Perfect confinement of crown ethers in MOF membrane for complete dehydration and fast transport of monovalent ions.

Fast transport of monovalent ions is imperative in selective monovalent ion separation based on membranes. Here, we report the in situ growth of crown ether@UiO-66 membranes at a mild condition, where dibenzo-18-crown-6 (DB18C6) or dibenzo-15-crown-5 is perfectly confined in the UiO-66 cavity. Crown ether@UiO-66 membranes exhibit enhanced monovalent ion transport rates and mono-/divalent ion selectivity, due to the combination of size sieving and interaction screening effects toward the complete monovalent ion dehydration. Specifically, the DB18C6@UiO-66 membrane shows a permeation rate (e.g., K+) of 1.2 mol per square meter per hour and a mono-/divalent ion selectivity (e.g., K+/Mg2+) of 57. Theoretical calculations and simulations illustrate that, presumably, ions are completely dehydrated while transporting through the DB18C6@UiO-66 cavity with a lower energy barrier than that of the UiO-66 cavity. This work provides a strategy to develop efficient ion separation membranes via integrating size sieving and interaction screening and to illuminate the effect of ion dehydration on fast ion transport.

A Homochiral Porous Organic Cage-Polymer Membrane for Enantioselective Resolution.

Membrane-based enantioselective separation is a promising method for chiral resolution due to its low cost and high efficiency. However, scalable fabrication of chiral separation membranes displaying both high enantioselectivity and high flux of enantiomers is still a challenge. Here, the authors report the preparation of homochiral porous organic cage (Covalent cage 3 (CC3)-R)-based enantioselective thin-film-composite membranes using polyamide (PA) as the matrix, where fully organic and solvent-processable cage crystals have good compatibility with the polymer scaffold. The hierarchical CC3-R channels consist of chiral selective windows and inner cavities, leading to favorable chiral resolution and permeation of enantiomers; the CC3-R/PA composite membranes display an enantiomeric excess of 95.2% for R-(+)-limonene over S-(-)-limonene and a high flux of 99.9 mg h-1 m-2. This work sheds light on the use of homochiral porous organic cages for preparing enantioselective membranes and demonstrates a new route for the development of next-generation chiral separation membranes.

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.

Accurate prediction of solvent flux in sub-1-nm slit-pore nanosheet membranes.

Nanosheet-based membranes have shown enormous potential for energy-efficient molecular transport and separation applications, but designing these membranes for specific separations remains a great challenge due to the lack of good understanding of fluid transport mechanisms in complex nanochannels. We synthesized reduced MXene/graphene hetero-channel membranes with sub-1-nm pores for experimental measurements and theoretical modeling of their structures and fluid transport rates. Our experiments showed that upon complete rejection of salt and organic dyes, these membranes with subnanometer channels exhibit remarkably high solvent fluxes, and their solvent transport behavior is very different from their homo-structured counterparts. We proposed a subcontinuum flow model that enables accurate prediction of solvent flux in sub-1-nm slit-pore membranes by building a direct relationship between the solvent molecule-channel wall interaction and flux from the confined physical properties of a liquid and the structural parameters of the membranes. This work provides a basis for the rational design of nanosheet-based membranes for advanced separation and emerging nanofluidics.

Electricity generation from carbon dioxide adsorption by spatially nanoconfined ion separation.

Selective ion transport underpins fundamental biological processes for efficient energy conversion and signal propagation. Mimicking these 'ionics' in synthetic nanofluidic channels has been increasingly promising for realizing self-sustained systems by harvesting clean energy from diverse environments, such as light, moisture, salinity gradient, etc. Here, we report a spatially nanoconfined ion separation strategy that enables harvesting electricity from CO2 adsorption. This breakthrough relies on the development of Nanosheet-Agarose Hydrogel (NAH) composite-based generators, wherein the oppositely charged ions are released in water-filled hydrogel channels upon adsorbing CO2. By tuning the ion size and ion-channel interactions, the released cations at the hundred-nanometer scale are spatially confined within the hydrogel network, while ångström-scale anions pass through unhindered. This leads to near-perfect anion/cation separation across the generator with a selectivity (D-/D+) of up to 1.8 × 106, allowing conversion into external electricity. With amplification by connecting multiple as-designed generators, the ion separation-induced electricity reaching 5 V is used to power electronic devices. This study introduces an effective spatial nanoconfinement strategy for widely demanded high-precision ion separation, encouraging a carbon-negative technique with simultaneous CO2 adsorption and energy generation.

