Carbon molecular sieve (CMS) membranes have emerged as attractive gas membranes due to their tunable pore structure and consequently high gas separation performances. In particular, polyimides (PIs) have been considered as promising CMS precursors because of their tunable structure, superior gas separation performance, and excellent thermal and mechanical strength. In the present work, polyphosphoric acid (PPA) was employed as both cross-linker and porogen, it created pores within the PI polymeric matrix, while it also effectively acting as a cross-linker to regulate the ultramicropores of the CMS membranes, thus simultaneously improving both permeability and selectivity of the CMS membranes. By employing PI/PPA hybrid with PPA content of 5 wt % as a precursor, the obtained CMS membrane exhibited a CO2 and He permeability of 1378.3 Barrer and 1431.4 Barrer, respectively, which was an approximately 10-fold increase compared to the precursor membrane. Under optimized conditions, the CO2/CH4 and He/CH4 selectivity of the obtained CMS membrane reached 81.5 and 89.9, respectively, which was 278% and 307% higher than that of the pristine PI membrane. In addition, the membrane exhibited good long-term stability during a one-week continuous test. This study clearly denoted PPA can be used for precisely tailoring the ultramicroporosity of CMS membranes.

Isoreticular chemistry, which enables property optimization by changing compositions without changing topology, is a powerful synthetic strategy. One of the biggest challenges facing isoreticular chemistry is to extend it to ligands with strongly coordinating substituent groups such as unbound -COOH, because competitive interactions between such groups and metal ions can derail isoreticular chemistry. It is even more challenging to have an isoreticular series of carboxyl-functionalized MOFs capable of encompassing chemically disparate metal ions. Here, with the simultaneous introduction of carboxyl functionalization and pore space partition, a family of carboxyl-functionalized materials is developed in diverse compositions from homometallic Cr3+ and Ni2+ to heterometallic Co2+/V3+, Ni2+/V3+, Co2+/In3+, Co2+/Ni2+. Cr-MOFs remain highly crystalline in boiling water. Unprecedentedly, one Cr-MOF can withstand the treatment cycle with 10m NaOH and 12m HCl, allowing reversible inter-conversion between unbound -COOH acid form and -COO- base form. These materials exhibit excellent sorption properties such as high uptake capacity for CO2 (100.2 cm3 g-1) and hydrocarbon gases (e.g., 142.1 cm3 g-1 for C2H2, 110.5 cm3 g-1 for C2H4) at 1 bar and 298K, high benzene/cyclohexane selectivity (up to ≈40), and promising separation performance for gas mixtures such as C2H2/CO2 and C2H2/C2H4.

Among a plethora of mixtures, the methane (CH4) and hydrogen (H2) mixture has garnered considerable attention for multiple reasons, especially in the framework of energy production and industrial processes as well as ecological considerations. Despite the fact that the CH4/H2 mixture performs many critical tasks, the presence of other gases, such as carbon dioxide, sulfur compounds like H2S, and water vapor, leads to many undesirable consequences. Thus purification of this mixture from these gases assumes considerable relevance. In the current research, first-principle calculations in the frame of density functional theory are carried out to propose a new functional group for vertically aligned carbon nanotubes (VA-CNTs) interacting preferentially with polar molecules rather than CH4 and H2 in order to obtain a more efficient methane and hydrogen separations The binding energies associated with the interactions between several chemical groups and target gases were calculated first, and then a functional group formed by a modified ethylene glycol and acetyl amide was selected. This functional group was attached to the CNT edge with an appropriate diameter, and hence the binding energies with the target gases and steric hindrance were evaluated. The binding energy of the most polar molecule (H2O) was found to be more than six times higher than that of H2, indicating a significant enhancement of the nanotube tip\'s affinity toward polar gases. Thus, this functionalization is beneficial for enhancing the capability of highly packed functionalized VA-CNT membranes to purify CH4/H2 gas mixtures.

