Two‐Dimensional Metal–Organic Framework Nanosheets for Membrane‐Based Gas Separation

Metal–organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass‐transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet‐based membranes remain as great challenges. A modified soft‐physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub‐10 nm‐thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H₂/CO₂ separation performance, with a separation factor of up to 166 and H₂ permeance of up to 8×10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at elevated testing temperatures owing to a well‐defined size‐exclusion effect. This nanosheet‐based membrane holds great promise as the next generation of ultrapermeable gas separation membrane.     

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.     

MIL-101(Cr) Microporous Nanocrystals Intercalating Graphene Oxide Membrane for Efficient Hydrogen Purification

Graphene oxide (GO) is a promising two-dimensional building block for fabricating high-performance gas separation membranes. Whereas the tortuous transport pathway may increase the transport distance and lead to a low gas permeation rate, introducing spacers into GO laminates is an effective strategy to enlarge the interlayer channel for enhanced gas permeance. Herein, we propose to intercalate CO₂-philic MIL-101(Cr) metal-organic framework nanocrystals into the GO laminates to construct a 2D/3D hybrid structure for gas separation. The interlayer channels were partially opened up to accelerate gas permeation. Meanwhile, the intrinsic pores of MIL-101 provided additional transport pathways, and the affinity of MIL-101 to CO₂ molecules resulted in higher H₂/CO₂ diffusion selectivity, leading to a simultaneous enhancement in gas permeance and separation selectivity. The MIL-101(Cr)/GO membrane with optimal structures exhibited outstanding and stable mixed-gas separation performance with H₂ permeance of 67.5 GPU and H₂/CO₂ selectivity of 30.3 during the 120-h continuous test, demonstrating its potential in H₂ purification application.     

Melamine-Doped Covalent Organic Framework Membranes for Enhanced Hydrogen Purification

Covalent organic frameworks (COFs) are promising materials for membrane separation thanks to their adjustable topological structures and surface properties of nanopores. Herein, a melamine (Me)-doped COF membrane was fabricated by chemically doping the melamine monomer into TpPa COF, which is formed by the condensation reaction between the 1,3,5-triformylphloroglucinol (Tp) and p-phenylenediamine (Pa) monomers via interfacial polymerization. The introduction of melamine monomer allows altering both the pore structure and pore surface of the TpPa COF membrane, leading to enhanced hydrogen purification performance. Specifically, the separation factor of H₂/CO₂ gas mixture by using the melamine doped TpPa COF (TpPaMe COF) membrane reaches 12.7, with a hydrogen permeance of 727 GPU, in sharp contrast to the relatively low separation factor and gas permeance of 7.5 and 618 GPU of the undoped TpPa membrane. Besides, the TpPaMe COF membrane shows good running stability, with H₂/CO₂ separation performance well surpasses the Robeson 2008 upper bound.     

Polymer Composite Membrane with Penetrating ZIF‐7 Sheets Displays High Hydrogen Permselectivity

Oriented and penetrating molecular sieving membranes display enhanced separation performance. A polyimide (PI) solution containing highly dispersed ZIF‐7(III) sheets in CHCl₃ was deposited on a glass side and subjected to flat‐scraping with a membrane fabricator. In this way we developed a novel oriented and penetrating ZIF‐7@PI mixed matrix membrane (MMM) with 50 wt. % ZIF‐7 loading. Because the height of the ZIF‐7 sheets (5 μm) is higher than the film thickness, every ZIF‐7 sheet penetrates both surfaces of the polyimide film. Since the ZIF‐7 channels are the dominant pathway for gas permeation, the ZIF‐7@PI MMM displays a high molecular sieve performance for the separation of H₂ (0.29 nm) from larger gas molecules. At 100 °C and 2 bar, the mixture separation factors of H₂/CO₂ and H₂/CH₄ are 91.5 and 128.4, with a high H₂ permeance of about 3.0×10^?7 mol m^?2 s^?1 Pa^?1, which is promising for hydrogen separation by molecular sieving.     

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.     

Preparation and separation properties of oxalylurea‐bridged silica membranes

Two new bridged alkoxysilanes, bis(triethoxysilylalkyl)‐N,N′‐oxalylureas (alkyl = methyl or n‐propyl), bearing a highly rigid and polar oxalylurea unit in the bridges, were employed as precursors of bridged silica membranes. The gas and water separation performance of the membranes prepared from the precursors using the sol–gel process was investigated. Interestingly, the membrane properties depended on the alkyl chain length. The membrane containing methylene units (alkyl = methyl) was porous and rather hydrophilic but the other with longer propylene units (alkyl = n‐propyl) was non‐porous and more hydrophobic. High H₂/SF₆ gas permeance ratios of 3100 and 1700, and NaCl rejections of 89 and 85% for 2000 ppm aqueous NaCl were obtained using the membranes containing methyl and n‐propyl, respectively. The membrane with alkyl = methyl also showed a high CO₂/N₂ permeance ratio of 20.6 at 50°C. These results indicate the potential applications of the membranes as gas and water separation materials. Copyright © 2015 John Wiley & Sons, Ltd.     

