CO2 Separation Performance Research Articles

Dynamic CO2 separation performance of nano-sized CHA zeolites under multi-component gas mixtures

To identify and evaluate promising adsorbents for CO2 separation, we synthesized CHA zeolites with different cations (Na+, K+, Cs+) and crystal sizes (45 nm – CHA45 and 500 nm – CHA500), and evaluated their explored CO2 adsorption performance from CO2/N2/He and CO2/CH4/He mixtures. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations predicted CO2, N2, and CH4 adsorption isotherms and CO2 mobilities, respectively, which were compared to experimental data. Breakthrough curve analysis was used to assess the CO2 dynamic adsorption performance. The breakthrough curve analysis shows the smaller crystal sizes (45 nm) enhance the CO2 separation due to shorter interacrystalline diffusion pathways. Notably, Cs-CHA45 removed 2.2 times more CO2 from CO2/N2/He than Cs-CHA500. K-CHA45 showed the highest CO2/N2 selectivity (108) and achieved 841mmol g−1 for CO2 capture from N2 and 721mmol g−1 for CO2 from CH4. These findings underscore the potential of CHA nanocrystals for effective CO2 separation in various applications.

Aminated ZIF‐8 to facilitate CO2 sieving through polyvinyl alcohol/ionic liquid membranes

AbstractCO2 separation technology at low pressure is most desirable in carbon capture projects to mitigate global warming. Facilitated transport membranes offer selective and effective CO2 permeation using a wide range of carbon carriers at low pressure. Porous fillers were recently included as they can carry abundant fixed carriers besides offering open channels for CO2 permeation. This study investigates the effects of amine‐modified zeolitic imidazolate framework‐8 (ZIF‐8) with well‐defined micropores and gas sieving ability in polyvinyl alcohol (PVA) membranes containing an ionic liquid that worked as mobile carriers. The effects of amine‐modified ZIF‐8 and silica nanoparticles on membrane properties and separation performance were also compared. Fourier transform infrared spectra confirmed the incorporation of ZIF‐8, secondary amine, IL anions, and silica nanoparticles in PVA membranes. Energy dispersive analysis showed the good dispersion of inorganic fillers. The amine‐modified silica nanoparticles resulted in higher thermal stability compared to the amine‐modified ZIF‐8 in PVA membranes containing [bmin][Ac] ionic liquid, as shown in the thermogravimetric analysis. However, the CO2 separation performance of PVA membranes containing [bmim][Ac] ionic liquid was improved more significantly by the amine‐modified ZIF‐8 with microporous structure. A CO2/N2 ideal selectivity of 85.65 and CO2 permeance up to 4,502.91 GPU were attained. Unlike the CO2/N2 ideal selectivity, the CO2 permeance was not significantly affected either using [bmin][Ac] or [bmin][BF4]. The humid gas greatly enhanced the CO2 permeance without much changes in the CO2/N2 ideal selectivity due to the promotion of facilitated transport. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Chitosan-polyethersulfone mixed matrix composite membranes utilizing amine and non-amine hafnium-MOFs for enhanced CO2 separation

Exploring the realm of advanced membranes with customizable separation capabilities holds great promise in CO2 separation. A particularly exciting path is the utilization of mixed matrix membranes (MMMs) to surpass the performance of commonly used polymeric membranes. In recent times, there has been a surge of interest in hafnium (Hf) metal–organic frameworks (MOFs) due to their multiple potential sites for CO2 adsorption. These MOFs feature four bridging hydroxyl groups (μ3-OH) positioned at the corners of the tetrahedral cavity, electronegative linker moieties, and Bronsted acid sites arising from undercoordinated metals. In this study, we synthesized task-specific UiO-66(Hf) and UiO-66-NH2(Hf) MOFs and integrated them into a chitosan (CS) matrix to explore their effects on CO2 separation performance of MMMs. Comprehensive analyses using various analytical techniques were conducted on synthesized MOFs and MMMs. At an optimal loading of 5 wt% of UiO-66-NH2(Hf) under humid conditions, the MMMs demonstrated a remarkable 408 % increment in CO2 permeance and a 113 % improvement in CO2/N2 selectivity compared to unfilled CS membranes. Notably, the UiO-66-NH2(Hf) MOF, enriched with amino ligands, exhibited superior dispersibility and enhanced CO2 separation ability compared to the UiO-66(Hf) MOF within the CS matrix. These findings not only approach the 2008 Robeson upper bound curve but also demonstrate consistency in the CO2 separation performance for over 120 hours of exposure at elevated temperatures (85°C) and a feed pressure of 2.21 bar under humid conditions. These challenging conditions, mirroring real-world applications, highlight the stability of the synthesized MMMs as efficient gas separation technologies.

