewed, particularly for the widely studied porous inorganic/organic hybrid crystals and ultrathin inorganic materials. Subsequently, recent progress on the ion transport properties in electrodes and electrolytes is reviewed for rechargeable batteries. Finally, current challenges in the ion transport behaviours in rechargeable batteries are analysed and some potential research approaches, such as bioinspired ultrafast ion transport structures and membranes, are proposed for future studies. It is expected that this review can give a comprehensive understanding on the ion transport mechanisms within crystals and provide some novel design concepts on promoting electrochemical ion storage capability in rechargeable batteries.     

Smart DNA Hydrogel Integrated Nanochannels with High Ion Flux and Adjustable Selective Ionic Transport

Nanochannels based on smart DNA hydrogels as stimulus‐responsive architecture are presented for the first time. In contrast to other responsive molecules existing in the nanochannel in monolayer configurations, the DNA hydrogels are three‐dimensional networks with space negative charges, the ion flux and rectification ratio are significantly enhanced. Upon cyclic treatment with K⁺ ions and crown ether, the DNA hydrogel states could be reversibly switched between less stiff and stiff networks, providing the gating mechanism of the nanochannel. Based on the architecture of DNA hydrogels and pH stimulus, cation or anion transport direction could be precisely controlled and multiple gating features are achieved. Meanwhile, G‐quadruplex DNA in the hydrogels might be replaced by other stimulus‐responsive DNA molecules, peptides, or proteins, and thus this work opens a new route for improving the functionalities of nanochannel by intelligent hydrogels.     

Selective Transport of Alkali—Metal Cations through Liquid Membranes by Non—Cyclic Carriers

The emission spectra of a series of naphthalene end-labeled oligo-oxyethylene(N-Pn-N) and their facilitated transport of cations across liquid membranes have been investigated.Alkali-metal cations enhance or inhibit the intramolecular excimer formation of N-Pn-N remarkably,suggesting that the polyether chain of N-Pn-N in solution complexes with the cations,and the orientation of the terminal chromophores depends on the cation size and the length of the polyether chain. These compounds are able to act as carriers to facilitate transport of alkali-metal cations through organic liquid membranes.The transport efficiencies are comparable with those of cyclic carriers such as crown ethers,and show remarkable selectivity.     

Anion–π Slides for Transmembrane Transport

The recognition and transport of anions is usually accomplished by hydrogen bonding, ion pairing, metal coordination, and anion–dipole interactions. Here, we elaborate on the concept to use anion–π interactions for this purpose. Different to the popular cation–π interactions, applications of the complementary π‐acidic surfaces do not exist. This is understandable because the inversion of the aromatic quadrupole moment to produce π‐acidity is a rare phenomenon. Here, we suggest that π‐acidic aromatics can be linked together to produce an unbendable scaffold with multiple binding sites for anions to move along across a lipid bilayer membrane. The alignment of multiple anion–π sites is needed to introduce a cooperative multi‐ion hopping mechanism. Experimental support for the validity of the concept comes from preliminary results with oligonaphthalenediimide (O‐NDI) rods. Predicted by strongly positive facial quadrupole moments, the cooperativity and chloride selectivity found for anion transport by O‐NDI rods were consistent with the existence of anion–π slides. The proposed mechanism for anion transport is supported by DFT results for model systems, as well as MD simulations of rigid O‐NDI rods. Applicability of anion–π slides to achieve electroneutral photosynthesis is elaborated with the readily colorizable oligoperylenediimide (O‐PDI) rods. To clarify validity, scope and limitations of these concepts, a collaborative research effort will be needed to address by computer modeling and experimental observations the basic questions in simple model systems and to design advanced multifunctional anion–π architectures.     