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.

Ultrathin Two-Dimensional Porous Fullerene Membranes for Ultimate Organic Solvent Separation.

Two-dimensional (2D) materials with high chemical stability have attracted intensive interest in membrane design for the separation of organic solvents. As a novel 2D material, polymeric fullerenes (C60)∞ with distinctive properties are very promising for the development of innovative membranes. In this work, we report the construction of a 2D (C60)∞ nanosheet membrane for organic solvent separation. The pathways of the (C60)∞ nanosheet membrane are constructed by sub-1-nm lateral channels and nanoscale in-plane pores created by the depolymerization of the (C60)∞ nanosheets. Attributing to ordered and shortened transport pathways, the ultrathin porous (C60)∞ membrane is superior in organic solvent separation. The hexane, acetone, and methanol fluxes are up to 1146.3±53, 900.4±41, and 879.5±42 kg ⋅ m-2 ⋅ h-1, respectively, which are up to 130 times higher than those of the state-of-the-art membranes with similar dye rejection. Our findings demonstrate the prospect of 2D (C60)∞ as a promising nanofiltration membrane in the separation of organic solvents from macromolecular compounds such as dyes, drugs, hormones, etc.

Charge-Gradient Sulfonated Poly(ether ether ketone) Membrane with Enhanced Ion Selectivity for Osmotic Energy Conversion.

Engineered asymmetric heterogeneous ion-selective membranes have become a focal point for their improved efficiency in harnessing osmotic energy from ionic solutions with varying salinity. However, achieving both energy conversion efficiency and excellent chemical stability necessitates effectively mitigating the formation of detrimental interface cracks between two different layers. We develop a charge-gradient sulfonated poly(ether ether ketone) (SPEEK) membrane (CG-SPEEK) on a large-scale using a straightforward coating method. As an osmotic energy generator, CG-SPEEK membrane achieves an impressive output power density of 9.2 W m-2 and exhibits ultrahigh cation selectivity (0.99), with an energy conversion efficiency of 48% at a 50-fold NaCl concentration gradient. The results highlight the ion diode effects of CG-SPEEK, driven by a charge density gradient that accelerates cation transport while suppressing ion concentration polarization. Density functional theory simulations provide further insights, revealing that the energy barrier for Na+ ion transport through CG-SPEEK membrane is lower than that through a homogeneous SPEEK membrane. This work not only enhances our understanding of ion transport dynamics but also establishes the CG-SPEEK membrane as a promising candidate for efficient osmotic energy conversion applications.

Dual-Channel-Ion Conductor Membrane for Low-Energy Lithium Extraction.

The development of energy-efficient and environmentally friendly lithium extraction techniques is essential to meet the growing global demand for lithium-ion batteries. In this work, a dual-channel ion conductor membrane was designed for a concentration-driven lithium-selective ion diffusion process. The membrane was based on a porous lithium-ion conductor, and its pores were modified with an anion-exchange polymer. Thus, the sintered lithium-ion conductors provided highly selective cation transport channels, and the functionalized nanopores with positive charges enabled the complementary permeation of anions to balance the transmembrane charges. As a result, the dual-channel membrane realized an ultrahigh Li+/Na+ selectivity of ∼1389 with a competitive Li+ flux of 21.6 mmol·m-2·h-1 in a diffusion process of the LiCl/NaCl binary solution, which was capable of further maintaining the high selectivity over 7 days of testing. Therefore, this work demonstrates the great potential of the dual-channel membrane design for high-performing lithium extraction from aqueous resources with low energy consumption and minimal environmental impact.

Nanoconfinement enabled non-covalently decorated MXene membranes for ion-sieving.