PVC-based mixed-matrix membranes based on IL@AC/NH2-MIL-101 nanocomposites for improved CO2 separation performance

Mixed matrix membranes (MMMs), an important class of organic-inorganic nanocomposite membranes, were developed to overcome some of the limitations of purely polymeric membranes. In this study to improve the separation performance of polyvinyl chloride (PVC) membranes, mixed matrix membranes (MMMs) were prepared from incorporating choline prolinate based ionic liquid (IL) in a the coke/metal-organic framework (MOF) (NH2-MIL-101(Cr)) as a filler in polyvinyl chloride (PVC), which can be viewed as a potential solution to the trade-off problem with polymeric membranes because of the combination of the processing versatility of polymers and the high gas separation capability. Coke/MOF/PVC and IL@AC/MOF/PVC MMMs with different filler loadings of 5, 10, and 15 wt% were prepared using solution casting method and characterized using Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) with Energy-Dispersive X-ray Spectroscopy (EDX) analyses, and Brunauer-Emmett-Teller (BET) surface area test. The porous structure of MMMs nanocomposites causes to which coke/MOF composite effectively accelerate gas diffusion in the PVC matrix. The permeability date was measured at 288.15, 298.15, 308.15 and 318.15 K and pressure up to 4 bar for CO2 and N2. According to the outcome, the addition of the IL([Cho][Pro]) filler, the permeability of the AC/MOF/PVC MMMs is increased compared to the pure PVC membrane. The MMMs have the highest gas separation efficiency and performance above Robson’s Upper Bound from 2008.

Constructing the high-efficiency “celluveyor conveyor” transport systems in membranes by IL@ZIF-8 for efficient CO2/CH4 separation

Inspired by the high-efficiency transport systems combined the “conveyor” transport pathways with the “celluveyor” transport pathways, the ionic liquid imide modified ZIF-8 (IL@ZIF-8) was prepared as a filler and incorporated into the self-polymerization-confined Pebax/polyethylene glycol methyl ether acrylate matrix (SPM) to prepare mixed matrix membranes (MMMs) for efficient CO2/CH4 separation. The incorporated IL@ZIF-8 can construct the high-efficiency “celluveyor conveyor” transport systems that consisted of the “celluveyor” transport pathways and the “conveyor” transport pathways, and it played important roles in MMMs. Therein, the “celluveyor” transport pathways can be constructed with the help of CO2 carriers (Zn2+) in oriented and ordered pore channels of IL@ZIF-8, contributing to promoting rapid CO2 transport in multiple direction. IL was uniformly distributed on ZIF-8, and it acted as “binder” between adjacent ZIF-8 in IL@ZIF-8. IL in IL@ZIF-8 can adsorb CO2 molecules as a consequence of its strong chemical affinity for CO2, and the “conveyor” transport pathways can be constructed with the help of CO2 carriers ([Tf2N]-) in IL for rapid CO2 transport between the adjacent ZIF-8, improving CO2 separation performance of MMMs. Consequently, it was possible to enhance the performance of CO2 separation by constructing the high-efficiency “celluveyor conveyor” transport systems in SPM/IL@ZIF-8 MMMs. Therefore, SPM/IL@ZIF-8 MMMs were endowed with the excellent CO2 separation performance. It showed an enhanced permeability for CO2, which increased by 96.9 %, and a better CO2/CH4 selectivity, which improved by 56.6 %, when compared to the performance of the pure SPM membrane. It implied that the constructed high-efficiency “celluveyor conveyor” transport systems in MMMs were a promising strategy for efficient CO2 separation.

Preparation and characterization of highly CO2 permeable and selective graphene oxide membranes by introducing gutter layers into porous substrates

Here, we present graphene oxide (GO)-based thin-film composite (TFC) membranes with enhanced CO2 separation performance using a surface-modified substrate for uniform GO depositions. We extensively characterized the surface properties of porous substrates to identify optimal conditions for universal and uniform GO selective layer. Our results reveal that incorporating polyvinylpyrrolidone (PVP) as a gutter layer is essential for achieving consistent and regular GO layer coating. As a result, the developed GO membranes demonstrate a CO2 permeance of 350 GPU, which is a ∼350 % improvement over the GO membranes without gutter layer, coupled with a higher selectivity for CO2/N2 and CO2/CH4 pairs. The results indicate the excellent potential for significantly enhanced CO2 separation performances with the development of suitable support membranes.

