Sustainable lithium extraction enabled by responsive metal-organic frameworks with ion-sieving adsorption effects.

Metal-organic frameworks (MOFs) are superior ion adsorbents for selectively capturing toxic ions from water. Nevertheless, they have rarely been reported to have lithium selectivity over divalent cations due to the well-known flexibility of MOF framework and the similar physiochemical properties of Li+ and Mg2+. Herein, we report an ion-sieving adsorption approach to design sunlight-regenerable lithium adsorbents by subnanoporous MOFs for efficient lithium extraction. By integrating the ion-sieving agent of MOFs with light-responsive adsorption sites of polyspiropyran (PSP), the ion-sieving adsorption behaviors of PSP-MOFs with 6.0, 8.5, and 10.0 Å windows are inversely proportional to their pore size. The synthesized PSP-UiO-66 with a narrowest window size of 6.0 Å shows high LiCl adsorption capacity up to 10.17 mmol g-1 and good Li+/Mg2+ selectivity of 5.8 to 29 in synthetic brines with Mg/Li ratio of 1 to 0.1. It could be quickly regenerated by sunlight irradiation in 6 min with excellent cycling performance of 99% after five cycles. This work sheds light on designing selective adsorbents using responsive subnanoporous materials for environmentally friendly and energy-efficient ion separation and purification.

Unlocking Direct Lithium Extraction in Harsh Conditions through Thiol-Functionalized Metal-Organic Framework Subnanofluidic Membranes.

Metal-organic framework (MOF) membranes with high ion selectivity are highly desirable for direct lithium-ion (Li+) separation from industrial brines. However, very few MOF membranes can efficiently separate Li+ from brines of high Mg2+/Li+ concentration ratios and keep stable in ultrahigh Mg2+-concentrated brines. This work reports a type of MOF-channel membranes (MOFCMs) by growing UiO-66-(SH)2 into the nanochannels of polymer substrates to improve the efficiency of MOF membranes for challenging Li+ extraction. The resulting membranes demonstrate excellent monovalent metal ion selectivity over divalent metal ions, with Li+/Mg2+ selectivity up to 103 since Mg2+ should overcome a higher energy barrier than Li+ when transported through the MOF pores, as confirmed by molecular dynamics simulations. Under dual-ion diffusion, as the Mg2+/Li+ mole ratio of the feed solution increases from 0.2 to 30, the membrane Li+/Mg2+ selectivity decreases from 1516 to 19, corresponding to the purity of lithium products between 99.9 and 95.0%. Further research on multi-ion diffusion that involves Mg2+ and three monovalent metal ions (K+, Na+, and Li+, referred to as M+) in the feed solutions shows a significant improvement in Li+/Mg2+ separation efficiency. The Li+/Mg2+ selectivity can go up to 1114 when the Mg2+/M+ molar concentration ratio is 1:1, and it remains at 19 when the ratio is 30:1. The membrane selectivity is also stable for 30 days in a highly concentrated solution with a high Mg2+/Li+ concentration ratio. These results indicate the feasibility of the MOFCMs for direct lithium extraction from brines with Mg2+ concentrations up to 3.5 M. This study provides an alternative strategy for designing efficient MOF membranes in extracting valuable minerals in the future.

Angstrom-scale ion channels towards single-ion selectivity.

Artificial ion channels with ion permeability and selectivity comparable to their biological counterparts are highly desired for efficient separation, biosensing, and energy conversion technologies. In the past two decades, both nanoscale and sub-nanoscale ion channels have been successfully fabricated to mimic biological ion channels. Although nanoscale ion channels have achieved intelligent gating and rectification properties, they cannot realize high ion selectivity, especially single-ion selectivity. Artificial angstrom-sized ion channels with narrow pore sizes <1 nm and well-defined pore structures mimicking biological channels have accomplished high ion conductivity and single-ion selectivity. This review comprehensively summarizes the research progress in the rational design and synthesis of artificial subnanometer-sized ion channels with zero-dimensional to three-dimensional pore structures. Then we discuss cation/anion, mono-/di-valent cation, mono-/di-valent anion, and single-ion selectivities of the synthetic ion channels and highlight their potential applications in high-efficiency ion separation, energy conversion, and biological therapeutics. The gaps of single-ion selectivity between artificial and natural channels and the connections between ion selectivity and permeability of synthetic ion channels are covered. Finally, the challenges that need to be addressed in this research field and the perspective of angstrom-scale ion channels are discussed.

