Metal–Organic Framework Crystal–Glass Composite Membranes with Preferential Permeation of Ethane

Metal–organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal–glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C₂H₆ permeance of 41 569 gas permeation units (GPU) and a C₂H₆/C₂H₄ selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C₂H₆ and promotes C₂H₆ transport in the membrane, and thus the GCG membrane exhibits ultrahigh C₂H₆ permeance and good C₂H₆/C₂H₄ selectivity.     

Ultramicroporous Covalent Organic Framework Nanosheets with Functionality Pair for Membrane C2H2/C2H4 Separation

Gas separation efficiency of covalent organic framework (COF) membrane can be greatly elevated through precise functionalization. A pair-functionalized COF membrane of 1,3,5-triformylphloroglucinol (TP) and isoquinoline-5,8-diamine (IQD) monomers in two and three nodes is designed and synthesized. TP-IQD is crystallized in a two-dimensional structure with a pore size of 6.5 Å and a surface area of 289 m² g⁻¹. This COF possesses N−O paired groups which cooperatively interact with C₂H₂ instead of C₂H₄. TP-IQD nanosheets of ≈10 μm in width and ≈4 nm in thickness are prepared by mechanical exfoliation; they are further processed with 6FDA-ODA polymer into a hybrid membrane. High porosity and functionality pair of TP-IQD offer the membrane with significantly increased C₂H₂ permeability and C₂H₂/C₂H₄ selectivity which are 160 % and 430 % higher of pure 6FDA-ODA. The boosted performance demonstrates high efficiency of the pair-functionality strategy for the synthesis of separation-led COFs.     

Crystallizing Self-Standing Covalent Organic Framework Membranes for Ultrafast Proton Transport in Flow Batteries

Covalent organic frameworks (COFs) display great potential to be assembled into proton conductive membranes for their uniform and controllable pore structure, yet constructing self-standing COF membrane with high crystallinity to fully exploit their ordered crystalline channels for efficient ionic conduction remains a great challenge. Here, a macromolecular-mediated crystallization strategy is designed to manipulate the crystallization of self-standing COF membrane, where the −SO₃H groups in introduced sulfonated macromolecule chains function as the sites to interact with the precursors of COF and thus offer long-range ordered template for membrane crystallization. The optimized self-standing COF membrane composed of highly-ordered nanopores exhibits high proton conductivity (75 mS cm⁻¹ at 100 % relative humidity and 20 °C) and excellent flow battery performance, outperforming Nafion 212 and reported membranes. Meanwhile, the long-term run of membrane is achieved with the help of the anchoring effect of flexible macromolecule chains. Our work provides inspiration to design self-standing COF membranes with ordered channels for permselective application.     

Ultrafast Semi-Solid Processing of Highly Durable ZIF-8 Membranes for Propylene/Propane Separation

ZIF-8 membranes have emerged as the most promising candidate for propylene/propane (C₃H₆/C₃H₈) separation through its precise molecular sieving characteristics. The poor reproducibility and durability, and high cost, thus far hinder the scalable synthesis and industrial application of ZIF-8 membranes. Herein, we report a semi-solid process featuring ultrafast and high-yield synthesis, and outstanding scalability for reproducible fabrication of ZIF-8 membranes. The membranes show excellent C₃H₆/C₃H₈ separation performance in a wide temperature and pressure range, and remarkable stability over 6 months. The ZIF-8 membrane features dimethylacetamide entrapped ZIF-8 crystals retaining the same diffusion characteristics but offering enhanced adsorptive selectivity for C₃H₆/C₃H₈. The ZIF-8 membrane was prepared on a commercial flat-sheet ceramic substrate. A prototypical plate-and-frame membrane module with an effective membrane area of about 300 cm² was used for efficient C₃H₆/C₃H₈ separation.     

Electrochemical Interfacial Polymerization toward Ultrathin COF Membranes for Brine Desalination

Ultrathin covalent organic framework (COF) membranes are urgently demanded in molecular/ionic separations. Herein, we reported an electrochemical interfacial polymerization strategy to fabricate ultrathin COF membranes with thickness of 85 nm, by actively manipulate self-healing effect and self-inhibiting effect. The resulting COF membrane exhibited superior performance in brine desalination with the permeation flux of 92 kg m⁻² h⁻¹ and the rejection of 99.96 %. Our electrochemical interfacial polymerization strategy enriches the fabrication approach of COF membranes and facilitates the rational design of ultrathin membranes.     

