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.

Achieving Colorful Ultralong-Lifetime Room-Temperature Phosphorescence Based on Benzocarbazole Derivatives through Resonance Energy Transfer.

It is of practical significance to develop polymer-based room-temperature phosphorescence (RTP) materials with ultralong lifetime and multicolor afterglow. Herein, the benzocarbazole derivatives were selected and combined with a poly(vinyl alcohol) (PVA) matrix by a coassembly strategy. Owing to the hydrogen-bonding interactions between benzocarbazole derivatives and the PVA matrix, the nonradiative transition and the quenching of triplet excitons are effectively inhibited. Therefore, the maximum phosphorescence emission lifetime of 2202.17 ms from ABfCz-PVA and the maximum phosphorescence quantum efficiency of 34.97% from ABtCz-PVA were obtained, respectively. In addition, commercially available dye molecules were selected to construct phosphorescent resonance energy transfer (PRET) systems for energy acceptors, enabling full-color afterglow emission in blue, green, yellow, red, and even white. Based on the characteristics of prepared RTP materials, multifunctional applications to flexibility, information encryption, and erasable drawing were deeply explored.

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.

Polyvinyl Alcohol-Citric Acid: A New Material for Green and Efficient Removal of Cationic Dye Wastewater.

The citric acid (CA) cross-linked polyvinyl alcohol (PVA) adsorbent, PVA-CA, was efficiently synthesized and its application to the removal of dyes in water, particularly the cationic dye, methylene blue (MB), was thoroughly investigated. The morphologies and physiochemical characteristics of PVA-CA were fully characterized by SEM, FT-IR, XRD, TGA, BET, and XPS. The effects of contact time, adsorbent dosage, MB concentration, solution pH, and temperature on the adsorption performance were compared using controllable methods. The maximum adsorption capacity of PVA-CA was 709.86 mg g-1 and the removal rate remained high through several adsorption-desorption cycles, demonstrating that such a composite absorbent has a good adsorption performance and recoverability. Further analysis by the density functional theory (DFT) showed that van der Waals interactions, electrostatic interactions and hydrogen bonding interactions between PVA-CA and MB played significant roles in the adsorption mechanism.

Synthesis, Optical Properties and Cellular Toxicity of Water-Soluble near Infrared-II Fluorescent Assemblies Based on Pillar[5]arene.

The main challenges in second near-infrared region molecular fluorophores are poor water solubility and unknown long-term toxicity at present. Herein, new NIR-II molecular fluorophores have been designed and employed to integrate biocompatible pillar[5]arene with 10 outer triethylene oxide groups for the synthesis of rotaxane IRCR. In addition, PEGylated pillar[5]arenes have been combined for the self-assembly of two supramolecular vesicular systems, i.e., PP5-IR1 and PP5-IR2, affording aqueous solubility and lowered cellular toxicity. In aqueous solution, all these fluorophores displayed room-temperature emission with λmax at 986-1013 nm and quantum yields of 0.54-1.45%. They also exhibited good chemical stability and reasonable self-assembled sizes, which may find potential applications in NIR-II imaging. In addition, PP5-IR1 can be used as a fluorescent chemosensor for selective recognition of glutathione through the cleavage of dinitrophenyl ether and release the fluorescent dye.

Stimuli-Responsive Ion Adsorbents for Sustainable Separation Applications.

Stimuli-responsive ion absorbents (SRIAs) with reversible ion adsorption and desorption properties have recently attracted immense attention due to their outstanding functionalities for sustainable separation applications. Over the past decade, a series of SRIAs that respond to single or multiple external stimuli (e.g., pH, gas, temperature, light, magnetic, and voltage) have been reported to achieve excellent ion adsorption capacity and selectivity while simultaneously allowing for their reusability. In contrast to traditional adsorbents that are mainly regenerated through chemical additives, SRIAs allow for reduced chemical and even chemical-free regeneration capacities, thereby enabling environmentally friendly and energy-efficient separation technologies. In this review, we systematically summarize the materials and strategies reported to date for synthesizing single-, dual-, and multiresponsive ion adsorbents. Following a discourse on the fundamental mechanisms that govern their adsorption and desorption under various external stimuli, we provide a concise discussion of the regeneration capacity and application of these responsive ion adsorbents for sustainable water desalination, toxic ion removal, and valuable ion extract and recovery. Finally, we discuss the challenges in developing and deploying these promising multifunctional responsive ion adsorbents together with strategies to overcome these limitations and provide prospects for their future.