Cyclodextrin-pillar[n]arene hybridized macrocyclic systems.

Cyclodextrin (CD) and pillar[n]arene are significant macrocyclic host molecules in supramolecular chemistry, and have either similar or contrasting physicochemical properties, for example, both can provide capable cavities available for recognizing various favorite guest molecules, while they usually possess different solubility in aqueous solutions, and exhibit diverse chiral characteristics. To balance their similarity and differences inherited from each chemical structure and incorporate both advantages, the CD-pillar[n]arene hybrid macrocyclic system was recently developed. In this review, we will focus on the preparation and application of CD-pillar[n]arene hybrid macrocyclic systems. Both noncovalent interactions and covalent bonds were employed in the synthesis strategies of building the hybrid macrocyclic system, which was in the form of host-guest inclusion, self-assembly, conjugated molecules, and polymeric structures. Furthermore, the CD-pillar[n]arene hybrid macrocyclic system has been primarily applied for the removal of organic pollutants from water, induced chirality, as well as photocatalysis due to the integration of both cavities from CD and pillar[n]arene as hybrid hosts and chiral characteristics inherited from their chemical structures.

Fullerene-containing pillar[n]arene hybrid composites.

The construction and application of fullerene-containing pillar[n]arene organic-inorganic hybrid composites/systems has been discussed and summarized. Both supramolecular interactions and covalent bonds were involved during the preparation process. By using supramolecular interactions, pillar[n]arenes mainly donate the hydrophobic and electron-rich cavity for complexing fullerene and its derivatives. The "bigger-sized" unmodified pillar[10]arene could directly include C60 in a stoichiometry of 1/1 via host-guest interaction, while the perfunctionalized "smaller-sized" pillar[5]arene with an enlarged channel-like structure could further interact with "size-fixed" fullerene. Additionally, recognition site-containing modified fullerene could integrate with the pillararene cavity for fabricating the functional supramolecular system, which could be further used for applications in photodevices. By forming stable covalent bonds, coupled pillar[n]arene and fullerene hybrid composites could be synthesized via either the modification of pillar[n]arenes with the fullerene subunits, or the utilization of fullerene as the partial structural skeleton for building pillar[n]arenes, in which diverse classic organic synthesis reactions were involved. Interestingly, those fullerene-containing pillar[n]arenes with free cavities could further participate in the formation of hierarchical architectures, such as mechanically interlocked molecules, by cooperating with the "dumbbell" molecule.

Efficient metal ion sieving in rectifying subnanochannels enabled by metal-organic frameworks.

Biological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal-organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K+, Na+ and Li+ in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca2+ and Mg2+, equivalent to a mono/divalent ion selectivity of 103. Moreover, by varying the pH from 3 to 8 the ion selectivity can be tuned further by a factor of 102 to 104. Theoretical simulations indicate that ion-carboxyl interactions substantially reduce the energy barrier for monovalent cations to pass through the MOFSNC, and thus lead to ultrahigh ion selectivity. These findings suggest ways to develop ion selective devices for efficient ion separation, energy reservation and power generation.

Crown ether-pillararene hybrid macrocyclic systems.

A combination of Nobel macrocycle-crown ether and star macrocycle-pillararenes together in organic synthesis and material science is significant in obtaining hybrid systems, with rigid/flexible structural architecture, induced planar chirality, a negative cooperative effect and multiple fused cyclic hosts. In this review, we will discuss the synthesis/preparation of crown ether-pillararene hybrid macrocyclic systems by covalent bonds, supramolecular interactions and mechanical bonds, leading to hybrid compounds, supramolecular assemblies and mechanically interlocked molecules. The practical applications of crown ether-containing pillararenes will also be discussed in diverse areas, such as molecular recognition via fused multiple macrocycles and ion channels as well as external stimuli-responsive smart materials. We also call the attention of related researchers towards academic and technical issues about topological structures and applied functions in this fresh new fused macrocyclic field.

Supramolecular brush polymers prepared from 1,3,4-oxadiazole and cyanobutoxy functionalised pillar[5]arene for detecting Cu2.

A supramolecular brush polymer Poly(P5-OXD) was constructed through the self-assembly of an A1/A2 disubstituted pillar[5]arene P5-OXD with a 1,3,4-oxadiazole unit and a cyanobutoxy group, exhibiting external stimuli responsiveness towards Cu2+ ions with an ON/OFF fluorescence signal output.

