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.     

Defect‐Free Mixed‐Matrix Membranes with Hydrophilic Metal‐Organic Polyhedra for Efficient Carbon Dioxide Separation

Defect‐free mixed‐matrix membranes (MMMs) were prepared by incorporating hydrophilic metal‐organic polyhedra (MOPs) into cross‐linked polyethylene oxide (XLPEO) for efficient CO₂ separation. Hydrophilic MOPs with triethylene glycol pendant groups, which were assembled by 5‐tri(ethylene glycol) monomethyl ether isophthalic acid and Cu^II ions, were uniformly dispersed in XLPEO without particle agglomeration. Compared to conventional neat XLPEO, the homogenous dispersion of EG₃‐MOPs in XLPEO enhanced CO₂ permeability of MMMs. Upon increasing the amount of EG₃‐MOPs, the membrane performance such as CO₂/N₂ selectivity was steadily improved because of unsaturated Cu^II sites at paddle‐wheel units, which was confirmed by Cu K‐edge XANES and TPD analysis. Therefore, such defect‐free MMMs with unsaturated metal sites would contribute to enhance CO₂ separation performance.     

Mixed‐Matrix Membranes

Research into extended porous materials such as metal‐organic frameworks (MOFs) and porous organic frameworks (POFs), as well as the analogous metal‐organic polyhedra (MOPs) and porous organic cages (POCs), has blossomed over the last decade. Given their chemical and structural variability and notable porosity, MOFs have been proposed as adsorbents for industrial gas separations and also as promising filler components for high‐performance mixed‐matrix membranes (MMMs). Research in this area has focused on enhancing the chemical compatibility of the MOF and polymer phases by judiciously functionalizing the organic linkers of the MOF, modifying the MOF surface chemistry, and, more recently, exploring how particle size, morphology, and distribution enhance separation performance. Other filler materials, including POFs, MOPs, and POCs, are also being explored as additives for MMMs and have shown remarkable anti‐aging performance and excellent chemical compatibility with commercially available polymers. This Review briefly outlines the state‐of‐the‐art in MOF‐MMM fabrication, and the more recent use of POFs and molecular additives.     

Azine‐Linked Covalent Organic Framework (COF)‐Based Mixed‐Matrix Membranes for CO2/CH4 Separation

Mixed‐matrix membranes (MMMs) comprising Matrimid and a microporous azine‐linked covalent organic frameworks (ACOF‐1) were prepared and tested in the separation of CO₂ from an equimolar CO₂/CH₄ mixture. The COF‐based MMMs show a more than doubling of the CO₂ permeability upon 16 wt % ACOF‐1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.     

High‐Performance Polymers for Membrane CO2/N2 Separation

This Concept examines strategies to design advanced polymers with high CO₂ permeability and high CO₂/N₂ selectivity, which are the key to the success of membrane technology for CO₂ capture from fossil fuel‐fired power plants. Specifically, polymers with enhanced CO₂ solubility and thus CO₂/N₂ selectivity are designed by incorporating CO₂‐philic groups in polymers such as poly(ethylene oxide)‐containing polymers and poly(ionic liquids); polymers with enhanced CO₂ diffusivity and thus CO₂ permeability are designed with contorted rigid polymer chains to obtain high free volume, such as polymers with intrinsic microporosity and thermally rearranged polymers. The underlying rationales for materials design are discussed and polymers with promising CO₂/N₂ separation properties for CO₂ capture from flue gas are highlighted.     

Engineering of the Filler/Polymer Interface in Metal–Organic Framework‐Based Mixed‐Matrix Membranes to Enhance Gas Separation

Traditional films cannot fully adapt to industrial applications and to intensified processes. Advanced mixed‐matrix membranes comprising metal–organic frameworks (MOF) embedded in a polymer matrix have been developed with the goal of breaking the trade‐off effect of traditional polymer membranes and achieving separation performance beyond Robeson's upper limit. The key challenges in the fabrication of MOF‐based mixed‐matrix membranes are an enhancement in compatibility between the inorganic filler and the polymer matrix, elimination of the irregular morphology and non‐selective interfacial defects, and further improvement in the gas‐separation performance. This review summarizes the recent advances in protocols and strategies in terms of designing interfacial interactions to enhance the MOF/polymer interface compatibility. This review aims at providing some meaningful insights into preparing MOF‐based mixed‐matrix membranes targeting ideal interfacial morphology and leading to excellent gas‐separation performance.     