Bio-Inspired Subnanofluidics: Advanced Fabrication and Functionalization.

Biological ion channels can realize high-speed and high-selective ion transport through the protein filter with the sub-1-nanometer channel. Inspired by biological ion channels, various kinds of artificial subnanopores, subnanochannels, and subnanoslits with improved ion selectivity and permeability are recently developed for efficient separation, energy conversion, and biosensing. This review article discusses the advanced fabrication and functionalization methods for constructing subnanofluidic pores, channels, tubes, and slits, which have shown great potential for various applications. Novel fabrication methods for producing subnanofluidics, including top-down techniques such as electron beam etching, ion irradiation, and electrochemical etching, as well as bottom-up approaches starting from advanced microporous frameworks, microporous polymers, lipid bilayer embedded subnanochannels, and stacked 2D materials are well summarized. Meanwhile, the functionalization methods of subnanochannels are discussed based on the introduction of functional groups, which are classified into direct synthesis, covalent bond modifications, and functional molecule fillings. These methods have enabled the construction of subnanochannels with precise control of structure, size, and functionality. The current progress, challenges, and future directions in the field of subnanofluidic are also discussed.

Functional Polymeric Systems for Advanced Industrial Applications.

Functional polymeric systems constitute a huge family of novel hierarchical architectures categorized by different polymeric shapes, such as linear, brush-like, star-like, dendrimer-like and network-like ones; various components, such as organic-inorganic hybrid oligomeric/polymeric materials and metal-ligated polymers; different features, such as porous polymers; and diverse approaching strategies and driving forces, such as conjugated/supramolecular/mechanical force-based polymers and self-assembled networks [...].

Construction of angstrom-scale ion channels with versatile pore configurations and sizes by metal-organic frameworks.

Controllable fabrication of angstrom-size channels has been long desired to mimic biological ion channels for the fundamental study of ion transport. Here we report a strategy for fabricating angstrom-scale ion channels with one-dimensional (1D) to three-dimensional (3D) pore structures by the growth of metal-organic frameworks (MOFs) into nanochannels. The 1D MIL-53 channels of flexible pore sizes around 5.2 × 8.9 Å can transport cations rapidly, with one to two orders of magnitude higher conductivities and mobilities than MOF channels of hybrid pore configurations and sizes, including Al-TCPP with 1D ~8 Å channels connected by 2D ~6 Å interlayers, and 3D UiO-66 channels of ~6 Å windows and 9 - 12 Å cavities. Furthermore, the 3D MOF channels exhibit better ion sieving properties than those of 1D and 2D MOF channels. Theoretical simulations reveal that ion transport through 2D and 3D MOF channels should undergo multiple dehydration-rehydration processes, resulting in higher energy barriers than pure 1D channels. These findings offer a platform for studying ion transport properties at angstrom-scale confinement and provide guidelines for improving the efficiency of ionic separations and nanofluidics.

An artificial sodium-selective subnanochannel.

Single-ion selectivity with high precision has long been pursued for fundamental bioinspired engineering and applications such as in ion separation and energy conversion. However, it remains a challenge to develop artificial ion channels to achieve single-ion selectivity comparable to their biological analogs, especially for high Na+/K+ selectivity. Here, we report an artificial sodium channel by subnanoconfinement of 4'-aminobenzo-15-crown-5 ethers (15C5s) into ~6-Å-sized metal-organic framework subnanochannel (MOFSNC). The resulting 15C5-MOFSNC shows an unprecedented Na+/K+ selectivity of tens to 102 and Na+/Li+ selectivity of 103 under multicomponent permeation conditions, comparable to biological sodium channels. A co-ion-responsive single-file transport mechanism in 15C-MOFSNC is proposed for the preferential transport of Na+ over K+ due to the synergetic effects of size exclusion, charge selectivity, local hydrophobicity, and preferential binding with functional groups. This study provides an alternative strategy for developing potential single-ion selective channels and membranes for many applications.

Applications of Advanced Nanomaterials in Sensor Devices.

Nanomaterials can be classified into diverse categories according to their various physical and chemical properties, dimensionality, production procedures, compositions, and homogeneity [...].

Pillar[n]arene-calix[m]arene hybrid macrocyclic structures.