Covalent modification is commonly used to tune the channel size and functionality of 2D membranes. However, common synthesis strategies used to produce such modifications are known to disrupt the structure of the membranes. Herein, we report less intrusive yet equally effective non-covalent modifications on Ti3C2Tx MXene membranes by a solvent treatment, where the channels are robustly decorated by protic solvents via hydrogen bond network. The densely functionalized (-O, -F, -OH) Ti3C2Tx channel allows multiple hydrogen bond establishment and its sub-1-nm size induces a nanoconfinement effect to greatly strengthen these interactions by maintaining solvent-MXene distance and solvent orientation. In sub-1-nm ion sieving and separation, as-decorated membranes exhibit stable ion rejection, and proton-cation (H+/Mn+) selectivity that is up to 50 times and 30 times, respectively, higher than that of pristine membranes. It demonstrates the feasibility of non-covalent methods as a broad modification alternative for nanochannels integrated in energy-, resource- and environment-related applications.

Construction of 2D/0D Graphene Oxide/Copper(I) Oxide-Incorporated Titanium Dioxide Mixed-Dimensional Membranes with Ultrafast Water Transport and Enhanced Antifouling Properties.

Graphene oxide (GO) membranes are emerging for water treatment. Meanwhile, challenges remain due to membrane fouling and their instability in aqueous solutions. Herein, a novel GO-based mixed-dimensional membrane with superior antifouling and nonswelling properties was prepared by assembling two-dimensional (2D) GO nanosheets and zero-dimensional (0D) copper(I) oxide-incorporated titanium dioxide photocatalyst (CT). The decoration of CT in GO nanosheets tuned the microstructure and surface hydrophilicity while creating more transport channels in CT/GO membranes. This resulted in a high water permeance of 171.5 L m-2 h-1 bar-1 and improved selectivity to various dye molecules (96.2-98.6%). Due to the significantly enhanced antibacterial properties of the CT nanoparticles, the growth of bacteria on the surface of the CT/GO membrane was suppressed (threefold less than that on the GO membrane). Moreover, the embedding of photocatalysts also allowed CT/GO membranes to exhibit ∼9-fold improvement in antibacterial activity and organic dye degradation performance under visible-light irradiation. This study offers a powerful solution to enhance the nanofiltration performance and antibacterial properties of GO membranes toward practical applications.

Pyro-layered heterostructured nanosheet membrane for hydrogen separation.

Engineering different two-dimensional materials into heterostructured membranes with unique physiochemical properties and molecular sieving channels offers an effective way to design membranes for fast and selective gas molecule transport. Here we develop a simple and versatile pyro-layering approach to fabricate heterostructured membranes from boron nitride nanosheets as the main scaffold and graphene nanosheets derived from a chitosan precursor as the filler. The rearrangement of the graphene nanosheets adjoining the boron nitride nanosheets during the pyro-layering treatment forms precise in-plane slit-like nanochannels and a plane-to-plane spacing of ~3.0 Å, thereby endowing specific gas transport pathways for selective hydrogen transport. The heterostructured membrane shows a high H2 permeability of 849 Barrer, with a H2/CO2 selectivity of 290. This facile and scalable technique holds great promise for the fabrication of heterostructures as next-generation membranes for enhancing the efficiency of gas separation and purification processes.

Partial quaternization promoted metal-organic frameworks for efficient photocatalytic removal of chromium(VI).

A one-step strategy is applied to partially quaternize the ligand of UiO-66-NH2, and the resultant UiO-66-N(CH3)3+ showed greatly improved photocatalytic performance for Cr(VI) reduction, with the apparent reaction rate constant k increasing by 8.3 times. This strategy could be used to effectively promote the performance of other MOFs-NH2, demonstrating general applicability.

Smart utilisation of reverse solute diffusion in forward osmosis for water treatment: A mini review.

