Microporous polymer adsorptive membranes with high processing capacity for molecular separation.

Trade-off between permeability and nanometer-level selectivity is an inherent shortcoming of membrane-based separation of molecules, while most highly porous materials with high adsorption capacity lack solution processability and stability for achieving adsorption-based molecule separation. We hereby report a hydrophilic amidoxime modified polymer of intrinsic microporosity (AOPIM-1) as a membrane adsorption material to selectively adsorb and separate small organic molecules from water with ultrahigh processing capacity. The membrane adsorption capacity for Rhodamine B reaches 26.114 g m-2, 10-1000 times higher than previously reported adsorptive membranes. Meanwhile, the membrane achieves >99.9% removal of various nano-sized organic molecules with water flux 2 orders of magnitude higher than typical pressure-driven membranes of similar rejections. This work confirms the feasibility of microporous polymers for membrane adsorption with high capacity, and provides the possibility of adsorptive membranes for molecular separation.

Constructing Strong Interfacial Interactions under Mild Conditions in MOF-Incorporated Mixed Matrix Membranes for Gas Separation.

Although mixed matrix membranes (MMM) possess remarkably improved gas separation performance compared to traditional polymeric membranes, membrane stability including CO2 plasticization and aging is still a serious issue due to the existence of interfacial defects. In this work, we report an efficient and less destructive route to cross-link the MOFs/polyimide (PI) MMM, where amine group-functionalized MOF (NH2-UiO-66) nanoparticles are thermally cross-linked with a carboxylic acid-functionalized PI (COOH-PI) matrix to form an amide bond at the interface at 150 °C under vacuum condition. Such a chemical cross-linking strategy conducted at a relatively mild condition improves membrane stability greatly while ensuring that the membrane structure is not destroyed. The resulting cross-linked MMM achieves enhanced mechanical strength with higher Young's modulus than a pristine polymer membrane. The CO2 antiplasticization pressure of the MMM after cross-linking is enhanced by 200% from ∼10 to >30 bar and the CO2 permeability of MMM only drops slightly from 995 to 735 Barrer after 450 days. At the same time, the separation performance of H2/CH4 gas pair surpasses the 2008 upper bound and that of CO2/CH4 gas pair nearly approaches the 2008 upper bound. The cross-linking strategy used herein provides a feasible and effective route for improving membrane stability and membrane performance in the MMM system for gas separation.

MOF Nanosheet-Based Mixed Matrix Membranes with Metal-Organic Coordination Interfacial Interaction for Gas Separation.

In the mixed matrix membrane (MMM), the interface between the filler and the polymer matrix will directly affect the gas separation performance of the membranes. Reasonable interfacial design in MMMs is thus important and necessary. In this work, metal-organic coordination interaction is used to construct the interface in metal-organic framework (MOF) nanosheet-based polyimide MMMs where ultrathin Co-benzenedicarboxylate MOF nanosheets (CBMNs) with a thickness less than 5 nm and a lateral size more than 5 µm are synthesized as fillers and a carboxyl-functionalized polyimide (6FDA-durene-DABA) is used as a polymer matrix. Because of the high aspect ratio (>1000) of CBMNs, abundant metal-organic coordination bonds are formed between Co2+ in CBMNs and the -COOH group in 6FDA-durene-DABA. As a result, the 6FDA-durene-DABA/CBMN MMMs exhibit improved separation performance for the CO2/CH4 and H2/CH4 gas pairs with H2/CH4 and CO2/CH4 selectivities up to 42.0 ± 4.0 and 33.6 ± 3.0, respectively. The enhanced interfacial interaction leads to the comprehensive separation performance of CO2/CH4 and H2/CH4 gas pairs approaching or surpassing the 2008 Robeson upper bound. In addition, the CO2 plasticization pressure of the MMMs is significantly enhanced up to ∼20 bar, which is 2 times that of the pure 6FDA-durene-DABA membrane. When separating a mixed gas of CO2/CH4, the selectivity of CO2/CH4 remains stable at around 23 and the CO2 permeability keeps around 400 barrer during the long-term test.

Effects on Carbon Molecular Sieve Membrane Properties for a Precursor Polyimide with Simultaneous Flatness and Contortion in the Repeat Unit.

Carbon molecular sieve (CMS)-based membrane separation is a promising solution for hydrogen separation due to its great advantages on perm-selectivity, thermal stability, and chemical stability. To prepare high-performance CMS membranes, the molecular structure of polymer precursors and their arrangements should be primarily considered. In this work, a benzimidazole-based 6FDA (2,2'-bis(3,4'-dicarboxyphenyl) hexafluoropropane dianhydride)-type polyimide (PABZ-6FDA-PI) is chosen as precursor to prepare the CMS membrane. Effects of chain flatness and contortion in the polyimide precursor on gas-separation performance of CMS membranes were studied in detail by gas adsorption and permeation experiment. The H2 permeability of CMS is up to 9500 Barrer and ideal selectivity of gas pairs of H2 /CH4 and H2 /CO2 is up to 3800 and 13, respectively. The comprehensive performance of hydrogen separation including H2 /CO2 , H2 /N2 , and H2 /CH4 gas pairs is located well above previously reported upper bounds for polymers.

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-C3 N4 ) 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.

Polymer of intrinsic microporosity-based macroporous membrane with high thermal stability as a Li-ion battery separator.