Constructing the positive electrostatic environments by nanosheet in mixed matrix membranes for efficient CO2 separation

Mixed Matrix Membranes (MMMs) have shown advantages in overcoming trade-off effects, but there is still an urgent need to enhance CO2 separation performance in the design of multifunctional fillers. To overcome the trade-off effects in MMMs, a rational design of fillers with selective recognition for CO2 molecules is an effective strategy. A microporous nanosheet Qc-5-Cu was synthesized and incorporated into a Pebax MH 1657 (Pebax) to prepare MMMs for efficiently separating CO2 from CH4. The H atoms of the aromatic rings on the surface of pores in Qc-5-Cu constructed positive electrostatic environments, which significantly improves the CO2/CH4 separation performance of MMMs. On one hand, the constructed positive electrostatic environments in the MMMs attracted the negatively charged O atoms of CO2 molecules through electrostatic attraction, which effectively accelerated CO2 transport. On the other hand, the positive electrostatic environments established a selective barrier for preventing CH4 transport, achieving high CO2/CH4 selectivity in MMMs. Compared to pure Pebax membrane, the Pebax/Qc-5-Cu-0.5 MMM exhibited a remarkable enhancement of 99.52 % in CO2 permeability (934.24 Barrer) and a significant increase of 37.64 % in CO2/CH4 selectivity (25.01). The constructed positive electrostatic environments of nanosheets in MMMs offers a potential prospect for efficient CO2/CH4 separation.

Integration of deep eutectic solvent with adsorption and membrane-based processes for CO2 capture: An innovative approach

CO2 capture strategies have been implemented to address climate change by reducing CO2 emissions from large-scale sources such as fossil fuel power plants and natural gas upgrading. Deep eutectic solvents (DESs) are a new class of green solvents with good CO2 affinity, simple synthesis steps, inexpensive raw materials, non-toxic and non-volatile properties. For these reasons, they are a promising platform for CO2 capture applications and have tremendous untapped potential to enhance the performance of the adsorption and membrane-based separation processes. Unlike existing reviews which have focused on the functionalities of DESs, as well as the physicochemical and CO2 solubility properties of DESs, this mini-review discusses the integration of DESs with adsorption and membrane processes to evaluate their CO2 separation performance. Moreover, simulation and computational studies on DES-based systems, including confinement in porous solids and membranes, are discussed. Finally, perspectives on developing DES-based adsorbents and DES-based membranes for the CO2 separation field are presented. This review provides insight into the potential of integrating DESs with CO2 capture technologies to enhance the performance of hybrid systems in relation to standalone approaches.

Enhancing CO2 Transport Across the PEG/PPG-Based Crosslinked Rubbery Polymer Membranes with a Sterically Bulky Carbazole-Based ROMP Comonomer.

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.

Theoretical perspectives on CO2 separation by ionic liquids: Addressing crucial questions

The global population explosion necessitates more natural resources for energy, making it a major factor in climate change. CO2 is a leading actor in the greenhouse gas effect, and advancements in CO2 capture processes have attracted researchers in recent years. Numerous technologies are practiced for CO2 separation. Nevertheless, due to the intricate nature of gases and different process conditions, most of them continue to face challenges. To overcome these challenges, researchers focus on finding or designing innovative materials compatible with various processes. From the discovery of high CO2 solubility of ionic liquids (ILs), these unique compounds have rapidly gained popularity for different applications like gas separation. Molecular simulations play a crucial role in supporting researchers in understanding the connection between the properties and chemical structure of newly developed materials as ILs in a time-efficient manner. Despite the growing number of molecular simulation studies, there is a gap in the review papers that effectively highlight the benefits and feasibility of the theoretical approach. Up to date, mostly experimental studies mainly focusing on gas transport mechanisms and the relationship between chemical composition and properties were summarized. Herein, we concentrated on molecular simulation studies investigating the adsorption- and membrane-based CO2 separation performance of confined ILs. We systematically addressed prominent questions posed by researchers in each simulation study, demonstrating how to examine confined ILs and interpret the resulting data in relation to gas separation performance. The most pertinent inquiries encompass the influence of ion type (cation or anion) on gas adsorption at the gas–liquid interface and through the confined IL phase, the significance of the confined form of cation or anion in gas transport, the impact of IL thickness on gas separation, and the discernible effects of the material in which ILs are confined. Therefore, we hope to guide researchers in developing innovative membranes or adsorbents by leveraging insights obtained from the answers to these questions derived from molecular simulations of confined ILs.