Uniformly Distributed Mixed Matrix Membranes via a Solution Processable Strategy for Propylene/Propane Separation

Aggregation of filler particles during the formation of mixed matrix membranes is difficult to avoid when filler loadings exceed a 10–15 wt %. Such agglomeration usually leads to poor membrane performance. In this work, using a ZIF-67 metal–organic framework (MOF) as filler along with surface modification of Ag₄tz₄ to improve processability and selective olefin adsorption, we demonstrate that highly loaded with a very low agglomeration degree membranes can be synthesized displaying unmatched separation selectivity (39) for C₃H₆/C₃H₈ mixtures and high permeability rates (99 Barrer), far surpassing previous reports in the literature. Through molecular dynamics simulation, the enhanced compatibility between ZIF-67 and polymer matrix with adding Ag₄tz₄ was proven and the tendency in gas permeability and C₃H₆ selectivity in the mixed matrix membranes (MMMs) were well explained. More importantly, the membrane showed a wide range of pressure and temperature resistance, together with remarkable long-term stability (>900 h). The modification method might help solve interface issues in MMMs and can be extended to the fabrication of other fillers to achieve high performance MMMs for gas separation.     

Stable Immobilization of Nickel Ions on Covalent Organic Frameworks for Panchromatic Photocatalytic Hydrogen Evolution

Post-coordination design on covalent organic frameworks (COFs) is an efficient strategy for elevating the photocatalytic activity of organic moiety. However, the rigid skeletons and densely layered stacking of two-dimensional (2D) COFs cannot be flexibly adapted for specific conformations of metal complexes, thereby impairing the metal-COF cooperation. Here, we adopt a solvothermal method to immobilize nickel(II) ions into a 2,2′-bipyridine-containing 2D COF, forming a stable coordination motif. Such the complex remarkably enhances the photocatalytic performance, giving an optimized H₂ evolution rate of as high as 51 300 μmol h⁻¹ g⁻¹, 2.5 times higher than the pristine COF. The evolved hydrogen gas can also be detected upon 700-nm light irradiation, while its analog synthesized by the traditional coordination method is photo-catalytically inert. This work provides a strategy for optimizing the metal-COF coordination system and strengthening a synergy for electronic regulation in photocatalysis.     

Magnetoresistance in Organic Spin Valves Based on Acid-Exfoliated 2D Covalent Organic Frameworks Thin Films

Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous materials, have made significant progress in their application to optoelectronic devices such as field-effect transistors, memristors, and photodetectors. However, the insoluble features of microcrystalline two-dimensional (2D) COF powders limit development of their thin film devices. Additionally, the exploration of spin transport properties in this category of π-conjugated skeleton materials remains vacant thus far. Herein, an imine-linked 2D Py-Np COF nanocrystalline powder was synthesized by Schiff base condensation of 4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayl)tetraaniline and naphthalene-2,6-dicarbaldehyde. Then, we prepared a large-scale free-standing Py-Np COF film via a top-down strategy of chemically assisted acid exfoliation. Moreover, high-quality COF films acted as active layers were transferred onto ferromagnetic La_0.67Sr_0.33MnO₃ (LSMO) electrodes for the first attempt to fabricate organic spin valves (OSVs) based on 2D COF materials. This COF-based OSV device with a configuration of LSMO/Py-Np COF/Co/Au demonstrated a remarkable magnetoresistance (MR) value up to −26.5 % at 30 K. Meanwhile, the MR behavior of the COF-based OSVs exhibited a highly temperature dependence and operational stability. This work highlights the enormous application prospects of 2D COFs in organic spintronics and provides a promising approach for developing electronic and spintronic devices based on acid-exfoliated COF thin films.     

Pore Geometry and Surface Engineering of Covalent Organic Frameworks for Anhydrous Proton Conduction

Developing new materials for anhydrous proton conduction under high-temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as −C=N−, −OH, −N=N− and −CF₃) to improve the utilization efficiency and host–guest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H₃PO₄, COFs can realize a proton conductivity of 2.33×10⁻² S cm⁻¹ under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80–160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high-temperature proton exchange membranes.     

Photo-Driven Quasi-Topological Transformation Exposing Highly Active Nitrogen Cation Sites for Enhanced Photocatalytic H2O2 Production

Herein, the exposure of highly-active nitrogen cation sites has been accomplished by photo-driven quasi-topological transformation of a 1,10-phenanthroline-5,6-dione-based covalent organic framework (COF), which contributes to hydrogen peroxide (H₂O₂) synthesis during the 2-electron O₂ photoreduction. The exposed nitrogen cation sites with photo-enhanced Lewis acidity not only act as the electron-transfer motor to adjust the inherent charge distribution, powering continuous and stable charge separation, and broadening visible-light adsorption, but also providing a large number of active sites for O₂ adsorption. The optimal catalyst shows a high H₂O₂ production rate of 11965 μmol g⁻¹ h⁻¹ under visible light irradiation and a remarkable apparent quantum yield of 12.9 % at 400 nm, better than most of the previously reported COF photocatalysts. This work provides new insights for designing photo-switchable nitrogen cation sites as catalytic centers toward efficient solar to chemical energy conversion.     