Structure Regulation of MOF Nanosheet Membrane for Accurate H2/CO2 Separation

High-purity H₂ production accompanied with a precise decarbonization opens an avenue to approach a carbon-neutral society. Metal–organic framework nanosheet membranes provide great opportunities for an accurate and fast H₂/CO₂ separation, CO₂ leakage through the membrane interlayer galleries decided the ultimate separation accuracy. Here we introduce low dose amino side groups into the Zn₂(benzimidazolate)₄ conformation. Physisorbed CO₂ served as interlayer linkers, gently regulated and stabilized the interlayer spacing. These evoked a synergistic effect of CO₂ adsorption-assisted molecular sieving and steric hinderance, whilst exquisitely preserving apertures for high-speed H₂ transport. The optimized amino membranes set a new record for ultrathin nanosheet membranes in H₂/CO₂ separation (mixture separation factor: 1158, H₂ permeance: 1417 gas permeation unit). This strategy provides an effective way to customize ultrathin nanosheet membranes with desirable molecular sieving ability.     

Fabrication of Crystalline Microporous Membrane from 2D MOF Nanosheets for Gas Separation

Metal‐organic frameworks (MOFs)‐based membranes have shown great potentials as applications in gas separation. In this work, a uniform membrane based on 2D MOF Ni₃(HITP)₂ (HITP=2,3,6,7,10,11‐hexaaminotriphenylene) was fabricated on ordered macroporous AAO via the filtration method. To fabricate the membrane, we obtained the Ni₃(HITP)₂ nanosheets as building blocks via a soft‐physical exfoliation method successfully that were confirmed by AFM and TEM. We also studied the H₂, CO₂ and N₂ adsorption isotherms of Ni₃(HITP)₂ powder at room temperature, which shows Ni₃(HITP)₂ has high heats of adsorption for CO₂ and high selectivity of CO₂ over N₂. Gas permeation tests indicate that the Ni₃(HITP)₂ membrane shows high permeance and selectivity of CO₂ over N₂, as well as good selectivity of H₂ over N₂. The ideal separation factors of CO₂/N₂ and H₂/N₂ from sing‐gas permeances are 13.6 and 7.8 respectively, with CO₂ permeance of 3.15×10^?6 mol?m^?2?s^?1?Pa^?1. The membrane also showed good stability, durability and reproducibility, which are of potential interest for practical applications in the CO₂ separations.     

A Uniformly Oriented MFI Membrane for Improved CO2 Separation

Membrane separation of CO₂ from natural gas, biogas, synthesis gas, and flu gas is a simple and energy‐efficient alternative to other separation techniques. But results for CO₂‐selective permeance have always been achieved by randomly oriented and thick zeolite membranes. Thin, oriented membranes have great potential to realize high‐flux and high‐selectivity separation of mixtures at low energy cost. We now report a facile method for preparing silica MFI membranes in fluoride media on a graded alumina support. In the resulting membrane straight channels are uniformly vertically aligned and the membrane has a thickness of 0.5 μm. The membrane showed a separation selectivity of 109 for CO₂/H₂ mixtures and a CO₂ permeance of 51×10^?7 mol m^?2 s^?1 Pa^?1 at ?35 °C, making it promising for practical CO₂ separation from mixtures.     

Preparation of high-permeance MFI membrane with the modified secondary growth method on the macroporous α-alumina tubular support

MFI membrane with high permeance was successfully synthesized on the macroporous (pore size of 3–4 μm) α-Al₂O₃ tubular support with a novel modified secondary growth method. Before the crystallization, the seeded support was wrapped with Teflon tape in order to focalize the growth of crystals in the region of seed layer. The as-synthesized membrane was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and single-gas permeation testing. The results indicated that the as-synthesized membrane had a thickness of 6–8 μm similar to the thickness of the seed layer and exhibited high gas permeance. At room temperature, the permeance of H₂ and the ideal separation factor of H₂/SF₆ reached 1.64 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 71, respectively. The permeance of single-gas increased with the increasing of temperature. The ideal separation factors of H₂/i-C₄H₁₀ and H₂/SF₆ decreased with the increasing of temperature from 298 to 473 K. At 473 K, the ideal separation factors of H₂/i-C₄H₁₀ and H₂/SF₆ were 12.16 and 11.08, which were still higher than their Knudsen ratios of 5.39 and 8.54, respectively.     

