Polymers Of Intrinsic Microporosity Research Articles

Facile Polymer of Intrinsic Microporosity-Modified Separator with Quite-Low Loading for Enhanced-Performance Lithium Metal Batteries.

Lithium metal batteries (LMBs) using Li metals as anodes are conspicuous for high-energy-density energy-storage devices. However, the nonuniform deposition of Li+ ions leading to uncontrolled Li dendrite growth, which adversely affects electrochemical performance and safety, has impeded the practical application of lithium metal batteries (LMBs). Herein, PIM-1, a type of polymer of intrinsic microporosity (PIM), was utilized for surface engineering of conventional polyolefin separators. This process resulted in the formation of a continuous and homogeneous coating across the separator, facilitating uniform Li+ ion flux and deposition, and consequently reducing dendrite formation. Notably, the loading mass was quite low (0.6 g/m2) through the convenient dipping method. The intrinsic micropores and polar groups (cyano and ether groups) of PIM-1 greatly improved the electrolyte wettability and ionic conductivity of commercial polypropylene (PP) separators. And the PIM-1 coating guided Li+ flux to achieve uniform Li deposition. Moreover, the polar groups (cyano and ether groups) of PIM-1 are beneficial to the desolvation of Li+-solvates. As a result, the synergetic effect of uniform Li+ flux, desolvation, and enhanced mechanical strength of separators brings about considerable improvement in cycle life, suppression of Li dendrite, and Coulombic efficiency for LMBs. As this surface engineering is simple, relatively low-cost, and effective, this work provides fresh insights into separators for LMBs.

Polymers of Intrinsic Microporosity Containing [2.2]Paracyclophane Moieties: Synthesis and Gas Sorption Properties

AbstractThe unique structure of [2.2]paracyclophane (PCP) with its rigidity, stability, and planar chirality has gained significant attention in polymer and material research. In this work, the incorporation of amino‐functionalized PCPs within polymers of intrinsic microporosity (PIMs) is reported for the first time. Three different PCP‐PIMs were prepared via a Tröger's base formation mechanism, and their structures characterized via solid‐state NMR, MALDI‐TOF, and SEM. Their porosity was evaluated using gas adsorption (N2 and CO2) based on theoretical calculations such as Brunauer–Emmett–Teller (BET), NLDFT pore size distribution (PSD) and ideal IAST CO2/N2 selectivity (15/85), a crucial separation when considering the capture of CO2 from flue gas. The surface areas were found to be between 200–230 m2 g−1 while the selectivity for CO2/N2 ranged from 46 to 70.

Exploring physical aging in PIM-1 using molecular dynamics

This comprehensive study explored the aging process of PIM-1, a ladder polymer of intrinsic microporosity (PIM), by applying molecular dynamics simulations for the first time. Through detailed analysis, our work illustrates the evolution of the polymer structure from a loosely packed, less dense state of the pristine polymer to a more tightly packed configuration due to physical aging. For this purpose, a novel molecular dynamics (MD) methodology was employed in the process toward equilibration of PIM-1. This structural transition was quantitatively captured by measuring key parameters such as density, fractional free volume (FFV), cohesive energy density (CED), d-spacing, surface area, and gas permeabilities. The simulations demonstrate a noticeable increase in density by approximately 7 % in aged PIM-1 compared to a fresh sample. This increase in density is accompanied by a corresponding decrease in FFV, suggesting a more compact molecular arrangement. The impact of these structural changes is evident in the gas transport properties. Permeabilities of all gases tested, He, H2, O2, N2, CO2 and CH4, decreased by 33 %–80 %. Moreover, the selectivity of gas pairs like CO2/CH4 and O2/N2 exhibited increasing trends due to aging, as previously reported in experimental work. Structural analysis performed on the fresh and aged structures indicated collapse of free volume over aging, by disappearance of pores larger than ∼6.5 Å. Furthermore, no intrachain rearrangement was observed during physical aging in the ladder PIM-1 structure; rather, the aging resulted in increased interchain packing efficiency. Our methodology can be employed to other PIM architectures, such as polyimides of intrinsic microporosity (PIM-PIs) as well as low-free volume glassy polymers.

