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.

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.

A review of struvite crystallization for nutrient source recovery from wastewater.

Nutrient recovery from wastewater not only reduces the nutrient load on water resources but also alleviates the environmental problems in aquatic ecosystems, which is a solution to achieve a sustainable society. Besides, struvite crystallization technology is considered a potential nutrient recovery technology because the precipitate obtained can be reused as a slow-release fertilizer. This review presents the basic properties of struvite and the theory of the basic crystallization process. In addition, the possible influencing variables of the struvite crystallization process on the recovery efficiency and product purity are also examined in detail. Then, the advanced auxiliary technologies for facilitating the struvite crystallization process are systematically discussed. Moreover, the economic and environmental benefits of the struvite crystallization process for nutrient recovery are introduced. Finally, the shortcomings and inadequacies of struvite crystallization technology are presented, and future research prospects are provided. This work serves as the foundation for the future use of struvite crystallization technology to recover nutrients in response to the increasingly serious environmental problems and resource depletion.

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.

Unidirectional and Selective Proton Transport in Artificial Heterostructured Nanochannels with Nano-to-Subnano Confined Water Clusters.

The construction of biological proton channel analogues has attracted substantial interest owing to their wide potential in separation of ions, sensing, and energy conversion. Here, metal-organic framework (MOF)/polymer heterogeneous nanochannels are presented, in which water molecules are confined to disordered clusters in the nanometer-sized polymer regions and to ordered chains with unique molecular configurations in the 1D sub-1-nm porous MOF regions, to realize unidirectional, fast, and selective proton transport properties, analogous to natural proton channels. Given the nano-to-subnano confined water junctions, experimental proton conductivities in the polymer-to-MOF direction of the channels are much higher than those in the opposite direction, showing a high rectification up to 500 and one to two orders of magnitude enhancement compared to the conductivity of proton transport in bulk water. The channels also show a good proton selectivity over other cations. Theoretical simulations further reveal that the preferential and fast proton conduction in the nano-to-subnano channel direction is attributed to extremely low energy barriers for proton transport from disordered to ordered water clusters. This study opens a novel approach to regulate ion permeability and selectivity of artificial ion channels.

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.

Effect of Anion Species on Ion Current Rectification Properties of Positively Charged Nanochannels.

Biological ion channels can realize delicate mass transport under complicated physiological conditions. Artificial nanochannels can achieve biomimetic ion current rectification (ICR), gating, and selectivity that are mostly performed in pure salt solutions. Synthetic nanochannels that can function under mixed ion systems are highly desirable, yet their performances are hard to be compared to those under pure systems. Seeking out the potential reasons by investigating the effect of mixed-system components on the ion-transport properties of the constructed nanochannels seems necessary and important. Herein, we report the effect of anions with different charges and sizes on the ICR properties of positively charged nanochannels. Among the investigated anions, the low-valent anions showed no impact on the ICR direction, while the high-valent component ferrocyanide [Fe(CN)64-] caused significant ICR inversion. The ICR inversion mechanism is evidenced to result from the adsorption of Fe(CN)64--induced surface charge reversal, which relates to solution concentration, pH conditions, and nanochannel sizes and applies to both aminated and quaternized nanochannels that are positively charged. Noticeably, Fe(CN)64- is found to interfere with the transport of protein molecules in the nanochannel. This work points out that the ion species from mixed systems would potentially impact the intrinsic ICR properties of the nanochannels. Replacing highly charged counterions with organic components would be promising in building up future nanochannel-based mass transport systems running under mixed systems.

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.

Monovalent Cation-Phenolic Crystals with pH-Driven Reversible Crystal Transformation.

The conversion of renewable plant polyphenol to advanced materials with tailorable properties and various functions is desirable and challenging. In this work, monovalent cation-phenolic crystals contained K+ or Na+ ions were synthesized by using plant polyphenol as an organic source in alkaline solution. The crystal structure was resolved, showing a laminar crystal structure with M+ as connecting nodes. The morphologies (e.g., rod-like and spindle-shaped) and chemical compositions of crystals could be tuned by changing the cations. Interestingly, these polymer crystals exhibited a pH-driven reversible crystal transformation. They transformed into their protonated crystalline form under acidic conditions (e.g., pH 2) and went back to the cation-bound crystalline form in alkaline solutions. Furthermore, the crystals proved excellent antioxidants and heavy metal ion adsorbents.

Thermoresponsive Amphoteric Metal-Organic Frameworks for Efficient and Reversible Adsorption of Multiple Salts from Water.