Polymers of intrinsic microporosity (PIMs) have numerous advantages such as good thermal stability (T g > 300 °C) and mechanical stability (tensile strength at break > 60 MPa) as well as excellent electrical insulation performance and chemical/electrochemical stability. Herein, a macroporous membrane made up of a polymer of intrinsic microporosity (PIM-1) was fabricated and used as a separator of a rechargeable Li-ion battery for the first time. The PIM-1-based separator showed good thermal resistance with T g > 300 °C, high electrolyte uptake, and excellent Li-ion conductivity.

Tuning the Gas Selectivity of Tröger's Base Polyimide Membranes by Using Carboxylic Acid and Tertiary Base Interactions.

Polyimide-based materials provide attractive chemistries for the development of gas-separation membranes. Modification of inter- and intra-chain interactions is a route to improve the separation performance. In this work, copolyimides with Tröger's base (TB) monomers are designed and synthesized. In particular, a series of copolyimides is synthesized with different contents of carboxylic acid groups (0-50 wt %) to alter the inter- and intra-chain interactions and enhance the basicity of the TB-polyimides. A detailed thermal and structural analysis is provided for the new copolyimides. Gas permeation data reveal a tunable trend in separation performance with increasing carboxylic acid group content. Importantly, this is one of the few examples of copolyimide membranes materials that show enhanced plasticization resistance to high-pressure gas feeds through physical cross-linking.

Carbon Molecular Sieve Membranes Derived from Tröger's Base-Based Microporous Polyimide for Gas Separation.

Carbon molecular sieve (CMS)-based membranes have attracted great attention because of their outstanding gas-separation performance. The polymer precursor is a key point for the preparation of high-performance CMS membranes. In this work, a microporous polyimide precursor containing a Tröger's base unit was used for the first time to prepare CMS membranes. By optimizing the pyrolysis procedure and the soaking temperature, three TB-CMS membranes were obtained. Gas-permeation tests revealed that the comprehensive gas-separation performance of the TB-CMS membranes was greatly enhanced relative to that of most state-of-the-art CMS membranes derived from polyimides reported so far.

A facile synthesis of contorted spirobisindane-diamine and its microporous polyimides for gas separation.

Microporous polyimides (PIM-PIs, KAUST-PIs) and polymers containing Tröger's base (TB) derivatives with improved permeability and selectivity have great importance for separation of environmental gas pairs. Despite the tremendous progress in this field, facile synthesis of microporous polymers at the industrial scale via designing new monomers is still lacking. In this study, a new potential approach for large scale synthesis of spirobisindane diamine (DAS) (3) has been reported from commercially available 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) and 3,4-difluoronitrobenzene. A series of DAS diamine based microporous polyimides were also synthesized. The resulting polymer membranes showed high mechanical and thermal properties with tunable gas separation performance.

Interfacial Design of Mixed Matrix Membranes for Improved Gas Separation Performance.

High-performance metal-organic framework (MOF)/polyimide (PI) mixed matrix membranes (MMMs) are fabricated by a facile strategy by designing the MOF/PI matrix interface via poly dopamine coating. The overall separation performance of the designed MMMs surpasses the state-of-the-art 2008 Robeson upper bound for the H2 /CH4 and H2 /N2 gas pairs and approaches the 2008 upper bound for the O2 /N2 gas pair.

Ultrathin membranes of single-layered MoS2 nanosheets for high-permeance hydrogen separation.

Single-layered MoS2-based ultrathin membranes with well-controlled thicknesses are prepared by a simple filtration method, and for the first time applied to gas separation. These membranes exhibit superior H2/CO2 separation performance and extremely high H2 permeance. The H2/CO2 separation performance surpasses the state-of-the-art upper-bound of polymeric and inorganic membranes.

Monoglyceride-based organogelator for broad-range oil uptake with high capacity.

Oil/water separation has been a worldwide subject because of increasing release of oil-containing wastewater as well as several marine oil spills. The phase-selective organogelators (PSOGs) are thought to offer a potential and effective implement for addressing this issue. An ideal PSOG for oil adsorption must fulfill some requirements involving effective gelation, easy synthesis, low cost, and recyclable for reuse. However, beyond those, the ability of gelation for a broad-range oil phase without selectivity is also important. However, most of the reported PSOGs have limitation in this respect thus far. In this paper, a new class of saturated 1-monoglyceride-derived organogelators can efficiently uptake almost all of the common fuel oils from water and gelate organic solvents with extremely low minimum gelation concentration (MGC). In addition, the oils in the gel and gelator molecules can be recovered quantitatively through simple vacuum distillation.

Tröger's Base-Based Microporous Polyimide Membranes for High-Performance Gas Separation.

It is a great challenge for polyimide to increase its permeability and at the same time to maintain its high selectivity. In this work, Tröger's Base (TB)-based polyimides through polymerizing Tröger's Base diamines with two kinds of anhydrides were successfully synthesized to enhance the permeability of polyimides for gas separation. The TB-polyimide membranes exhibited greatly improved gas separation performance for H2/CH4, H2/N2, He/CH4, and CO2/CH4 gas pairs, among which the separation performance of 6-FDA-based TB-polyimides approaches or slightly exceeds the 2008 Robeson upper bound. Our results revealed that the TB unit with rigid and in-built amine structure plays an important role for increasing the permeability of polyimides and simultaneously maintaining high selectivity. In addition, the TB-based polyimide membranes exhibited extremely high solubility selectivity for the CO2/N2 gas pair up to 62.7 due to a strong affinity between CO2 and nitrogen atoms of tertiary amine in TB.