Solution-processable polymers of intrinsic microporosity for selective silver removal from aqueous solution and subsequent disinfection by silver-laden coatings

Silver ions (Ag+) in waterways pose a growing threat to the environment and living organisms. Achieving an effective and green process for Ag+ removal requires an adsorbent with excellent specificity for silver ions and easy recoverability after fouling or blocking. However, this remains a major challenge. To address this concern, we developed a high-performance adsorbent by grafting polymers of intrinsic microporosity (PIM) with thioamide groups. This thioamide-modified PIM (TPIM-1) adsorbent exhibited an exceptional adsorption capacity of 656 mg g−1 and high selectivity (distribution coefficient of 833.3 mL g−1, selectivity coefficient of 346 over Cd2+) for aqueous Ag+ removal. TPIM-1 also features good solubility in selected solvents, allowing regeneration through a dissolution separation precipitation (DSP) procedure once fouling or blocking occurs. Over 80 % of the adsorption capacity was recovered after nine continuous regeneration cycles, showcasing potential cost-effective reusability. Density Functional Theory (DFT) results reveal that the grafted thioamide groups play a critical role in selective Ag+ adsorption, with a binding energy of 54 kcal mol−1. In addition, the Ag+-loaded PIM-coated glass surface showed excellent antibacterial ability, inhibiting the growth of Bacillus subtilis and E. coli. This study provides a viable strategy for the development of a low-carbon footprint silver removing adsorbent from wastewater.

Polymers of intrinsic microporosity with alkaline pyrrolidine and piperidine functional groups for high-temperature proton exchange membranes

Recently, the polymers of intrinsic microporosity (PIMs) exhibit good potential in high-temperature proton exchange membrane fuel cells (HT-PEMFCs) due to their tunable microporosity and functionality. In this paper, alkaline pyrrolidine and piperidine functional groups were introduced onto PIM-1 via the classical Mannich reaction obtaining PIM-1/PIM-Py-50 and PIM-1/PIM-MePi-50. It was found that, compared with commercial Meta-polybenzimidazole (m-PBI) membrane, PIMs membranes showed superior retention of phosphoric acid (PA) and conductivity due to their grafting alkaline groups and rich micropores. After equilibration under 80 °C/40 % relative humidity (RH) for 150 h, the PA retention of PA doped PIM-1/PIM-Py-50 (PIM-1/PIM-Py-50/PA) and PA doped PIM-1/PIM-MePi-50 (PIM-1/PIM-MePi-50/PA) membranes were 74.13 % and 68.52 %, respectively, much higher than PA doped m-PBI (m-PBI/PA) (45.73 %). PIMs membranes maintain excellent dimensional and conductivity stability at 160 °C operating conditions, e.g. PIM-1/PIM-Py-50/PA membrane showed area swelling retention and volume swelling retention of 84.69 % and 82.19 % after 230 h at 160 °C. In addition, with the similar PA uptake, PIMs membranes displayed higher conductivity and peak power density (PPD) at 160 °C. In the accelerated stress test (AST) the PPD of the fuel cell (FC) with the PIM-1/PIM-Py-50/PA membrane remained 81.25 % after 200 aggressive start-up/shut-down cycles at 80 °C. Therefore, PIM-based membranes alkaline groups exhibit a wider temperature operating window, providing theoretical guidance for the design and study of the next generation of high-temperature proton exchange membranes (HT-PEMs).

