Oriented 1D Metal-Organic Frameworks for Selective Chemisorption by a Substitution-Insertion Mechanism.

Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and purification of targeted systems. Herein, oriented 1D NH2-CuBDC·H2O metal-organic frameworks (MOFs) featuring accessible CuII sites are successfully fabricated by bottom-up interfacial polymerization. The prepared MOFs, as deliberately self-assembled secondary particles, exhibit a visually detectable coordination-responsive characteristic induced by the nucleophilic substitution and competitive coordination of guest molecules. As a versatile phase-change chemosorbent, the MOFs exhibit unprecedented NH3 capture (18.83 mmol g-1 at 298 K) and bioethanol dehydration performance (enriching ethanol from 99% to 99.99% within 10 min by direct adsorption separation of liquid mixtures of ethanol and water). Furthermore, the raw materials for preparing the 1D MOFs are inexpensive and readily available, and the facile regeneration with water washing at room temperature effectively minimizes the energy consumption and cost of recycling, enabling it to be the most valuable adsorbent for the removal and separation of target substances.

Covalent Organic Framework Membranes with Regulated Orientation for Monovalent Cation Sieving.

Continuous covalent organic framework (COF) thin membranes have garnered broad concern over the past few years due to their merits of low energy requirements, operational simplicity, ecofriendliness, and high separation efficiency in the application process. This study marks the first instance of fabricating two distinct, self-supporting COF membranes from identical building blocks through solvent modulation. Notably, the precision of the COF membrane's separation capabilities is substantially enhanced by altering the pore alignment from a random to a vertical orientation. Within these confined channels, the membrane with vertically aligned pores and micron-scale stacking thickness demonstrates rapid and selective transportation of Li+ ions over Na+ and K+ ions, achieving Li+/K+ and Li+/Na+ selectivity ratios of 38.7 and 7.2, respectively. This research not only reveals regulated orientation and layer stacking in COF membranes via strategic solvent selection but also offers a potent approach for developing membranes specialized in Li+ ion separation.

Microporous polyarylate membranes based on 3D phenolphthalein for molecular sieving.

Thin-film composite (TFC) membranes have gradually replaced some traditional technologies in the extraction, separation, and concentration of high value-added pharmaceutical ingredients due to their controllable microstructure. Nevertheless, devising solvent-stable, scalable TFC membranes with high permeance and efficient molecule selectivity is urgently needed to improve the separation efficiency in the separation process. Here, we propose phenolphthalein, a commercial acid-base indicator, as an economical monomer for optimizing the micropore structure of selective layers with thickness down to 30 nanometers formed by in situ interfacial reactions. Molecular dynamics simulations indicate that the polyarylate membranes prepared using three-dimensional phenolphthalein monomers exhibit tunable microporosity and higher pore interconnectivity. Moreover, the TFC membranes show a high methanol permeance (9.9 ± 0.1 liters per square meter per hour per bar) and small molecular weight cutoff (≈289 daltons) for organic micropollutants in organic solvent systems. The polyarylate membranes exhibit higher mechanical strength (2.4 versus 0.8 gigapascals) compared to the traditional polyamide membrane.

Ultrafast Interfacial Self-Assembly toward Bioderived Polyester COF Membranes with Microstructure Optimization.

The precise manipulation of the microstructure (pore size, free volume distribution, and connectivity of the free-volume elements), thickness, and mechanical characteristics of membranes holds paramount significance in facilitating the effective utilization of self-standing membranes. In this contribution, the synthesis of two innovative ester-linked covalent-organic framework (COF) membranes is first reported, which are generated through the selection of plant-derived ellagic acid and quercetin phenolic monomers in conjunction with terephthaloyl chloride as a building block. The optimization of the microstructure of these two COF membranes is systematically achieved through the application of three different interfacial electric field systems: electric neutrality, positive electricity, and negative electricity. It is observed that the positively charged system facilitates a record increase in the rate of membrane formation, resulting in a denser membrane with a uniform pore size and enhanced flexibility. In addition, a correlation is identified wherein an increase in the alkyl chain length of the surfactants leads to a more uniform pore size and a decrease in the molecular weight cutoff of the COF membrane. The resulting COF membrane exhibits an unprecedented combination of high water permeance, superior sieving capability, robust mechanical strength, chemical robustness for promising membrane-based separation science and technology.