Boron Nitride Membranes with a Distinct Nanoconfinement Effect for Efficient Ethylene/Ethane Separation

A BN membrane with a distinct nanoconfinement effect toward efficient ethylene/ethane separation is presented. The horizontal and inclined self‐assembly of 2D BN nanosheets endow the BN membrane with abundant percolating nanochannels, and these nanochannels are further decorated by reactive ionic liquids (RILs) to tailor their sizes as well as to achieve nanoconfinement effect. The noncovalent interactions between RIL and BN nanosheets favor the ordered alignment of the cations and anions of RIL within BN nanochannels, which contributes to a fast and selective ethylene transport. The resultant membranes exhibit an unprecedented separation performance with superhigh C₂H₄ permeance of 138 GPU and C₂H₄/C₂H₆ selectivity of 128 as well as remarkably improved long‐term stability for 180 h, outperforming reported state‐of‐the‐art membranes.     

Continuous Porous Aromatic Framework Membranes with Modifiable Sites for Optimized Gas Separation

Continuous microporous membranes are widely studied for gas separation, due to their low energy premium and strong molecular specificity. Porous aromatic frameworks (PAFs) with their exceptional stability and structural flexibility are suited to a wide range of separations. Main-stream PAF-based membranes are usually prepared with polymeric matrices, but their discrete entities and boundary defects weaken their selectivity and permeability. The synthesis of continuous PAF membranes is still a major challenge because PAFs are insoluble. Herein, we successfully synthesized a continuous PAF membrane for gas separation. Both pore size and chemistry of the PAF membrane were modified by ion-exchange, resulting in good selectivity and permeance for the gas mixtures H₂/N₂ and CO₂/N₂. The membrane with Br^? as a counter ion in the framework exhibited a H₂/N₂ selectivity of 72.7 with a H₂ permeance of 51844 gas permeation units (GPU). When the counter ions were replaced by BF₄^?, the membrane showed a CO₂ permeance of 23058 GPU, and an optimized CO₂/N₂ selectivity of 60.0. Our results show that continuous PAF membranes with modifiable pores are promising for various gas separation situations.     

Modular Customization and Regulation of Metal–Organic Frameworks for Efficient Membrane Separations

Metal–organic frameworks (MOFs) are considered ideal membrane candidates for energy-efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long-standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect-free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H₂/CO₂ separation performance sequence is achieved (separation factor of 1656–5.4, H₂ permeance of 964–2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non-destructive modification separately towards the MOF module. This work establishes a universal full-chain demonstration for membrane fabrication-separation validation-microstructure modification and opens an avenue for exclusive customization of membranes for important separations.     

Cross‐Linking between Sodalite Nanoparticles and Graphene Oxide in Composite Membranes to Trigger High Gas Permeance,Selectivity, and Stability in Hydrogen Separation

Thin membranes (900 nm) were prepared by direct transformation of infiltrated amorphous precursor nanoparticles, impregnated in a graphene oxide (GO) matrix, into hydroxy sodalite (SOD) nanocrystals. The amorphous precursor particles rich in silanols (Si?OH) enhanced the interactions with the GO, thus leading to the formation of highly adhesive and stable SOD/GO membranes via strong bonding. The cross‐linking of SOD nanoparticles with the GO in the membranes promoted both the high gas permeance and enhanced selectivity towards H₂ from a mixture containing CO₂ and H₂O. The SOD/GO membranes are moisture resistance and exhibit steady separation performance (H₂ permeance of about 4900 GPU and H₂/CO₂ selectivity of 56, with no degradation in performance during the test of 50 h) at high temperature (200 °C) under water vapor (4 mol %).     

Graphene Oxide Membranes with Heterogeneous Nanodomains for Efficient CO2 Separations

Achieving high membrane performance in terms of gas permeance and carbon dioxide selectivity is an important target in carbon capture. Aiming to manipulate the channel affinity towards CO₂ to implement efficient separations, gas separation membranes containing CO₂‐philic and non‐CO₂‐philic nanodomains in the interlayer channels of graphene oxide (GO) were formed by intercalating poly(ethylene glycol) diamines (PEGDA). PEGDA reacts with epoxy groups on the GO surface, constructing CO₂‐philic nanodomains and rendering a high sorption capacity, whereas unreacted GO surfaces give non‐CO₂‐philic nanodomains, rendering low‐friction diffusion. Owing to the orderly stacking of nanochannels through cross‐linking and the heterogeneous nanodomains with moderate CO₂ affinity, a GO‐PEGDA500 membrane exhibits a high CO₂ permeance of 175.5 GPU and a CO₂/CH₄ selectivity of 69.5, which is the highest performance reported for dry‐state GO‐stacking membranes.     