Ultramicroporous cardo-pendant polyamide nanofilms for enhanced organic solvent nanofiltration

Permeable, selective, and stable polymeric membranes are essential for efficient molecular separation in organic solvents. Polymers of intrinsic microporosity (PIMs) with rigid and twisted chain structures offer abundant pores for high solvent permeability and are emerging as an ideal membrane material. However, guaranteeing high separation selectivity and stability is challenging owing to the wide pore size distribution and low swelling resistance in organic solvents. In this work, we developed intrinsically ultramicroporous polyamides (PAs) with cardo-pendant groups to create crosslinking, ultrathin, and defect-free nanofilms for organic solvent nanofiltration. The molecular simulation confirmed the pivotal role of cardo-pendant group structures in the amine monomers and exhibited their effect in creating pore channel structures within the PAs. Distinctive rigid fluorenyl-based cardo-pendant groups were introduced in amine monomers to finely tailor the packing of PA chains for high ultramicroporosity and a finely tuned pore size. We further achieved the growth of such PAs using a cyclic deposition strategy, in-situ generating highly crosslinking nanofilms with an ultralow thickness of 23–36 nm without structure relaxation. As such, the typically-designed PA membranes demonstrated high and stable solvent permeance (e.g., 18 L m−2 h−1 bar−1 for methanol) and high solute rejection (up to 95 % rejection of 306 Da Azure I), which is superior to its counterparts and current PIM membranes, presenting a new perspective for efficient organic solvent nanofiltration.

Intrinsically microporous polyimide membranes with synergistic aromatic and alicyclic linking groups for efficient molecular separation

Polymers of intrinsic microporosity (PIMs) are widely recognized for having great potential in reforming membrane technology for molecular separation within organic solvents, due to their rich and appropriate pore structures with a size < 2 nm. However, the swelling in organic solvents has a significant effect on their pore structures due to the amorphous and linear nature, resulting in the permeability and selectivity performances of developed PIM membranes being far from ideal. In this work, we synthesized an advanced polyimide of intrinsic microporosity by integrating a Tröger’s base (TB) structure with an synergistic structure of aromatic (naphthalenediimide, NDI) and alicyclic (bicyclooctenediimide, BCODI) linking groups. The TB with a rigid and twisted structure was used to furnish a basis for inhibiting chain packing for high overall free volume. The ultra-rigid NDI units maintained such a tailored high free volume and provided superior solvent resistance. The relatively flexible and polar BCODI units promoted local chain mobility to tailor uniform pore size distribution and increased affinity for polar solvents. The innovative design fostered the formation of stable, uniform, and highly solvent-accessible intrinsic micropores. The prepared TFC membrane exhibited good organic solvent separation capabilities, achieving an ethanol permeance of 7.6 L m-2 h−1 bar−1 and a low molecular weight cut-off (MWCO) of approximately 470 Da. This work contributes significantly to the strategic design of PIMs for preparing high-performance membranes for realistic chemical-related separation application scenarios.

Blended Membrane of Polyethylene‐Glycol‐Grafted‐PIM‐1 and Tröger's Base Polymer for the Separation of Pentose and Hexose

AbstractMonosaccharides are vital building blocks in bioengineering applications; however, their extraction from intricate mixtures is challenging and uses substantial amounts of energy. Polymers of intrinsic microporosity (PIMs) offer an innovative avenue for separating monosaccharides. We modified PIM‐1membranes to improve the glucose/xylose separation by incorporating polyethylene glycol monomethyl ether (mPEG). The optimal mPEG (molecular weight: 1000 Da; mass fraction: 2.5 %; solvent: methanol) delivered a xylose separation coefficient of 2.62. With the hybrid membrane of PIM‐1‐mPEG (50 w.t.%) and hydrophilic Tröger's base polymerer (DMBP‐TB, 50 w.t.%), the separation factor for xylose/glucose in an aqueous solution was 2.51 for single‐stage running and 11.32 after five‐stage running. There are large fractions of micropores for PIM‐1‐mPEG, and there is difference on solute‐membrane interactions for pentose/hexose, which are regarded to be the main driving force for the high pentose/hexose selectivity in methanol. The blending of PIM‐1‐mPEG and DMBP‐TB, integrates the microporosity and hydrophilicity, finally endues the high pentose/hexose selectivity in aqueous solution. These microporous membranes are promising materials for efficiently separating monosaccharides and jnl&gt; small organic molecules while minimizing energy consumption. We established a solid foundation for further exploring microporous membranes for various applications, notably in bioengineering.