A series of poly(ethylene glycol)-block-poly(propylene glycol) (PEG/PPG)- and 5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide)-based crosslinked rubbery polymer membranes, denoted as PEG/PPG-2CZPImide (x:y), are prepared from the norbornene-functionalized PEG/PPG oligomer (NB-PEG/PPG-NB) and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide-NB) via ring-opening metathesis polymerization (ROMP). The molar ratio (x:y) of the NB-PEG/PPG-NB (x) to 2CZPImide-NB (y) monomers is varied from 10:1 to 6:1. X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and pure gas permeability studies reveal that the comonomer 2CZPImide-NB successfully increases the d-spacing among the crystalline PEG/PPG segments, hence enhancing the diffusivity of gases through the membranes. The synthesized membranes exhibit good CO2 separation performance, with CO2 permeabilities ranging from 311.1 to 418.1 Barrer and CO2/N2 and CO2/CH4 selectivities of 39.4-52.0 and 13.4-16.0, respectively, approaching the 2008 Robeson upper bound. Moreover, PEG/PPG-2CZPImide (6:1), displaying optimal CO2 permeability and CO2/N2 and CO2/CH4 selectivities, shows long-term stability against physical aging and plasticization resistance up to 20 days and 10 atm, respectively.

Ionic liquids (ILs) are prized for their selective dissolution of carbon dioxide (CO2), leading to their widespread use in ionogel membranes for gas separation. Despite their advantages, creating sustainable ionogel membranes with high IL contents poses challenges due to limited mechanical strength, leakage risks, and poor recyclability. Herein, we leverage copolymerized and supramolecularly bound ILs to develop ionogel membranes with high mechanical strength, zero leakage, and excellent self-healing and recycling capabilities. These membranes exhibit superior ideal selectivity for gas separation compared to other reported ionogel membranes, achieving a CO2/nitrogen selectivity of 61.7 and a CO2/methane selectivity of 24.6, coupled with an acceptable CO2 permeability of 186.4 Barrer. Additionally, these gas separation ionogel membranes can be upcycled into ionic skins for sensing applications, further enhancing their utility. This research outlines a strategic approach to molecularly engineer ionogel membranes, offering a promising pathway for developing sustainable, high-performance materials for advanced gas separation technologies.

We report hydroxyl-functionalized microporous polymers with tunable benzaldehyde groups for gas separation membranes. These polymers were synthesized via acid-catalyzed Friedel-Crafts polycondensation. The tunability in d-spacing and fractional free volume of these polymers depends on the para position substituents (-H, -F, -Cl, and -Br) of the benzaldehyde. Specifically, the size and polarity of the para position substituent influence the polymer chain-packing structure. Consequently, the hydroxyl-functionalized microporous polymer membrane with a larger para position substituent in the benzaldehyde group exhibited improved gas permeability. This improvement is due to enhanced gas diffusivity resulting from the inefficient polymer chain-packing structure. Furthermore, these membranes demonstrated enhanced CO2 plasticization resistance, attributable to the rigid, contorted polymer structure and the hydrogen bonding interactions between hydroxyl groups. This study provides insights into the relationship between the polymer chain-packing structure, tunable para position substituents, and molecular transport.

With the rapid growth of the economy, people are increasingly reliant on energy sources. However, in recent years, the energy crisis has gradually intensified. As a clean energy source, methane has garnered widespread attention for its development and utilization. This study employed both large-scale computational screening and machine learning to investigate the adsorption and diffusion properties of thousands of metal-organic frameworks (MOFs) in six gas binary mixtures of CH4 (H2/CH4, N2/CH4, O2/CH4, CO2/CH4, H2S/CH4, He/CH4) for methane purification. Firstly, a univariate analysis was conducted to discuss the relationships between the performance indicators of adsorbents and their characteristic descriptors. Subsequently, four machine learning methods were utilized to predict the diffusivity/selectivity of gas, with the light gradient boosting machine (LGBM) algorithm emerging as the optimal one, yielding R2 values of 0.954 for the diffusivity and 0.931 for the selectivity. Furthermore, the LGBM algorithm was combined with the SHapley Additive exPlanation (SHAP) technique to quantitatively analyze the relative importance of each MOF descriptor, revealing that the pore limiting diameter (PLD) was the most critical structural descriptor affecting molecular diffusivity. Finally, for each system of CH4 mixture, three high-performance MOFs were identified, and the commonalities among high-performance MOFs were analyzed, leading to the proposals of three design principles involving changes only to the metal centers, organic linkers, or topological structures. Thus, this work reveals microscopic insights into the separation mechanisms of CH4 from different binary mixtures in MOFs.