Tunning CO2 Separation Performance of Ionic Liquids through Asymmetric Anions

This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [C₂mim][CF₃BF₃] and [C₂mim][CF₃SO₂C(CN)₂], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [C₂mim]⁺ cation. [C₂mim][CF₃BF₃] and [C₂mim][CF₃SO₂C(CN)₂] single gas separation performance towards CO₂, N₂, and CH₄ at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO₂ permeation results, [C₂mim][CF₃BF₃] showed an undermined value of 710 Barrer at 293.15 K and 1 bar of feed pressure when compared to [C₂mim][BF₄], whereas for the [C₂mim][CF₃SO₂C(CN)₂] IL an unexpected CO₂ permeability of 1095 Barrer was attained at the same experimental conditions, overcoming the results for the remaining ILs used for comparison. The prepared membranes exhibited diverse permselectivities, varying from 16.9 to 22.2 for CO₂/CH₄ and 37.0 to 44.4 for CO₂/N₂ gas pairs. The thermophysical properties of the [C₂mim][CF₃BF₃] and [C₂mim][CF₃SO₂C(CN)₂] ILs were also determined in the range of T = 293.15 K up to T = 353.15 K at atmospheric pressure and compared with those for other ILs with the same cation and anion’s with similar chemical moieties.     

Amine‐Appended Hierarchical Ca‐A Zeolite for Enhancing CO2/CH4 Selectivity of Mixed‐Matrix Membranes

An amine‐appended hierarchical Ca‐A zeolite that can selectively capture CO₂ was synthesized and incorporated into inexpensive membrane polymers, in particular polyethylene oxide and Matrimid, to design mixed‐matrix membranes with high CO₂/CH₄ selectivities. Binary mixture permeation testing reveals that amine‐appended mesoporous Ca‐A is highly effective in improving CO₂/CH₄ selectivity of polymeric membranes. In particular, the CO₂/CH₄ selectivity of the polyethylene oxide membrane increases from 15 to 23 by incorporating 20 wt % amine‐appended Ca‐A zeolite. Furthermore, the formation of filler/polymer interfacial defects, which is typically found in glassy polymer‐zeolite pairs, is inhibited owing to the interaction between the amine groups on the external surface of zeolites and polymer chains. Our results suggest that the amine‐appended hierarchial Ca‐A, which was utilized in membrane fabrication for the first time, is a good filler material for fabricating a CO₂‐selective mixed‐matrix membrane with defect‐free morphology.     

Reverse‐Selective Microporous Membrane for Gas Separation

Sort the bigs from the smalls : Reverse‐selective membranes, through which bigger molecules selectively permeate, are attractive for developing chemical processes. A new adsorption‐based reverse‐selective membrane that utilizes a Na cation occluded in a zeolitic framework is presented. The membrane developed enables the selective permeation and separation of bigger polar molecules, such as methanol and water, from hydrogen above 473 K.

     

Two‐Dimensional Microporous Material‐based Mixed Matrix Membranes for Gas Separation

Since the discovery of graphene and its derivatives, the development and application of two‐dimensional (2D) materials have attracted enormous attention. 2D microporous materials, such as metal‐organic frameworks (MOFs), covalent organic frameworks (COFs), graphitic carbon nitride (g‐C₃N₄) and so on, hold great potential to be used in gas separation membranes because of their high aspect ratio and homogeneously distributed nanometer pores, which are beneficial for improving gas permeability and selectivity. This review briefly summarizes the recent design and fabrication of 2D microporous materials, as well as their applications in mixed matrix membranes (MMMs) for gas separation. The enhanced separation performances of the membranes and their long‐term stability are also introduced. Challenges and the latest development of newly synthesized 2D microporous materials are finally discussed to foresee the potential opportunities for 2D microporous material‐based MMMs.     

IrIII‐based Octahedral Metalloligands Derived Primitive Cubic Frameworks for Enhanced CO2/N2 Separation

We developed a metalloligand strategy to construct porous frameworks, viz. the combined use of Ir^III‐based octahedral metalloligands and the linear unit [Ni(cyclam)] easily afforded two isostructural complexes 1 and 2 with primitive cubic frameworks. Both complexes show good CO₂/N₂ separation property.     

MOF Scaffold for a High‐Performance Mixed‐Matrix Membrane

A novel composite membrane consisting of an interconnected MOF scaffold coated with cross‐linked poly(ethylene glycol) (PEG) has been developed. As a result of its unique structure, the membrane shows an exceptional 18‐fold permeability enhancement as compared to pristine PEG membranes, without compromising the selectivity. This performance is unattainable with current mixed‐matrix membranes (MMMs). Our optimized membrane has a permeability of 2700 Barrer with a CO₂/N₂ selectivity of 35, which surpasses the latest Robeson upper bound.     