Photothermal Conversion Porous Organic Polymers: Design, Synthesis, and Applications.

Solar energy is a primary form of renewable energy, and photothermal conversion is a direct conversion process with tunable conversion efficiency. Among various kinds of photothermal conversion materials, porous organic polymers (POP) are widely investigated owing to their controllable molecular design, tailored porous structures, good absorption of solar light, and low thermal conductivity. A variety of POP, such as conjugated microporous polymers (CMP), covalent organic frameworks (COF), hyper-crosslinked porous polymers (HCP), polymers of intrinsic microporosity (PIM), porous ionic polymers (PIP), are developed and applied in photothermal conversion applications of seawater desalination, latent energy storage, and biomedical fields. In this review, a comprehensive overview of the recent advances in POP for photothermal conversion is provided. The micro molecular structure characteristics and macro morphology of POP are designed for applications such as seawater desalination, latent heat energy storage, phototherapy and photodynamic therapy, and drug delivery. Besides, a probe into the underlying mechanism of structural design for constructing POP with excellent photothermal conversion performance is methodicalized. Finally, the remaining challenges and prospective opportunities for the future development of POP for solar energy-driven photothermal conversion applications are elucidated.

Molecular Structure Effects on Ionic Diode Performance in Desalination: Ultrahigh Rectification in Butylated Intrinsically Microporous Polyamine (PIM‐EA‐TB)

AbstractIonic diodes are components in ionic circuits for AC‐electricity driven desalination and ion extraction processes. Independent of the ionic diode type/mechanism, achieving ionic current rectification at high ionic strengths is challenging but important, for example in seawater desalination and treatment of brine. Here, the butylation of a molecularly rigid (glassy) polymer of intrinsic microporosity (PIM‐EA‐TB) is shown to give anionic diodes with ultrahigh rectification effects (associated with interfacial resistivity) even in high ionic strength aqueous 2 M NaCl solution. The effect is rationalised based on polymer structure affecting ion transport.

Merging polymers of intrinsic microporosity and porous carbon-based zinc oxide composites in novel mixed matrix membranes for efficient gas separation

Mixed matrix membranes (MMMs) have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers. However, achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge, due to the difficulty of achieving an optimal match between polymers and fillers. In this study, we incorporate a porous carbon-based zinc oxide composite (C@ZnO) into high-permeability polymers of intrinsic microporosity (PIMs) to fabricate MMMs. The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility, mitigating the formation of non-selective voids in the resulting MMMs. Concurrently, C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs. As a result, the CO2 permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer, while the CO2/N2 and CO2/CH4 selectivity reached 21.5 and 14.4, respectively, substantially surpassing the 2008 Robeson upper bound. Additionally, molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO2 affinity of C@ZnO. In summary, we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.

Amidoxime-functionalized tetraphenylethylene ladder polymer for efficient membrane-based gas separations