Transport of Ca^2＋ Ion through a Bubbling Pseudo—emulsion Liquid Membrane with Calixarenes and Calixcrowns as Carriers

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Ammonium across a Selective Polymer Inclusion Membrane: Characterization,Transport, and Selectivity

The recovery of ammonium from urine requires distinguishing and excluding sodium and potassium. A polymer inclusion membrane selective for ammonium is developed using an ionophore based on pyrazole substituted benzene. The interactions of the components are studied, as well as their effect on transport and selectivity. Spectroscopic and thermogravimetric measurements show no extensive physical interactions of the components, and that the plasticizer reduces the intermolecular forces (rigidity) of the membrane. The ionophore turns the membrane more rigid, although it increases its swelling degree and therefore the affinity of cations. A ratio of plasticizer (DEHP) and polymer (PVC) of 1:3 in mass gives the highest ammonium flux. Tested contents of ionophore (2 and 5 wt%) show that the higher the content of the ionophore, the fastest the flux is (7.5 × 10⁻³ mmol cm⁻² h⁻¹). Selectivity of NH₄⁺ over Na⁺ and over K⁺ is reduced from 13.07 to 9.33 and from 14.15 to 9.57 correspondingly.

     

Nanofluidic Ion Transport and Energy Conversion through Ultrathin Free‐Standing Polymeric Carbon Nitride Membranes

Ions transport through confined space with characteristic dimensions comparable to the Debye length has many applications, for example, in water desalination, dialysis, and energy conversion. However, existing 2D/3D smart porous membranes for ions transport and further applications are fragile, thermolabile, and/or difficult to scale up, limiting their practical applicability. Now, polymeric carbon nitride alternatively allows the creation of an ultrathin free‐standing carbon nitride membrane (UFSCNM), which can be fabricated by simple CVD polymerization and exhibits excellent nanofluidic ion‐transport properties. The surface‐charge‐governed ion transport also endows such UFSCNMs with the function of converting salinity gradients into electric energy. With advantages of low cost, facile fabrication, and the ease of scale up while supporting high ionic currents, UFSCNM can be considered as an alternative for energy conversion systems and new ionic devices.     

Transport of hydrated nitrate and nitrite ions through graphene nanopores in aqueous medium

Nitrate () and nitrite () ions are naturally occurring inorganic ions that are part of the nitrogen cycle. High doses of these ions in drinking water impose a potential risk to public health. In this work, molecular dynamics simulations are carried out to study the passage of nitrate and nitrite ions from water through graphene nanosheets (GNS) with hydrogen-functionalized narrow pores in presence of an external electric field. The passage of ions through the pores is investigated through calculations of ion flux, and the results are analyzed through calculations of various structural and thermodynamic properties such as the density of ions and water, ion–water radial distribution functions, two-dimensional density distribution functions, and the potentials of mean force of the ions. Current simulations show that the nitrite ions can pass more in numbers than the nitrate ions in a given time through GNS hydrogen-functionalized pore of different geometry. It is found that the nitrite ions can permeate faster than the nitrate ions despite the former having higher hydration energy in the bulk. This can be explained in terms of the competition between the number density of the ions along the pore axis and the free energy barrier calculated from the potential of mean force. Also, an externally applied electric field is found to be important for faster permeation of the nitrite over the nitrate ions. The current study suggests that graphene nanosheets with carefully created pores can be effective in achieving selective passage of ions from aqueous solutions.     

Assessment of Mass Transport through Polymeric Electrolyte Membrane by Means of Potentiometric Measures

Summary: This work aims to present a simple methodology to evaluate the proton transport of polymeric electrolyte membranes for fuel cells (PEMFC). The device consists of two ‘L’ tubes with a flanged edge, jointed by a metallic union that allows changing the different membranes to be analyzed. Through Fick´s equations, the matter that flows through the membrane can be assessed. For instance, a composite membrane made of SPSU containing TPA and modified with bis-benzimidazole derivatives as cross-linker showed flux and diffusion coefficient of 2.27.10⁻¹² gm⁻² s⁻¹ and 2.18.10⁻⁷ m² s⁻¹, respectively. These results are 65% larger than the SPSU membranes. The device also allows visualizing, for instance, that the difference between the water columns under atmospheric pressure is not levelled; which means that the pore diameters are sufficiently small to hinder the water molecules crosses them. The conductance values have been found 10⁻³ S and 10⁻⁴ S to composite membrane and sulfonated membrane, respectively, while the Nafion® membrane presented value at same order of composite membrane.     