Revealing the Transient Concentration of CO2 in a Mixed‐Matrix Membrane by IR Microimaging and Molecular Modeling

Through IR microimaging the spatially and temporally resolved development of the CO₂ concentration in a ZIF‐8@6FDA‐DAM mixed matrix membrane (MMM) was visualized during transient adsorption. By recording the evolution of the CO₂ concentration, it is observed that the CO₂ molecules propagate from the ZIF‐8 filler, which acts as a transport “highway”, towards the surrounding polymer. A high‐CO₂‐concentration layer is formed at the MOF/polymer interface, which becomes more pronounced at higher CO₂ gas pressures. A microscopic explanation of the origins of this phenomenon is suggested by means of molecular modeling. By applying a computational methodology combining quantum and force‐field based calculations, the formation of microvoids at the MOF/polymer interface is predicted. Grand canonical Monte Carlo simulations further demonstrate that CO₂ tends to preferentially reside in these microvoids, which is expected to facilitate CO₂ accumulation at the interface.     

CO2 Separation by Imide/Imine Organic Cages

Two novel imide/imine-based organic cages have been prepared and studied as materials for the selective separation of CO₂ from N₂ and CH₄ under vacuum swing adsorption conditions. Gas adsorption on the new compounds showed selectivity for CO₂ over N₂ and CH₄. The cages were also tested as fillers in mixed-matrix membranes for gas separation. Dense and robust membranes were obtained by loading the cages in either Matrimid® or PEEK-WC polymers. Improved gas-transport properties and selectivity for CO₂ were achieved compared to the neat polymer membranes.     

High-Flux Carbon Molecular Sieve Membranes for Gas Separation

Carbon membranes have great potential for highly selective and cost-efficient gas separation. Carbon is chemically stable and it is relative cheap. The controlled carbonization of a polymer coating on a porous ceramic support provides a 3D carbon material with molecular sieving permeation performance. The carbonization of the polymer blend gives turbostratic carbon domains of randomly stacked together sp² hybridized carbon sheets as well as sp³ hybridized amorphous carbon. In the evaluation of the carbon molecular sieve membrane, hydrogen could be separated from propane with a selectivity of 10 000 with a hydrogen permeance of 5 m³(STP)/(m²hbar). Furthermore, by a post-synthesis oxidative treatment, the permeation fluxes are increased by widening the pores, and the molecular sieve carbon membrane is transformed from a molecular sieve carbon into a selective surface flow carbon membrane with adsorption controlled performance and becomes selective for carbon dioxide.     

A Flexible Pro‐porous Coordination Polymer: Non‐conventional Synthesis and Separation Properties Towards CO2/CH4 Mixtures

The novel coordination polymers [Cu(Hoxonic)(H₂O)]_n ( 1 ) and [Cu(Hoxonic)(bpy)_0.5]_n ? 1.5 n H₂O ( 2?H₂O ) (H₃oxonic: 4,6‐dihydroxy‐1,3,5‐triazine‐2‐carboxylic acid; bpy: 4,4′‐bipyridine) have been isolated and structurally characterised by ab initio X‐ray powder diffraction. The dense phase 1 contains 1D zig‐zag chains in which Hoxonic dianions bridge square‐pyramidal copper(II) ions, apically coordinated by water molecules. On the contrary, 2?H₂O , prepared by solution and solventless methods, is based on 2D layers of octahedral copper(II) ions bridged by Hoxonic ligands, further pillared by bpy spacers. The resulting pro‐porous 3D network possesses small hydrated cavities. The reactivity, thermal, magnetic and adsorptive properties of these materials have been investigated. Notably, the adsorption studies on 2 show that this material possesses unusual adsorption behaviour. Indeed, guest uptake is facilitated by increasing the thermal energy of both the guest and the framework. Thus, neither N₂ at 77 K nor CO₂ at 195 K are incorporated, and CH₄ is only minimally adsorbed at 273 K and high pressures (0.5 mmol g^?1 at 2500 kPa). By contrast, CO₂ is readily incorporated at 273 K (up to 2.5 mmol g^?1 at 2500 kPa). The selectivity of 2 towards CO₂ over CH₄ has been investigated by means of variable‐temperature zero coverage adsorption experiments and measurement of breakthrough curves of CO₂/CH₄ mixtures. The results show the highly selective incorporation of CO₂ in 2 , which can be rationalised on the basis of the framework flexibility and polar nature of its voids.