Recent advances in solution-processible polymers of intrinsic microporosity (PIM) have attracted extensive research efforts in membrane-based gas separations due to their significantly enhanced gas permeability originating from inefficient chain packing. However, PIM-based membrane materials exhibit typically only moderate gas-pair selectivity, which is often insufficient especially for challenging gas separations containing highly sorbing feed components such as CO2. More importantly, they suffer from CO2-induced polymer chain dilation commonly referred as plasticization, which leads to poor separation performance under aggressive CO2/CH4 mixed-gas testing conditions. In this work, we conducted amidoxime (AO)-functionalization on a microporous tetraphenylethylene-based ladder polymer (TPE-PIM) by reacting its nitrile groups with hydroxyl amine under reflux conditions. Because of strong inter-chain hydrogen bonding, AO-functionalized TPE polymer (AO-TPE) exhibited a tightened and rigidified microstructure with 64 % reduction in Brunauer-Emmett-Teller (BET) surface area (175 m2/g) as compared to TPE-PIM (485 m2/g) derived from N2 adsorption isotherms at 77 K. As a result, fresh AO-TPE showed decreased gas permeability concurrent with a two-fold increase in CO2/CH4 selectivity (from 18 to 40) compared to TPE-PIM. Under aggressive 50:50 CO2:CH4 mixed-gas testing conditions, AO-TPE showed a strong plasticization resistance with decreased CH4 permeability over total feed pressure ranging from 4 to 30 bar. At 20 bar total pressure, AO-TPE demonstrated a mixed-gas CO2/CH4 selectivity of 37.7 as compared to 14.5 for TPE-PIM. The simple AO functionalization strategy holds promise to be an effective post-modification method to increase gas selectivity and alleviate the detrimental effects from CO2-induced plasticization.

Bioinspired Organic Porous Coupling Agent for Enhancement of Nanoparticle Dispersion and Interfacial Strength.

Composite materials have significantly advanced with the integration of inorganic nanoparticles as fillers in polymers. Achieving fine dispersion of these nanoparticles within the composites, however, remains a challenge. This study presents a novel solution inspired by the natural structure of Xanthium. We have developed a polymer of intrinsic microporosity (PIM)-based porous coupling agent, named PCA. PCA's rigid backbone structure enhances interfacial interactions through a unique intermolecular interlocking mechanism. This approach notably improves the dispersion of SiO2 nanoparticles in various organic solvents and low-polarity polymers. Significantly, PCA-modified SiO2 nanoparticles embedded in polyisoprene rubber showed enhanced mechanical properties. The Young's modulus increases to 30.7 MPa, compared to 5.4 MPa in hexadecyltrimethoxysilane-modified nanoparticles. Further analysis shows that PCA-modified composites not only become stiffer but also gain strength and ductility. This research demonstrates a novel biomimetic strategy for enhancing interfacial interactions in composites, potentially leading to stronger, more versatile composite materials.

Hypercrosslinked porous and coordination polymer materials for electrolyte membranes in lithium‐metal batteries

AbstractRechargeable lithium‐metal batteries (LMBs) hold great promise for providing high‐energy density. However, their widespread commercial adoption has been inhibited by critical challenges, for example, the capacity fading from irreversible processes at electrolyte/electrode interfaces and safety concerns originating from the inhomogeneous lithium deposition. Polymer electrolytes benefiting from enhanced electrolyte/electrode contact and low interfacial impedance provide a variable solution to address these challenges and enable a high‐energy and flexible battery system. Although promising, inefficient bulky ionic conductivity and poor mechanical stability confront the stable operation of polymer electrolytes in tangible batteries, which highly requires the development of innovative polymer electrolyte chemistries. Among various polymer materials, microporous polymers stand out due to their abundant porosity and customizable micropore structure, positioning them as promising candidates for next‐generation electrolyte membranes. This review, therefore, summarizes recent advances in electrolyte membranes based on two new chemistries, hypercrosslinked polymers (HCPs) and porous coordination polymers (PCPs). Other microporous polymers, such as covalent organic polymers, porous organic cages, and polymers of intrinsic microporosity, are also discussed with an emphasis on their applications in LMBs. Most importantly, by reviewing the design strategies, synthesis protocols, and performance in LMBs, we gain insights into the design principles of high‐performance electrolyte membranes based on HCPs and PCPs and highlight potential future research directions.