Sulfonated Sub-1-nm Metal-Organic Framework Channels with Ultrahigh Proton Selectivity.

Biological proton channels are sub-1-nm protein pores with ultrahigh proton (H+) selectivity over other ions. Inspired by biological proton channels, developing artificial proton channels with biological-level selectivity is of fundamental significance for separation science. Herein we report synthetic proton channels fabrication based on sulfonated metal-organic frameworks (MOFs), UiO-66-X, X = SAG, NH-SAG, (NH-SAG)2 (SAG: sulfonic acid groups), which have sub-1-nm windows and a high density of sulfonic acid groups mimicking natural proton channels. The ion conductance of UiO-66-X channels follows the sequence: H+ ≫ K+ > Na+> Li+, and the sulfonated UiO-66 derivative channels show proton selectivity much higher than that of the pristine UiO-66 channels. Particularly, the UiO-66-(NH-SAG)2 channels exhibit ultrahigh proton selectivities, H+/Li+ up to ∼100, H+/Na+ of ∼80, and H+/K+ of ∼70, which are ∼3 times of that of UiO-66-NH-SAG channels, and ∼15 times of that of UiO-66@SAG channels. The ultrahigh proton selectivity in the sulfonated sub-1-nm MOF channels is mainly attributed to the narrow window-cavity pore structure functionalized with nanoconfined high-density sulfonic acid groups that facilitate fast proton transport and simultaneously exclude other cations. Our work opens an avenue to develop functional MOF channels for selective ion conduction and efficient ion separation.

The synthesis and applications of porphyrin-containing pillararenes.

Porphyrin-pillararene hybrid compounds/systems have attracted much more attention due to the synergistic effect generated by combining two significant macrocycles together in supramolecular chemistry. On the one side, porphyrin units can serve as the N-donor to coordinate with metal cations, acting as a good supplement to the supramolecular recognition abilities of pillararene cavities. On the other side, pillararenes can be grafted to bunches of various functional groups by efficient and easy modification procedures in order to improve the water-solubility of porphyrins for different applications, such as in biomedicine, as well as to enrich the family of porphyrin-based supramolecular architectures. Diverse bonds and interactions have been employed in the fabrication of porphyrin-pillararene hybrid compounds/systems, including covalent bonds and noncovalent interactions, as well as mechanical bonds. Thus, the obtained porphyrin-pillararene hybrid compound, supramolecular self-assembly, and mechanically interlocked molecules have wide applications, e.g., as hetero-ditopic receptors, in detection and sensing, as building blocks for advanced self-assembled materials, in drug delivery and release systems, in photodynamic therapies, and in light-harvesting devices.

Efficient Gating of Ion Transport in Three-Dimensional Metal-Organic Framework Sub-Nanochannels with Confined Light-Responsive Azobenzene Molecules.

1D nanochannels modified with responsive molecules are fabricated to replicate gating functionalities of biological ion channels, but gating effects are usually weak because small molecular gates cannot efficiently block the large channels in the closed states. Now, 3D metal-organic framework (MOF) sub-nanochannels (SNCs) confined with azobenzene (AZO) molecules achieve efficient light-gating functionalities. The 3D MOFSNCs consisting of a MOF UiO66 with ca. 9-12 Šcavities connected by ca. 6 Štriangular windows work as angstrom-scale ion channels, while confined AZO within the MOF cavities function as light-driven molecular gates to efficiently regulate the ion flux. The AZO-MOFSNCs show good cyclic gating performance and high on-off ratios up to 17.8, an order of magnitude higher than ratios observed in conventional 1D AZO-modified nanochannels (1.3-1.5). This work provides a strategy to develop highly efficient switchable ion channels based on 3D porous MOFs and small responsive molecules.

Cation-based Structural Tuning of Pyridine Dipyrrolate Cages and Morphological Control over Their Self-assembly.