To reserve planar chirality, enhance molecular recognition, and build advanced self-assemblies, hybrid macrocyclic hosts containing rigid pillar[n]arene and flexible calix[m]arene were designed, prepared and investigated for interesting applications. This review summarizes and discusses different synthetic strategies for constructing hybrid macrocyclic structures. Pillar[n]arene dimer with rigid aromatic double bridges provided the possibility of introducing calix[m]arene cavities, where the planar chirality was reserved in the structure of pillararene. The capacity for molecular recognition was enhanced by hybrid macrocyclic cavities. Interestingly, the obtained pillar[n]arene-calix[m]arene could self-assemble into "channels" and "honeycomb" in both the solid state and solution phase as well as donate the molecular architecture as the wheel for the formation of mechanically interlocked molecules, such as rotaxane. In addition, the pillar[n]arene and calix[m]arene could also be coupled together to produce pillar[n]arene embeded 1,3-alternate and cone conformational calix[m]arene derivatives, which could catalyze the oxidative polymerization of aniline in aqueous solutions. Except for building hybrid cyclophanes by covalent bonds, weak supramolecular interactions were used to prepare pillar[n]arene-calix[m]arene analogous composites with other pillar-like pillar[n]pyridiniums and calix-like calix[m]pyrroles, exhibiting reasonable performances in enhancing molecular recognition and trapping solvent molecules.

Challenges and Opportunities of Chemiresistors Based on Microelectromechanical Systems for Chemical Olfaction.

Microelectromechanical-system (MEMS)-based semiconductor gas sensors are considered one of the fastest-growing, interdisciplinary high technologies during the post-Moore era. Modern advancements within this arena include wearable electronics, Internet of Things, and artificial brain-inspired intelligence, among other modalities, thus bringing opportunities to drive MEMS-based gas sensors with higher performance, lower costs, and wider applicability. However, the high demand for miniature and micropower sensors with unified processes on a single chip imposes great challenges. This review focuses on recent developments and pitfalls in MEMS-based micro- and nanoscale gas sensors and details future trends. We also cover the background of the topic, seminal efforts, current applications and challenges, and opportunities for next-generation systems.

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.

Pillar[n]arene-Mimicking/Assisted/Participated Carbon Nanotube Materials.

The recent progress in pillar[n]arene-assisted/participated carbon nanotube hybrid materials were initially summarized and discussed. The molecular structure of pillar[n]arene could serve different roles in the fabrication of attractive carbon nanotube-based materials. Firstly, pillar[n]arene has the ability to provide the structural basis for enlarging the cylindrical pillar-like architecture by forming one-dimensional, rigid, tubular, oligomeric/polymeric structures with aromatic moieties as the linker, or forming spatially "closed", channel-like, flexible structures by perfunctionalizing with peptides and with intramolecular hydrogen bonding. Interestingly, such pillar[n]arene-based carbon nanotube-resembling structures were used as porous materials for the adsorption and separation of gas and toxic pollutants, as well as for artificial water channels and membranes. In addition to the art of organic synthesis, self-assembly based on pillar[n]arene, such as self-assembled amphiphilic molecules, is also used to promote and control the dispersion behavior of carbon nanotubes in solution. Furthermore, functionalized pillar[n]arene derivatives integrated carbon nanotubes to prepare advanced hybrid materials through supramolecular interactions, which could also incorporate various compositions such as Ag and Au nanoparticles for catalysis and sensing.

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.

Hybrid Macrocyclic Polymers: Self-Assembly Containing Cucurbit[m]uril-pillar[n]arene.

Supramolecular self-assembly by hybrid macrocycles containing both cucurbit[m]uril (CB[m]) and pillar[n]arene was discussed and summarized in this review. Due to different solubility, diverse-sized cavities, and various driving forces in recognizing guests, the role of CB[m] and pillar[n]arene in such hybrid macrocyclic systems could switch between competitor in capturing specialized guests, and cooperator for building advanced hybridized macrocycles, by controlling their characteristics in host-guest inclusions. Furthermore, both CB[m] and pillar[n]arene were employed for fabricating advanced supramolecular self-assemblies such as mechanically interlocked molecules and supramolecular polymers. In those self-assemblies, CB[m] and pillar[n]arene played significant roles in, e.g., microreactor for catalyzing particular reactions to bridge different small pieces together, molecular "joint" to connect different monomers into larger assemblies, and "stabilizer" in accommodating the guest molecules to adopt a favorite structure geometry ready for assembling.

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.