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 μmol g⁻¹ h⁻¹), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.     

Hierarchical Microtubular Covalent Organic Frameworks Achieved by COF-to-COF Transformation

Pore environment and aggregated structure play a vital role in determining the properties of porous materials, especially regarding the mass transfer. Reticular chemistry imparts covalent organic frameworks (COFs) with well-aligned micro/mesopores, yet constructing hierarchical architectures remains a great challenge. Herein, we reported a COF-to-COF transformation methodology to prepare microtubular COFs. In this process, the C₃-symmetric guanidine units decomposed into C₂-symmetric hydrazine units, leading to the crystal transformation of COFs. Moreover, the aggregated structure and conversion degree varied with the reaction time, where the hollow tubular aggregates composed of mixed COF crystals could be obtained. Such hierarchical architecture leads to enhanced mass transfer properties, as proved by the adsorption measurement and chemical catalytic reactions. This self-template strategy was successfully applied to another four COFs with different building units.     

Tuning the Stacking Modes of Ultrathin Two-Dimensional Metal–Organic Framework Nanosheet Membranes for Highly Efficient Hydrogen Separation

Two-dimensional (2D) metal–organic framework (MOF) membranes are considered potential gas separation membranes of the next generation due to their structural diversity and geometrical functionality. However, achieving a rational structure design for a 2D MOF membrane and understanding the impact of MOF nanosheet stacking modes on membrane separation performance remain challenging tasks. Here, we report a novel kind of 2D MOF membrane based on [Cu₂Br(IN)₂]_n (IN=isonicotinato) nanosheets and propose that synergetic stacking modes of nanosheets have a significant influence on gas separation performance. The stacking of the 2D MOF nanosheets is controlled by solvent droplet dynamic behaviors at different temperatures of drop coating. Our 2D MOF nanosheet membranes exhibit high gas separation performances for H₂/CH₄ (selectivity >290 with H₂ permeance >520 GPU) and H₂/CO₂ (selectivity >190 with H₂ permeance >590 GPU) surpassing the Robeson upper bounds, paving a potential way for eco-friendly H₂ separation.     

Tuning the Adsorption Selectivity of ZIF-8 by Amorphization

Amorphous metal–organic frameworks (a_mMOFs) with a partially collapsed structure are a new category of porous hybrid materials. Here, solid-state amorphization of ZIF-8 was achieved by mechanical compression at 0.75 GPa. The compression-induced amorphous ZIF-8 (a_mZIF-8) had a collapsed structure, but retained partial porosity. Benefiting from the deformed channel, the resultant a_mZIF-8 exhibited preferable adsorption of C₃H₆, resulting in higher thermodynamic adsorption selectivity of C₃H₆/C₃H₈ (6.72) than the crystalline counterparts (1.06). Further, a_mZIF-8 achieved complete separation of an equimolar C₃H₆/C₃H₈ mixture with the first breakthrough of C₃H₈. a_mZIF-8 also displayed an enhancement in CO₂/N₂ and CO₂/CH₄ adsorption selectivities. More importantly, a self-standing a_mZIF-8 membrane with boundary-free microstructure was constructed for the first time, and exhibited separation potential for H₂/CH₄, CO₂/N₂, CO₂/CH₄, and C₃H₆/C₃H₈ with ideal selectivities of 14.79, 12.83, 16.23, and 2.67, respectively.     

Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene

Developing hydrogen-bonded organic frameworks (HOFs) that combine functional sites, size control, and storage capability for targeting gas molecule capture is a novel and challenging venture. However, there is a lack of effective strategies to tune the hydrogen-bonded network to achieve high-performance HOFs. Here, a series of HOFs termed as HOF-ZSTU-M (M=1, 2, and 3) with different pore structures are obtained by introducing structure-directing agents (SDAs) into the hydrogen-bonding network of tetrakis (4-carboxyphenyl) porphyrin (TCPP). These HOFs have distinct space configurations with pore channels ranging from discrete to continuous multi-dimensional. Single-crystal X-ray diffraction (SCXRD) analysis reveals a rare diversity of hydrogen-bonding models dominated by SDAs. HOF-ZSTU-2 , which forms a strong layered hydrogen-bonding network with ammonium (NH₄⁺) through multiple carboxyl groups, has a suitable 1D “pearl-chain” channel for the selective capture of propylene (C₃H₆). At 298 K and 1 bar, the C₃H₆ storage density of HOF-ZSTU-2 reaches 0.6 kg L⁻¹, representing one of the best C₃H₆ storage materials, while offering a propylene/propane (C₃H₆/C₃H₈) selectivity of 12.2. Theoretical calculations and in situ SCXRD provide a detailed analysis of the binding strength of C₃H₆ at different locations in the pearl-chain channel. Dynamic breakthrough tests confirm that HOF-ZSTU-2 can effectively separate C₃H₆ from multi-mixtures.     