Different pyridine dipyrrolate cages including cage-based dimers and polymers may be fabricated in a controlled manner from the same two starting materials, namely, an angular ligand 1 and Zn(acac)2, by changing the counter cation source. With tetrabutylammonium (TBA+) and dimethyl viologen (DMV2+), Cage-3 and Cage-5 are produced. In these cages, two ligands act as bridges and serve to connect together two cage subunits to produce higher order ensembles. In Cage-3 and Cage-5, the TBA+ and DMV2+ counter cations lie outside the cavities of the respective cages. This stands in contrast to what is seen with a previously reported system, Cage-1, wherein dimethylammonium (DMA+) counter cations reside within the cage cavity. When the counter cations are tetraethylammonium (TEA+) and bis(cyclopentadienyl) cobalt(III) (Cp2Co+), polymeric cage materials, PC-1 and PC-2, are formed, respectively. The counter cations thus serve not only to balance charge but also to tune the structural features as a whole. The organic cations used in the present study also act to modulate the further assembly of individual cages. The present cation-based tuning emerges as a new method for a fine-tuning of the multidimensional morphology of self-assembled inorganic materials.

Pillararene-based self-assembled amphiphiles.

Pillararenes are a unique group of supramolecular macrocycles, presenting important features and potential applications on account of their intrinsic structural properties and functionality. Developing pillararene-based self-assembled amphiphiles (PSAs) is an efficient approach to translate pillararenes into functional systems and materials for facilitating their practical applications. In this review article, we highlight recent significant advancements in PSAs. A new standard according to the number, solubility, and amphiphilicity of building blocks is employed for dividing PSAs into different categories. The fabrication of PSAs based on various building blocks and supramolecular interactions, and the formation of amphiphile-based self-assemblies are then discussed based on this standard. Furthermore, interesting stimulus-responsiveness to various factors, such as pH, redox, temperature, light, ionic effect, and host-guest competition, generated by the functional groups on various building blocks is summarized, and the corresponding supramolecular interactions in PSAs and their self-assemblies are elaborated. In addition, some important applications of PSAs and their assemblies are discussed. This review not only provides fundamental findings on the construction of PSAs, but also foresees future research directions in this rapidly developing area.

Homochiral MOF-Polymer Mixed Matrix Membranes for Efficient Separation of Chiral Molecules.

Homochiral metal-organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high-quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF-polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL-53-NH2 nanocrystals by post-synthetic modification with amino acids, such as l-histidine (l-His) and l-glutamic acid (l-Glu). The MIL-53-NH-l-His and MIL-53-NH-l-Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1-phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large-scale homochiral MOF-based MMMs for chiral separation.

Magnetic Gated Biomimetic Artificial Nanochannels for Controllable Ion Transportation Inspired by Homing Pigeon.

The homing pigeon-inspired artificial nanochannel can be modulated by moderate magnetic field in a fast and noncontacting way. The ionic current, as well as rectifying ability and conductance is controlled by the magnetic field reversibly through elastic deformation of the nanochannel. Different gating effects are obtained at the two sides of the asymmetrically conical nanochannel due to the different response models. The magnetic gated nanochannel system also exhibits an excellent stability and a quick response in a noncontacting way, which may be promising in electronic devices related to biological or healthcare applications.

Incorporation of Homochirality into a Zeolitic Imidazolate Framework Membrane for Efficient Chiral Separation.

Homochiral metal-organic frameworks (MOFs) have gained much attention because of their chiral properties and disposition for chiral separation. However, the fabrication of high-quality homochiral MOF membranes remains challenging because of the difficulty in controlling growth of MOF membranes with chiral functionalities. A homochiral zeolitic imidazolate framework-8 (ZIF-8) membrane is reported for efficient chiral separation. The membrane is synthesized by incorporating a natural amino acid, l-histidine (l-His), into the framework of ZIF-8. The homochiral l-His-ZIF-8 membrane exhibits a good selectivity for the R-enantiomer of 1-phenylethanol over the S-enantiomer, showing a high enantiomeric excess value up to 76 %.

Functionalized Boron Nitride Nanosheets: A Thermally Rearranged Polymer Nanocomposite Membrane for Hydrogen Separation.

Amino functionalized boron nitride nanosheets (FBN) were incorporated into a crosslinked, thermally rearranged polyimide (XTR) to fabricate FBN-XTR nanocomposite membrane. The FBN-XTR membrane exhibited a small decrease in H2 permeability but demonstrated a remarkably increased H2 gas selectivity over other gases, compared with XTR. The XTR membrane heat-treated at 425 °C had a H2 permeability of 210 Barrers and a H2 /CH4 separation factor of 24.1, whereas the nanocomposite membrane with 1 wt % FBN exhibited a H2 permeability of 110 Barrers and H2 /CH4 separation factor of 275, an order of magnitude greater. At 1 wt % FBN loading, the FBN-XTR membrane showed three times higher tensile strength and 60 % higher elongation than pristine XTR membrane. In addition, FBN-XTR was found to be able to be readily processed into thin-film membranes for practical H2 separation applications.