Polymers of intrinsic microporosity with internal dihedral lock for efficient gas separation

Polymers of intrinsic microporosity (PIMs) stand out as promising membrane materials with exceptional separation performance. In this study, we crafted a highly efficient gas separation membrane using an emerging material, called cyclohexyl-fused spirobiindane-based PIM (CCS-PIM). The CCS-PIM features a robust and rigid microporous structure with a high specific surface area (SBET ​= ​704.6 ​m2/g), exhibiting excellent CO2-selective adsorption capacity. The CO2 adsorption uptake is 0.78 ​mmol/g at 273 ​K and 0.15 ​bar, leading to IAST selectivity of 25.2 for CO2/N2 (15/85 v/v) and 16.7 for CO2/CH4 (50/50 v/v) at 298 ​K. The precisely tuned pore size of the CCS-PIM membrane leads to an enhanced molecular sieving effect, showcasing superior selectivity across various gas pair separations. It demonstrates an O2/N2 selectivity of 6.03 and a CO2/CH4 selectivity of 26.1, surpassing the 2008 Robeson upper bounds. This study suggests a strategic method to improve gas separation efficiency by customizing a locked PIM structure with precise molecular sieving through the insertion of variously sized rings.

Techno-economic and environmental life cycle assessment of next-generation fiber-encapsulated nanoscale hybrid materials for direct air carbon capture

A techno-economic and environmental life cycle assessment was conducted for manufacturing two novel types of solid sorbents used for direct air CO2 capture (DAC). One type of solid sorbent comprised Polyacrylonitrile (PAN)/Organopolysilizane (OPSZ)/nanoscale organic hybrid materials (NOHM), and the other comprised polymers of intrinsic microporosity (PIM)/NOHM. These solid sorbents were assumed to be manufactured via an unconventional route: electrospinning as fibers. Economic analyses revealed that manufacturing costs for a 0.73 MT/year capacity plant were $831 and $1398/kg of electrospun fiber in the case of PAN/OPSZ/NOHM and PIM/NOHM, respectively. The costs were higher for PIM/NOHM owing to high raw material prices (Spirobisindane and tetrafluoroterephthalonitrile), which are used only in manufacturing PIM. Scaling up the plant capacity from 0.73 to 30 MT/year decreased the manufacturing cost by nearly half from $831 to $379 in the case of PAN/OPSZ/NOHM, depicting the economies of scale effect. A life cycle assessment (LCA) of both types of solid sorbent was performed using OpenLCA software, the Ecoinvent v 3.5 database, and the TRACI LCI assessment method. The Global Warming Potential (GWP) of PAN/OPSZ/NOHM and PIM/NOHM was observed to be 151 × 10−3 and 166 × 10−3 kg CO2 eq. per kg CO2 captured in the DAC plant, respectively. These GWP values were nearly five times as high as those observed for other solid sorbents existing in the literature, such as PEI on silica gel, carbonate on silica, and carbonate on activated carbon, owing to the large amounts of electricity used in the electrospinning unit operation.

An Ultrathin Composite Polymer Electrolyte Dual-Reinforced by a Polymer of Intrinsic Microporosity (PIM-1) and Poly(tetrafluoroethylene) (PTFE) Porous Membrane.

The performances of solid-state polymer electrolytes are urgently required to be further improved for high energy density lithium metal batteries. Herein, a highly reinforced ultrathin composite polymer electrolyte (PLPP) is successfully fabricated in a large scale by densely filling the well-dispersed mixture of polyethylene oxide (PEO), Li-salt (LiTFSI) and a polymer of intrinsic microporosity (PIM-1) into porous poly(tetrafluoroethylene) (PTFE) matrix. Based on the macro-plus-micro synergistic enhancement of the PTFE with excellent mechanical properties and the soluble PIM-1 with suitable functional groups, the PLPP electrolyte exhibits excellent properties including mechanical stress, thermal stability, lithium-ion transference number, voltage window and ionic conductivity, which are all superior to the typical PEO/LiTFSI electrolytes. As a result, the Li/PLPP/Li symmetric cell can stably cycle for > 2000h, and the LiFePO4/PLPP/Li full cell exhibits excellent rate performance (>10 C) and high cycling stability with an initial capacity of 158.8 mAh g-1 and a capacity retention of 78.8% after 300 cycles. In addition, the excellent mechanical properties as well as the wide voltage window reasonably result in the stable operation of full cells with either high-loading cathode up to 28.1mg cm-2 or high voltage cathode with high energy density.