Solar Light Driven H2O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

A chemically stable 2D microporous COF ( PMCR-1 ) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term stable photocatalytic H₂O₂ production rate (60 h) from pure and sea water under visible light. The H₂O₂ production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π–π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H₂O₂ formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well-defined micropores of PMCR-1 enable size-selective photocatalytic oxidation.     

Inverse CO2/C2H2 Separation with MFU-4 and Selectivity Reversal via Postsynthetic Ligand Exchange

Although many porous materials, including metal–organic frameworks (MOFs), have been reported to selectively adsorb C₂H₂ in C₂H₂/CO₂ separation processes, CO₂-selective sorbents are much less common. Here, we report the remarkable performance of MFU-4 (Zn₅Cl₄(bbta)₃, bbta=benzo-1,2,4,5-bistriazolate) toward inverse CO₂/C₂H₂ separation. The MOF facilitates kinetic separation of CO₂ from C₂H₂, enabling the generation of high purity C₂H₂ (>98 %) with good productivity in dynamic breakthrough experiments. Adsorption kinetics measurements and computational studies show C₂H₂ is excluded from MFU-4 by narrow pore windows formed by Zn−Cl groups. Postsynthetic F⁻/Cl⁻ ligand exchange was used to synthesize an analogue ( MFU-4-F ) with expanded pore apertures, resulting in equilibrium C₂H₂/CO₂ separation with reversed selectivity compared to MFU-4 . MFU-4-F also exhibits a remarkably high C₂H₂ adsorption capacity (6.7 mmol g⁻¹), allowing fuel grade C₂H₂ (98 % purity) to be harvested from C₂H₂/CO₂ mixtures by room temperature desorption.     

A Covalent Organic Framework as a Long-life and High-Rate Anode Suitable for Both Aqueous Acidic and Alkaline Batteries

Aqueous rechargeable batteries are prospective candidates for large-scale grid energy storage. However, traditional anode materials applied lack acid-alkali co-tolerance. Herein, we report a covalent organic framework containing pyrazine (C=N) and phenylimino (−NH−) groups (HPP-COF) as a long-cycle and high-rate anode for both acidic and alkaline batteries. The HPP-COF′s robust covalent linkage and the hydrogen bond network between −NH− and water molecules collectively improve the acid-alkaline co-tolerance. More importantly, the hydrogen bond network promotes the rapid transport of H⁺/OH⁻ by the Grotthuss mechanism. As a result, the HPP-COF delivers a superior capacity and cycle stability (66.6 mAh g⁻¹@ 30 A g⁻¹, over 40000 cycles in 1 M H₂SO₄ electrolyte; 91.7 mAh g⁻¹@ 100 A g⁻¹, over 30000 cycles @ 30 A g⁻¹ in 1 M NaOH electrolyte). The work opens a new direction for the structural design and application of COF materials in acidic and alkaline batteries.     

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2H2/C2H4 and C2H2/CO2 Separations in Metal–Organic Frameworks

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal–organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra-microporous MOFs (SNNU-98-M, M=Mn, Co, Ni, Zn). SNNU-98 exhibit high volumetric C₂H₂ uptake capacity under low and ambient pressures (175.3 cm³ cm⁻³ @ 0.1 bar, 222.9 cm³ cm⁻³ @ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C₂H₂/C₂H₄, 22.7 for C₂H₂/CO₂). Remarkably, SNNU-98-Mn can efficiently separate C₂H₂ from C₂H₂/CO₂ and C₂H₂/C₂H₄ mixtures with a benchmark C₂H₂/C₂H₄ (1/99) breakthrough time of 2325 min g⁻¹, and produce 99.9999 % C₂H₄ with a productivity up to 64.6 mmol g⁻¹, surpassing values of reported MOF adsorbents.     

Porous Covalent Organic Framework Based Hydrogen-Bond Nanotrap for the Precise Recognition and Separation of Gold

Utilizing weak interactions to effectively recover and separate precious metals in solution is of great importance but the practice remains a challenge. Herein, we report a novel strategy to achieve precise recognition and separation of gold by regulating the hydrogen-bond (H-bond) nanotrap within the pore of covalent organic frameworks (COFs). It is found that both COF-HNU25 and COF-HNU26 can efficiently capture Au^III with fast kinetics, high selectivity, and uptake capacity. In particular, the COF-HNU25 with the high density of H-bond nanotraps exhibits an excellent gold uptake capacity of 1725 mg g⁻¹, which is significantly higher than that (219 mg g⁻¹) of its isostructural COF (COF-42) without H-bond nanostrap in the pores. Importantly, the uptake capacity is strongly correlated to the number of H-bonds between phenolic OH in the COF and [AuCl₄]⁻ in water, and multiple H-bond interactions are the key driving force for the excellent gold recovery and reusability of the adsorbent.