Synthesis of metal-doped covalent triazine frameworks: Incorporation into 6FDA-Durene polyimide for CO2 separation through mixed matrix membranes

The development of advanced mixed matrix membranes (MMMs) is expanding through the design of functionalized materials and efficient hybrid mass transfer mechanisms to meet the growing needs for practical and cost-effective gas separation technologies. Here, a novel series of transition metal-doped covalent triazine frameworks (M2+CTFs) was synthesized and incorporated into a 6FDA-Durene polyimide (PI) matrix in the range of 0–0.5 wt% to prepare cost-effective facilitated transport MMMs with high CO2 separation performance. Qualitative and quantitative analyses including FTIR, XPS, CHN, XRF, BET, XRD, TGA, DLS, FESEM, EDX, and TEM were carried out. The presence of nucleophilic N sites and electron-rich heterocycles in highly porous CTFs (through the π–π-stacking interactions with CO2 molecules), together with transition metal ions (Fe2+, Cu2+, and Zn2+) as the fixed site active carriers (with strong CO2 facilitated transport through the π complexation/decomplexation reaction), improves the affinity for CO2 molecules, facilitates their transport, and subsequently increases the CO2/non-polar gas selectivity of MMMs. The resultant M2+CTF/PI MMMs successfully surpass the 2008 upper bound at filler loading of 0.4 wt% for CO2/CH4 and CO2/N2 separations. Embedding M2+CTFs into the PI matrix improves the mechanical properties of the membranes. The Zn2+CTF/PI MMM represents the best separation performance with a CO2 permeability of 1408 Barrer, a CO2/N2 selectivity of 37, and a CO2/CH4 selectivity of 39, which represents a 120 %, 111 %, and 110 % increase compared to the neat PI membrane at a feed pressure of 2 bar. The excellent results of the present study indicate the high potential of cost-efficient synthesized M2+CTF particles and related facilitated transport MMMs for possible application in industrial processes.

Polymer-modified nanofillers for enhancing CO2 separation performance of MMMs: A comparative study on the role of bridging ligands

Advanced CO2 separation technology is one of the key technologies for reducing carbon emissions and can make significant contributions to reducing the negative impact of the greenhouse effect on human survival. Membrane separation technology is regarded as a new generation of carbon capture technology because of its great potential to reduce carbon capture energy consumption and improve net carbon capture efficiency. Mixed matrix membranes (MMMs) can break through the performance limit of traditional polymer membranes, but the influence of bridging agents for post-modifying nanofillers on membrane structure and properties needs further systematic investigation. In this work, four types of ligands were selected for synthesizing polymer-modified nanofillers and then incorporated into poly (vinylamine) (PVAm) to prepare MMMs. The comparative analysis results indicate that bridging ligands with superior flexibility are conducive to enhancing the gas permeability within the pores by diminishing the compactness of the polymer shell. The constructed phase interface transition area with uniformly enhanced mechanical strength demonstrates the improved interface compatibility between the matrix and nanofillers bridged via the flexible ligand. Techno-economic evaluation verifies the industrial application potential of the optimal MMMs targeting CO2 capture from post-combustion gas.

Preparation mixed matrix membranes with different types of Al2O3-NOHMs for enhancing CO2 separation performance

ABSTRACT Nano-organic hybrid materials (Al2O3-NOHMs) were synthesized with nano-alumina as the core, γ-(2,3-epoxypropyl) propyl trimethoxysiane (KH560) as the corona, and three of polyetheramine M2070, D2000, M1000 as the canopy, respectively. Al2O3-NOHMs were used as fillers to prepare MMMs with Pebax as substrate to improve the CO2 separation performance. The Al2O3-NOHMs were characterized by TEM and rheological properties. The results showed that the synthesized Al2O3-NOHMs were liquid-like and had a core-shell structure, which can effectively reduce Al2O3 agglomeration in the membrane. FT-IR analysis of MMMs showed that Al2O3-NOHMs and Pebax were physically blended, TGA indicated that Al2O3-NOHMs do not affect the thermal stability of the membrane, and XRD indicated that the addition of Al2O3-NOHMs destroyed the interchain hydrogen bond of Pebax and reduced the crystallinity of MMMs. The gas permeability of the membrane was tested under ideal gas conditions, compared with pure membrane, the CO2 permeability of Al2O3-NOHM(M2070)/Pebax MMMs and Al2O3-NOHM(D2000)/Pebax MMMs reached 137.15 Barrer (24.68%) and 147.52 Barrer (34.11%), and the selectivity of CO2/N2 reached 77.82 (58.84%) and 72.31 (47.59%) at 30°C and 0.3 MPa, respectively, surpassing 2008 Robeson upper bound.