Covalent Organic Network Membranes with Tunable Nanoarchitectonics from Macrocycle Building Blocks for Graded Molecular Sieving.

Traditional piperazine-based polyamide membranes usually suffer from the intrinsic trade-off relationship between selectivity and permeance. The development of macrocycle membranes with customized nanoscale pores is expected to address this challenge. Herein, we introduce 1,4-diazacyclohexane (2N), 1,4,7-triazacyclononane (3N), and 1,4,8,11-tetraazacyclotetradecane (4N) as molecular building blocks to construct the nanoarchitectonics of polyamide membranes prepared from interfacial polymerization (IP). The permeance of covalent organic network membranes follows the trend of 4N-TMC > 3N-TMC > 2N-TMC, while the molecular weight cutoff (MWCO) also follows the same trend of 4N-TMC > 3N-TMC > 2N-TMC, according to their nanopore size of the membranes. The microporosity, orientation, and surface chemistry of covalent organic network membranes can be rationally designed by macrocycle building units. The ordered nanoarchitectonics allows the membranes to attain an excellent performance in graded molecular sieving. Importantly, the novel covalent organic network membranes with tunable nanoarchitectonics prepared from macrocycle building units exhibited high water permeance (32.5 LMH/bar) and retained long-term stability after 100 h of test and bovine serum albumin fouling. These results reveal the enormous potential of 3N-TMC and 4N-TMC membranes in saline textile wastewater treatments and precise molecular sieving.

Flexible Covalent Organic Network with Ordered Honeycomb Nanoarchitecture for Molecular Separations.

Membranes with precisely defined nanostructure are desirable for energy-efficient molecular separations. The emergence of membranes with honeycomb lattice or topological nanopores is of fundamental importance. The tailor-made nanostructure and morphology may have huge potential to resolve the longstanding bottlenecks in membrane science and technology. Herein, inspired by honeycomb architecture, we demonstrate an effective and scalable route based on interfacial polymerization (IP) to generate flexible and ordered covalent organic network (CON) membranes for liquid-phase molecular separations. The aperture size of a CON membrane can be reasonably designed through the strong covalent bond between molecular building blocks. The fabricated CON membrane formed by IP showed an obviously size-dependent sieving of molecules, yielding a stepwise conversion from low rejection to the expected high rejection. Moreover, the CON membrane was also found to have the sieving capability for tetracycline and ciprofloxacin, ascribed to the effect of size exclusion by an ordered single-nanoscale channel (<1 nm). This approach provides a viable strategy for creating target-sized channels from molecular-level design and demonstrates their potential for accurate molecular separations.

A 2D Soft Covalent Organic Framework Membrane Prepared via a Molecular Bridge.

Highly flexible and robust self-standing covalent organic framework (COF) membranes with rapid preparation are important but technically challenging for achieving precise separation. Herein , a novel imine-based 2D soft covalent organic framework (SCOF) membrane with a large area of 226.9 cm2 , via ingeniously selecting an aldehyde flexible linker and a trigonal building block, is reported. The soft 2D covalent organic framework membrane is rapidly formed (≈5 min) based on the sodium dodecyl sulfate (SDS) molecular channel constructed at the water/dichloromethane (DCM) interface, which is the record-fast SCOF membrane formation and 72 times faster than that in the reported literature. MD simulation and DFT calculation elucidate that the dynamic, self-assembled SDS molecular channel facilitates faster and more homogeneous transfer of amine monomers in the bulk, thereby forming a soft 2D self-standing COF membrane with more uniform pores. The formed SCOF membrane exhibits superb sieving capability for small molecules, robustness in strong alkaline (5 mol L-1 NaOH), acid (0.1 mol L-1 HCl), and various organic solutions, and sufficient flexibility with a large curvature of 2000 m-1 for membrane-based separation science and technology.

Decimeter-Scale Atomically Thin Graphene Membranes for Gas-Liquid Separation.