Water transport coefficient distribution through the membrane in a polymer electrolyte fuel cell

The net water transport coefficient through the membrane, defined as the ratio of the net water flux from the anode to cathode to the protonic flux, is used as a quantitative measure of water management in a polymer electrolyte fuel cell (PEFC). In this paper we report on experimental measurements of the net water transport coefficient distribution for the first time. This is accomplished by making simultaneous current and species distribution measurements along the flow channel of an instrumented PEFC via a multi-channel potentiostat and two micro gas chromatographs. The net water transport coefficient profile along the flow channels is then determined by a control-volume analysis under various anode and cathode inlet relative humidity (RH) at 80 °C and 2 atm. It is found that the local current density is dominated by the membrane hydration and that the gas RH has a large effect on water transport through the membrane. Very small or negative water transport coefficients are obtained, indicating strong water back diffusion through the 30 μm Gore-Select^® membrane used in this study.     

Electrochemical Elucidation of the Facilitated Ion Transport Across a Bilayer Lipid Membrane in the Presence of Neutral Carrier Compounds

The ion transport facilitated by neutral carrier compounds (valinomycin, nonactin) has been investigated by cyclic voltammetry in the several electrolyte solutions (KF, KCl, KBr, KNO₃, KSCN, KClO₄), and we demonstrated the effect of the counter anions on the facilitated transport of K⁺ from the viewpoint of electroneutrality. Voltammograms for the ion transport were generated at steady state and the current density between W1 and W2, j_W1–W2, increased with the absolute value of the applied membrane potential, E_W1–W2. Then, the magnitude of j_W1–W2 at a certain E_W1–W2 increased with the hydrophobicity of the counter anion. It was proved that the logarithm of |j_W1–W2|at a certain E_W1–W2 is almost proportional to the hydration energy of the counter anion. This indicates that not only K⁺ but also the counter anion distributes into the BLM. Therefore, the magnitude of j_W1–W2 at a certain E_W1–W2 increased with an increase of pH, because the hydroxide ion was served as a counter anion. Based on the variation of the zero‐current potential in case of various asymmetrical ionic compositions, it is found that the amount of cation transport is much larger than that of anion transport.     

Voltage‐Driven Reversible Insertion into and Leaving from a Lipid Bilayer: Tuning Transmembrane Transport of Artificial Channels

Three new artificial transmembrane channel molecules have been designed and synthesized by attaching positively charged Arg‐incorporated tripeptide chains to pillar[5]arene. Fluorescent and patch‐clamp experiments revealed that voltage can drive the molecules to insert into and leave from a lipid bilayer and thus switch on and off the transport of K⁺ ions. One of the molecules was found to display antimicrobial activity toward Bacillus subtilis with half maximal inhibitory concentration (IC₅₀) of 10 μM which is comparable to that of natural channel‐forming peptide alamethicin.     

Potassium Ion-selective Electrode with a Sensitive Ion-to-Electron Transducer Composed of Porous Laser-induced Graphene and MoS2 Fabricated by One-step Direct Laser Writing

In this study, an ion-selective electrode with a sensitive ion-to-electron transducer composed of porous laser-induced graphene (LIG) and MoS₂ (LIG-MoS₂/ISE) was fabricated to measure the potassium ion concentration in a greenhouse nutrient solution for soilless culture. Additionally, a more effective and low-cost method was proposed for the large-batch production and manufacture of potassium ion-selective electrodes (K⁺-ISEs) using the direct laser writing technique, which differs considerably from existing methods. Moreover, the sensing mechanism of the proposed LIG-MoS₂/ISE for potassium ion detection was investigated. The morphology and physical properties of the LIG-MoS₂/SC-K⁺-ISEs were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy and energy-dispersive spectroscopy. Potentiometric measurements, chronopotentiometry, potentiometric water layer tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to evaluate the analytical performance of the newly developed K⁺-ISEs. A Nernstian slope of 30.1 mV/decade for the activity of potassium ions in a concentration range from 10⁻⁷ to 10⁻² M was determined. The EIS and chronopotentiometry results revealed that the LIG-MoS₂/SC-K⁺-ISE had a larger resistance and double-layer capacitance than the LIG/SC-K⁺-ISE. The ion-selective membrane (ISM) and solid-contact layer did not have any water film between them, according to the potentiometric water layer test. The results proved that the LIG-MoS₂ nanocomposite could possibly be used as a sensitive ion-to-electron transducer to fabricate K⁺-ISEs. The K⁺-ISE fabrication method using the direct laser writing technique had a higher efficiency, enabling its broad application prospects in agriculture.