The main challenge in the preparation of MOF-based mixed matrix membranes is to construct a good interface morphology to improve the gas separation performance and stability of the membranes. Herein, high-aspect-ratio ZIF-8 nanoplates for H2/CO2 separation membranes were synthesized by direct template conversion. The ZIF-8 nanoplates were prepared with the commercial Matrimid polymer to form MMMs by the flat scraping method. The homogeneous dispersion of high-aspect-ratio nanoplates in the membrane and the good compatibility between the filler and the matrix caused by the thermal annealing operation improve the gas separation performance and mechanical properties of MMMs. The H2/CO2 selectivity of MMMs loaded with 30 wt % ZIF-8 nanoplates increased to 10.3, and the H2 permeability was 330.1 Barrer. This synthesis method can be extended to prepare various ZIF nanoplates with elevated aspect ratios to obtain excellent performance fillers for gas separation of MMMs. In addition, the thermal annealing operation allows more efficient gas separation in polymer membranes and is a feasible way to design excellent and stable MMMs.

Noble gas xenon (Xe) is an excellent anesthetic gas, but its rarity, high cost and constrained production prohibits wide use in medicine. Here, we have developed a closed-circuit anesthetic Xe recovery and reusage process with highly effective CO2-specific adsorbent CUPMOF-5 that is promising to solve the anesthetic Xe supply problem. CUPMOF-5 possesses spacious cage cavities interconnected in four directions by confinement throat apertures of ~3.4 Å, which makes it an ideal molecular sieving of CO2 from Xe, O2, N2 with the benchmark selectivity and high uptake capacity of CO2. In situ single-crystal X-ray diffraction (SCXRD) and computational simulation solidly revealed the vital sieving role of the confined throat and the sorbent-sorbate induced-fit strengthening binding interaction to CO2. CUPMOF-5 can remove 5 % CO2 even from actual moist exhaled anesthetic gases, and achieves the highest Xe recovery rate (99.8 %) so far, as verified by breakthrough experiments. This endows CUPMOF-5 great potential for the on-line CO2 removal and Xe recovery from anesthetic closed-circuits.

Xenon (Xe) is a commercially valuable element found in trace amounts in the off-gas from used nuclear fuel. Recovering Xe from these streams provides a cost-effective means to increase its supply. However, achieving high-purity Xe recovery is challenging due to the need for separation from nearly identical krypton (Kr). Metal-organic frameworks (MOFs), a class of crystalline porous materials, show potential to separate Xe and Kr by utilizing differences in their kinetic diameters, allowing for selective separation. In this work, we study the impact of pore aperture and volume on selective Xe recovery using four robust aluminum MOFs: Al-PMOF, Al-PyrMOF, Al-BMOF and MIL-120, all with conserved structural topology. The pore topology in each MOF is dictated by the dimensions of the tetracarboxylate ligand employed, with larger ligands leading to MOFs with increased pore size and volume. Our experimental and computational investigations revealed that MIL-120 exhibits the highest affinity (21.94 kH(Xe) = 21.94 mmol g-1 bar-1) for Xe among all MOFs, while Al-BMOF demonstrates the highest Xe/Kr selectivity of 14.34. We evaluated the potential of both MIL-120 and Al-BMOF for Xe recovery through breakthrough analysis using a mixture of 400 ppm Xe:40 ppm Kr. Our results indicate that due to its larger pore volume, Al-BMOF captured more Xe than MIL-120, demonstrating superior Xe/Kr separation efficiency.