A Dual-Responsive Bola-Type Supra-amphiphile Constructed from a Water-Soluble Calix[4]pyrrole and a Tetraphenylethene-Containing Pyridine Bis-N-oxide.

Complexation between a water-soluble calix[4]pyrrole and a ditopic pyridine N-oxide derivative in aqueous media produces a bola-type supra-amphiphile that self-assembles to produce higher order morphologies, including multilamellar vesicles and micelles depending on the pH. The present bola-type supra-amphiphile exhibits strong fluorescence due to structural changes and aggregation induced by host-guest complexation. The resulting structures may be used to recognize, encapsulate, and release non-fluorescent, water-soluble small molecules.

Supramolecular Self-Assembly Induced Adjustable Multiple Gating States of Nanofluidic Diodes.

Artificial nanochannels, inheriting smart gating functions of biological ion channels, promote the development of artificial functional nanofluidic devices for high-performance biosensing and electricity generation. However, gating states of the artificial nanochannels have been mainly realized through chemical modification of the channels with responsive molecules, and their gating states cannot be further regulated once the nanochannel is modified. In this work, we employed a new supramolecular layer-by-layer (LbL) self-assembly method to achieve reversible and adjustable multiple gating features in nanofluidic diodes. Initially, a self-assembly precursor was modified into a single conical nanochannel, then host molecule-cucurbit[8]uril (CB[8]) and guest molecule, a naphthalene derivative, were self-assembled onto the precursor through an LbL method driven by host-enhanced π-π interaction, forming supramolecular monolayer or multilayers on the inner surface of the channel. These self-assemblies with different layer numbers possessed remarkable charge effects and steric effects, exhibiting a capability to regulate the surface charge density and polarity, the effective diameter, and the geometric asymmetry of the single nanochannel, realizing reversible gating of the single nanochannel among multiple rectification and ion-conduction states. As an example of self-assembly of supramolecular networks in nanoconfinements, this work provides a new approach for enhancing functionalities of artificial nanochannels by LbL supramolecular self-assemblies. Meanwhile, since the host molecule, CB[8], used in this work can interact with different kinds of biomolecules and stimuli-responsive chemical species, this work can be further extended to build a novel stable multiple-state research platform for a variety of uses such as sensing and controllable release.

Self-Assembled Pyridine-Dipyrrolate Cages.

An inherently nonlinear pyridine dipyrrolate ligand, namely 2,6-bis(3,4-diethyl-5-carboxy-1H-pyrrol-2yl)pyridine (compound 1), is able to distinguish between different zinc(II) cation sources, namely Zn(acac)2 and Zn(OAc)2, respectively. This differentiation is manifest both in terms of the observed fluorescent behavior in mixed organic media and the reaction chemistry. Treatment of 1 with Zn(acac)2 gives rise to a cage dimer, cage-1, wherein two molecules of compound 1 act as double bridging units to connect two individual cage subunits. As inferred from X-ray crystallographic studies, this cage system consists of discrete zinc dimers with hydroxide bridges that, with the assistance of bound DMF solvent molecules, serve to fix the geometry and orientation of the pyridine dipyrrolate building blocks. When a different zinc source, Zn(OAc)2, is used to carry out an ostensibly similar complexation reaction with compound 1, an acetate-bridged 1D abacus-like cage polymer is obtained as inferred from X-ray diffraction analysis. This extended solid state structure, cage-2, contains individual zinc dimer cage submits and appears stabilized by solvent molecules (DMF) and the counteranion (acetate). Rod-like assemblies are also observed by DLS and SEM. This construct, in contrast to cage-1, proved fluorescent in mixed organic media. The structure of the ligand itself (i.e., in the absence of Zn(II)) was confirmed by X-ray crystallographic analysis and was found to assemble into a supramolecular polymer. Conversion to a dimer form was seen upon the addition of TBAOAc. On the basis of the metric parameters, the structures seen in the solid state are stabilized via hydrogen bonding interactions involving solvent molecules.