Regenerable, high-efficiency salt sorption materials are highly desirable for water treatment. Here, a thermoresponsive, amphoteric metal-organic framework (MOF) material is reported that can adsorb multiple salts from saline water at room temperature and effectively release the adsorbed salts into water at elevated temperature (e.g., 80 °C). The amphoteric MOF, integrated with both cation-binding carboxylic groups and anion-binding tertiary amine groups, is synthesized by introducing a polymer with tertiary amine groups into the cavities of a water-stable MOF such as MIL-121 with carboxylic groups inside its frameworks. The amphoterized MIL-121 exhibits excellent salt adsorption properties, showing stable adsorption-desorption cycling performances and high LiCl, NaCl, MgCl2 , and CaCl2 adsorption capacities of 0.56, 0.92, 0.25, and 0.39 mmol g-1 , respectively. This work provides a novel, effective strategy for synthesizing new-generation, environmental-friendly, and responsive salt adsorption materials for efficient water desalination and purification.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Periodic oscillation of ion conduction of nanofluidic diodes using a chemical oscillator.

Periodic ion-conduction oscillation of biological ion channels in a living system is essential for numerous life processes. Here we report an oscillatory nanofluidic system that can self-regulate its ion-conduction states under constant conditions. The oscillatory nanofluidic system is constructed by integrating a chemical oscillator into an artificial single nanochannel system. Oscillating chemical reactions of the pH oscillator carried out inside the nanochannel are used to switch the surface properties of the channel between highly and lowly charged states, thus realizing an autonomous, continuous and periodic oscillation of the ion conductance of the channel between high and low ion-conduction states. The ion-conduction switching is characterized by the periodic ion current oscillation of the nanochannel measured under constant conditions. The oscillation period of the nanofluidic devices decreased gradually with increasing the working temperature. This study is a potential step toward the ability to directly convert chemical energy to ion-conduction oscillation in nanofluidics. On the basis of these findings, we believe that a variety of artificial oscillatory nanofluidic systems will be achieved in future by integrating artificial functional nanochannels with diverse oscillating chemical reactions.

Hydrogel-polyurethane interpenetrating network material as an advanced draw agent for forward osmosis process.

Water desalination and purification are critical to address the global issue of the shortage of clean water. Forward osmosis (FO) desalination is an emerging low-cost technology for clean water production from saline water. The lack of a suitable draw agent is one of hurdle for the commercialization of FO desalination technology. Recently, the thermoresponsive hydrogel has been demonstrated to be a potential draw agent for the FO process. However, the commonly used hydrogel powder shows a much lower flux than other kind of draw agent such as inorganic salts. In this work, a hydrogel-polyurethane interpenetrating network (HPIPN) with monolith form was prepared by controlling the radical polymerization of the monomers (N-isopropylacrylamide and sodium acrylate) in the macropores (∼400 µm) of commercial polyurethane foam (PUF). These HPIPN composites show a flux as high as 17.9 LMH, which is nearly 8 times than that of hydrogel powders (2.2 LMH). The high flux is attributed to the 3-D continuous hydrogel-polyurethane interpenetrating network, which can effectively enhance the water transport inside the monolith.

Robust Thermoresponsive Polymer Composite Membrane with Switchable Superhydrophilicity and Superhydrophobicity for Efficient Oil-Water Separation.

Herein, we report for the first time on the fabrication of a robust, thermoresponsive polymer membrane produced by the combination of an elastic polyurethane (TPU) microfiber web and poly(N-isopropylacrylamide) (PNIPAM). PNIPAM hydrogel is evenly coated on the surface of TPU microfibers, and thus, the wettability of TPU-PNIPAM membrane is amplified by taking advantage of the hierarchical structure and increased surface roughness. The TPU-PNIPAM membrane possesses switchable superhydrophilicity and superhydrophobicity as the temperature of membrane changes from 25 to 45 °C. The composite membrane is shown successfully able to separate a 1 wt % oil-in-water emulsion and 1 wt % water-in-oil emulsion at 25 and 45 °C, respectively, with a high separation efficiency of ≥99.26%. Furthermore, the composite membranes show excellent mechanical properties, and they are highly flexible and mechanically tough. The smart composite membranes reported here have shown great potential for further development for practical high-efficiency oil-water separations.

Bioinspired Smart Gate-Location-Controllable Single Nanochannels: Experiment and Theoretical Simulation.

pH-activated gates intelligently govern the ion transport behaviors of a wide range of bioinspired ion channels, but the mechanisms between the gate locations and the functionalities of the ion channels remain poorly understood. Here, we construct an artificial gate-location-tunable single-nanochannel system to systematically investigate the impact of the gate location on the ion transport property of the biomimetic ion channel. The gate-location-controllable single nanochannels are prepared by asymmetrically grafting pH-responsive polymer gates on one side of single nanochannels with gradual shape transformation. Experimental ion current measurements show that the gating abilities and rectification effects of the pH-gated nanochannels can be gradually altered by precisely locating the artificial pH gates on the different sites of the channels. The experimental gate-location-dependent gating and rectification of ion current in the bioinspired ion channel system is further well confirmed by theoretical simulation. This work, as an example, provides a new avenue to optimize the smart ion transport features of diverse artificial nanogate devices via precisely locating the gates on the appropriate sites of the artificial nanochannels.