Graphene holds great potential for fabricating ultrathin selective membranes possessing high permeability without compromising selectivity and has attracted intensive interest in developing high-performance separation membranes for desalination, natural gas purification, hemodialysis, distillation, and other gas-liquid separation. However, the scalable and cost-effective synthesis of nanoporous graphene membranes, especially designing a method to produce an appropriate porous polymer substrate, remains very challenging. Here, we report a facile route to fabricate decimeter-scale (∼15 × 10 cm2) nanoporous atomically thin membranes (NATMs) via the direct casting of the porous polymer substrate onto graphene, which was produced by chemical vapor deposition (CVD). After the vapor-induced phase-inversion process under proper experimental conditions (60 °C and 60% humidity), the flexible nanoporous polymer substrate was formed. The resultant skin-free polymer substrate, which had the proper pore size and a uniform spongelike structure, provided enough mechanical support without reducing the permeance of the NATMs. It was demonstrated that after creating nanopores by the O2 plasma treatment, the NATMs were salt-resistant and simultaneously showed 3-5 times higher gas (CO2) permeance than the state-of-the-art commercial polymeric membranes. Therefore, our work provides guidance for the technological developments of graphene-based membranes and bridges the gap between the laboratory-scale "proof-of-concept" and the practical applications of NATMs in the industry.

Functions of Ionic Liquids in Preparing Membranes for Liquid Separations: A Review.

Membranes are widely used for liquid separations such as removing solute components from solvents or liquid/liquid separations. Due to negligible vapor pressure, adjustable physical properties, and thermal stability, the application of ionic liquids (ILs) has been extended to fabricating a myriad of membranes for liquid separations. A comprehensive overview of the recent developments in ILs in fabricating membranes for liquid separations is highlighted in this review article. Four major functions of ILs are discussed in detail, including their usage as (i) raw membrane materials, (ii) physical additives, (iii) chemical modifiers, and (iv) solvents. Meanwhile, the applications of IL assisted membranes are discussed, highlighting the issues, challenges, and future perspectives of these IL assisted membranes in liquid separations.

Fabrication of Bioinspired Gallic Acid-Grafted Chitosan/Polysulfone Composite Membranes for Dye Removal via Nanofiltration.

In this work, we have developed a novel and facile method to prepare gallic acid-grafted chitosan/polysulfone (PS) composite membranes for dye removal from aqueous solutions. First, the gallic acid was grafted onto the eco-friendly chitosan through a free-radical grafting copolymerization reaction. Second, the gallic acid-grafted chitosan conjugates were codeposited onto the top surface of PS substrates by electrostatic interactions in order to transform the ultrafiltration membrane to the thin and defect-free nanofiltration membrane. The morphology and chemical composition of the as-prepared composite membranes were fully characterized by various spectroscopy and microscopy techniques. Moreover, after the optimization of preparation parameters, the obtained membrane displayed a high rejection of 97.2% for Congo red with a high permeance of 14.0 L h-1 m-2 bar-1. Furthermore, the composite membranes also exhibited good rejections for other dyes with different molecular weights such as Evan blue (97.3%), Acid red 94 (97.6%), and Alcian blue 8GX (98%) on the basis of size exclusion, accompanied with good permeance of 12.9, 11.9, and 10.9 L h-1 m-2 bar-1, respectively, which shows potential for scale-up industrial applications.

Corrosion Engineering To Synthesize Ultrasmall and Monodisperse Alloy Nanoparticles Stabilized in Ultrathin Cobalt (Oxy)hydroxide for Enhanced Electrocatalysis.

Two-dimensional (2D) nanomaterials decorated with ultrasmall and well-alloyed bimetallic nanoparticles (NPs) have many important applications. Developing a facile and scalable 2D material/hybrid synthesis strategy is still a big challenge. Herein, a top-down corrosion strategy is developed to prepare ultrathin cobalt (oxy)hydroxide nanosheets decorated with ultrasmall (∼1.6 nm) alloy NPs. The formation of ultrathin (oxy)hydroxide nanosheets has a restrain effect to prevent the growth of small NPs into bigger ones. Thanks to the ultrathin 2D nature and strong electronic interaction between Co(OH)2 and alloy NPs, the Pt-based binary alloy NPs are greatly stabilized by the Co(OH)2 nanosheets and the hybrids exhibit much enhanced electrocatalytic performance for water splitting. Especially, the mass activities of the PtPd- and PtCu-decorated samples for hydrogen evolution are ∼8 times that of Pt/C. When used as both cathode and anode electrocatalysts to split water, the hybrid nanosheets outperform the commercial Pt/C-RuO2 combination. At 10 mA cm-2, the needed potential is only 1.53 V. This work provides us a highly controllable and scalable means to produce clean 2D nanomaterials decorated with a series of alloy NPs such as PtPd, PtCu, AuNi, and so forth.