Forward osmosis (FO) has been widely studied as a promising technology in wastewater treatment, but undesirable reverse solute diffusion (RSD) is inevitable in the FO process. The RSD is generally regarded as a negative factor for the FO process, resulting in the loss of draw solutes and reduced FO efficiency. Conventional strategies to address RSD focus on reducing the amount of reverse draw solutes by fabricating high selective FO membranes and/or selecting the draw solute with low diffusion. However, since RSD is inevitable, doubts have been raised about the strategies to cope with the already occurring reverse draw solutes in the feed solution, and the feasibility to positively utilise the RSD phenomenon to improve the FO process. Herein, we review the state-of-the-art applications of RSD and their benefits such as improving selectivity and maintaining the stability of the feed solution for both independent FO processes and FO integrated processes. We also provide an outlook and discuss important considerations, including membrane fouling, membrane development and draw/feed solution properties, in RSD utilisation for water and wastewater treatment.

Scalable high yield exfoliation for monolayer nanosheets.

Although two-dimensional (2D) materials have grown into an extended family that accommodates hundreds of members and have demonstrated promising advantages in many fields, their practical applications are still hindered by the lack of scalable high-yield production of monolayer products. Here, we show that scalable production of monolayer nanosheets can be achieved by a facile ball-milling exfoliation method with the assistance of viscous polyethyleneimine (PEI) liquid. As a demonstration, graphite is effectively exfoliated into graphene nanosheets, achieving a high monolayer percentage of 97.9% at a yield of 78.3%. The universality of this technique is also proven by successfully exfoliating other types of representative layered materials with different structures, such as carbon nitride, covalent organic framework, zeolitic imidazolate framework and hexagonal boron nitride. This scalable exfoliation technique for monolayer nanosheets could catalyze the synthesis and industrialization of 2D nanosheet materials.

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.

A Homochiral Poly(2-oxazoline)-based Membrane for Efficient Enantioselective Separation.

Chiral separation membranes have shown great potential for the efficient separation of racemic mixtures into enantiopure components for many applications, such as in the food and pharmaceutical industries; however, scalable fabrication of membranes with both high enantioselectivity and flux remains a challenge. Herein, enantiopure S-poly(2,4-dimethyl-2-oxazoline) (S-PdMeOx) macromonomers were synthesized and used to prepare a new type of enantioselective membrane consisting of a chiral S-PdMeOx network scaffolded by graphene oxide (GO) nanosheets. The S-PdMeOx-based membrane showed a near-quantitative enantiomeric excess (ee) (98.3±1.7 %) of S-(-)-limonene over R-(+)-limonene and a flux of 0.32 mmol m-2 h-1 . This work demonstrates the potential of homochiral poly(2,4-disubstituted-2-oxazoline)s in chiral discrimination and provides a new route to the development of highly efficient enantioselective membranes using synthetic homochiral polymer networks.

Photo-controllable Ion-Gated Metal-Organic Framework MIL-53 Sub-nanochannels for Efficient Osmotic Energy Generation.

By closing and opening ion channels, electric eels are able to convert ion concentration gradients into electricity. Inspired by electric eels, considerable artificial sub-nanoscale ion channels with high ion selectivity and transportation efficiency have been designed for harvesting the osmotic energy between ionic solutions of different salinities, but constructing smart ion-gated sub-nanochannels for effective ion transport is still a huge challenge. Herein, photo-controllable sub-nanochannels of metal-organic framework (MOF) NH2-MIL-53 encapsulated with spiropyrans (SP-MIL-53) were fabricated by a facile in situ growth strategy. Interestingly, the highly ordered sub-nanochannels of SP-MIL-53 were switched on and off to efficiently regulate the ion flux by the light-driven isomerization of SP, which made it a smart ionic gate with a high on-off ratio of 16.2 in 10 mM KCl aqueous solution via UV irradiation. Moreover, the ion-gated sub-nanochannel membrane yielded a high power density of 8.3 W m-2 under a 50-fold KCl concentration gradient in the open state. Density functional theory calculations revealed that K+ ions in SP-MIL-53 sub-nanochannels had a higher mobility constant (3.61 × 10-2) with UV irradiation than without UV illumination (2.33 × 10-22). This work provides an effective way to develop smart ion-gating sub-nanochannels for capturing salinity gradient power.