Metal–Organic Framework (MOF) Template Based Efficient Pt/ZrO2@C Catalysts for Selective Catalytic Reduction of H2 Below 90 °C

Selective catalytic reduction (SCR) of NO_x with H₂ as a reductant is the most promising denitration technology at low temperature. Achieving the conversion of NO_x into N₂ at ambient temperature not only prolongs the service life of the catalyst, but also provides more freedom for the arrangement of denitration units throughout the flue gas treatment equipment. However, the development of highly efficient, stable, and environmentally benign supported platinum‐based catalysts for H₂‐SCR at ambient temperature is still a major challenge. Herein, a 0.5 wt % Pt/ZrO₂@C catalyst, which was composed of carbon‐coated octahedral ZrO₂ with highly dispersed Pt particles, was prepared by using a new stabilization strategy based on UiO‐66‐NH₂ (a zirconium metal–organic framework) as a template. The catalytic performance of this Pt/ZrO₂@C in H₂‐SCR was tested and confirmed to achieve near 100 % NO_x conversion at 90 °C. Also, 70 % N₂ selectivity of the catalyst was achieved. The morphology, structure, and porous properties of the as‐synthesized nanocomposites were characterized by using data obtained from field‐emission SEM, TEM, XRD, Raman spectroscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and N₂ adsorption–desorption isotherms. The results show that residual carbon formed by pyrolysis treatment is coated on octahedral ZrO₂, and effectively prevents the agglomeration of platinum particles on the surface.     

Pebax‐Based Membrane Filled with Two‐Dimensional Mxene Nanosheets for Efficient CO2 Capture

Mixed matrix membranes (MMMs) made from inorganic fillers and polymers is a kind of promising candidate for gas separation. In this work, two‐dimensional MXene nanosheets were synthesized and incorporated into a polyether‐polyamide block copolymer (Pebax) matrix to fabricate MMM for CO₂ capture. The physicochemical properties of MXene nanosheets and MXene/Pebax membranes were studied systematically. The introduction of MXene nanosheets provided additional molecular transport channels and meanwhile enhanced the CO₂ adsorption capacity, thereby enhancing both the CO₂ peremance and CO₂/N₂ selectivity of Pebax membrane. The optimized MXene/Pebax membrane with a MXene loading of 0.15 wt % displayed a high separation performance with a CO₂ permeance of 21.6 GPU and a CO₂/N₂ selectivity of 72.5, showing potential application in CO₂ capture.     

Gas adsorption in Mg‐porphyrin‐based porous organic frameworks: A computational simulation by first‐principles derived force field

A novel type of porous organic frameworks, based on Mg‐porphyrin, with diamond‐like topology, named POF‐Mgs is computationally designed, and the gas uptakes of CO₂, H₂, N₂, and H₂O in POF‐Mgs are investigated by Grand canonical Monte Carlo simulations based on first‐principles derived force fields (FF). The FF, which describes the interactions between POF‐Mgs and gases, are fitted by dispersion corrected double‐hybrid density functional theory, B2PLYP‐D3. The good agreement between the obtained FF and the first‐principle energies data confirms the reliability of the FF. Furthermore our simulation shows the presence of a small amount of H₂O (≤ 0.01 kPa) does not much affect the adsorption quantity of CO₂, but the presence of higher partial pressure of H₂O (≥ 0.1 kPa) results in the CO₂ adsorption decrease significantly. The good performance of POF‐Mgs in the simulation inspires us to design novel porous materials experimentally for gas adsorption and purification. © 2017 Wiley Periodicals, Inc.     

Fabrication of a Hydrogen‐Bonded Organic Framework Membrane through Solution Processing for Pressure‐Regulated Gas Separation

Ordered and flexible porous frameworks with solution processability are highly desirable to fabricate continuous and large‐scale membranes for the efficient gas separation. Herein, the first microporous hydrogen‐bonded organic framework (HOF) membrane has been fabricated by an optimized solution‐processing technique. The framework exhibits the superior stability because of the abundant hydrogen bonds and strong π–π interactions. Thanks to the flexible HOF structure, the membrane possesses the unprecedented pressure‐responsive H₂/N₂ separation performance. Furthermore, the scratched membrane can be healed by the treatment of solvent vapor, achieving the recovery of separation performance.