Polymer of Intrinsic Microporosity as Binders for both Acidic and Alkaline Oxygen Reduction Electrocatalysis

AbstractIn this work, a new polymeric binder (polymer of intrinsic microporosity, PIM‐1) has been investigated and discussed to prepare and characterize composite materials for the cathodic oxygen reduction reaction. The new binder is a polymer of intrinsic microporosity, a family of organic compounds with molecularly rigid (glassy) structure, good mechanical and chemical stability. Their influence on the electrocatalytic behaviour of a commercial electrocatalyst during the oxygen reduction reaction in acidic and alkaline media has been investigated, discussed and compared to the behaviour of common cationic and anionic polymer binders, using rotating disk electrode (RDE) techniques. Polymers of intrinsic microporosity perform similarly well, and sometimes better (due to rigidity and gas permeation) when compared to commercial binders. Thus, herein, we showed that PIMs do represent a very promising and versatile alternative as binders in electrocatalysis.

Effects of metal acetate addition on the gas separation properties of polymers of intrinsic microporosity PIM-1 and PIM-Py

Gas separation properties are reported for self-standing polymer of intrinsic microporosity (PIM) films after addition of palladium (II) acetate or iron (II) acetate by solid state or liquid state mixing. Membranes, with thicknesses in the range 35–55 μm, were prepared from three high molar mass PIMs, two different branched versions of the much-reported PIM-1 (PIM-1a and PIM-1b) and of PIM-Py. Addition of either Fe(OAc)2 or Pd(OAc)2 to all three PIMs led to a reduction in permeability and increase in selectivity, but the permeability reduction was much greater for Pd(OAc)2, which is able to interact with branch points in the PIM and crosslink the polymer. CO2/CH4 selectivity of membranes containing Pd(OAc)2 was poor upon aging, especially after solid state addition to the PIM-1 polymers, for which CO2 permeabilities dropped to below 200 Barrer after 85 days. Hydrogen permeability and H2/N2 selectivity of membranes containing Pd(OAc)2 did more closely follow conventional permeability/selectivity trade off upon aging. This illustrates the profound differences that can arise in gas permeation properties and aging behaviour from variations in chemical structure and macromolecular characteristics, and from the addition of metal acetates that interact with the polymer in different ways.

High Gas Permeability in Aged Superglassy Membranes with Nanosized UiO‐66−NH2/cPIM‐1 Network Fillers

AbstractSuperglassy membranes synthesised by polymers of intrinsic microporosity (PIMs) suffer from physical aging and show poor gas permeance over time, especially thin membranes, due to the fast rearrangement of nonequilibrium polymer chains. Herein, we constructed a novel PIM‐1 thin film nanocomposite membrane (TFN) using nanosized UiO‐66−NH2 (≈10 nm)/carboxylated PIM‐1 (cPIM‐1) as the composite filler. Unlike conventional fillers, which interact with the polymer only via the surface, the UiO‐66−NH2/cPIM‐1 forms a stable three‐dimensional (3D) network intertwining with the polymer chains, being very effective to impede chain relaxation, and thus physical aging. Nanosizing of UiO‐66−NH2 was achieved by regulating the nucleation kinetics using carbon quantum dots (CQD) during the synthesis. This led to increased surface area, and hence more functional groups to bond with cPIM‐1 (via hydrogen bonding between −NH2 and −COOH groups), which also improved interfacial compatibility between the 3D network and polymer chains avoiding defect formation. As a result, the novel TFN showed significantly improved performance in gas separation along with reduced aging (i.e. ≈6 % loss in CO2 permeability over 63 days); the aged membranes had a CO2 permeance of 2504 GPU and ideal selectivity values of 37.2 and 23.8 for CO2/N2 and CO2/CH4, respectively.