One-pot in situ synthesis of ZIF particles to prepare thin-film nanocomposite membranes for CO2 separation

Mixed matrix membranes (MMMs) are more likely to break the Robeson upper bound because they combine the pros of both organic and inorganic membranes. However, in the conventional MMM preparation processes, multi-steps are normally needed and, in many cases, the particle agglomeration and consequent non-selective voids are unavoidable, resulting in poor carbon dioxide (CO2) separation performances. In addition, the agglomeration makes it challenging to fabricate thin-film nanocomposite (TFN) membranes. In this study, zeolitic imidazolate framework (ZIF)-8- and ZIF-67-based TFN membranes were fabricated via a facile one-pot in situ synthesis protocol. The ZIF particles were synthesized in the polymeric solution, then the TFN membranes were fabricated by a dip coating method. With a casting solution concentration of 1.5 wt.%, a selective layer with a thickness of ∼300 nm can be prepared on the porous polyacrylonitrile (PAN) support. The results of thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), Fourier Transform Infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) showed that ZIFs were successfully synthesized in the casting solution. At 35 °C and 2 bar, the membrane containing 5 wt.% ZIF-67 had a CO2 permeance of 223.35 gas permeation unit (GPU), which was 16.55 % higher than that of pure Pebax.

Highly selective CO2 permeable double-network ionogel membrane containing 1-ethyl-3-methylimidazolium dicyanamide

A double-network (DN) ionogel membrane containing 1-ethyl-3-methylimidazolium dicyanamide ([C2mim][DCA]) was developed and evaluated for its mechanical robustness and its CO2 permeation properties. Polyvinyl alcohol (PVA) was used as the initial network for the DN ionogel membrane. It forms a partially-crystalline physical crosslinking within [C2mim][DCA] and acts as a sacrificial bond to toughen the ionogel. A loosely crosslinked poly(N,N-dimethylacrylamide) (PDMAAm) network was formed by free-radical polymerization to interpenetrate with the physically crosslinked PVA network. The more the gel was elongated, the more the physical crosslinking in the PVA network were broken and the more energy was dissipated. As a result, the ion gel toughened. Owing to its excellent toughness, the developed DN ionogel membrane retained 93 wt% of [C2mim][DCA] and exhibited the CO2 permeability and the CO2 perm-selectivity over N2 of 2920 barrer and 61, respectively, the highest level of CO2 separation performance among the latest CO2 separation membranes. The DN ionogel membrane kept the CO2 separation performance required for CO2 capture from flue gases from coal-fired power plants even at 80 °C and 80 % relative humidity.

Bimetallic MOF-74-based mixed matrix membrane for efficient CO2 separation

The bimetallic Ni(Zn)-MOF-74 nanoparticles were fabricated by the metal substitution method and doped into a polyether-polyamide block copolymer (Pebax 1657) matrix to obtain mixed matrix membrane (MMM) for CO2/CH4 separation. The pore structure and chemical properties of Ni(Zn)-MOF-74 nanoparticles were controlled by changing the molar ratio of Ni/Zn, and the effect of heterometallic on the gas separation performance of MMMs was studied. In particular, when the molar ratio of Ni/Zn was 2:1, the Pebax/Ni(Zn)-MOF-74-21 MMMs has the optimal CO2 separation performance. The main reason was that Ni(Zn)-MOF-74-21 has the smallest pore size (0.68 nm) and abundant CO2 adsorption sites, which could effectively prevent the entry of CH4 molecules after preferentially adsorbing one or two CO2 molecules, and improve the selectivity of CO2/CH4 molecules. Furthermore, the unreplaced pore size of 1.48 nm and the increased polymer chain spacing in Ni(Zn)-MOF-74-21 nanoparticles could provide a fast transport channel for CO2 and improve the permeability of MMMs. The developed Pebax/Ni(Zn)-MOF-74-21 MMMs loaded with 2 wt% filler displayed a CO2/CH4 selectivity of 33.7 and a high CO2 permeability of 719.9 barrer, exceeding the gas separation performance of many previously reported MOF-74-based MMMs. The results showed that the development and design of bimetallic organic framework was an important way to obtain high performance MOF-74-based MMM.

Molecular Dynamics Simulations of Gas Transport Properties in Cross-Linked Polyamide Membranes: Tracing the Morphology and Addition of Silicate Nanotubes.

This study employs molecular dynamics (MD) simulations to fundamentally provide insight into the role of cross-link density in the CO2 separation properties of interfacially polymerized polyamide (PA) membranes. For this purpose, two atomistic models of pure polyamide membranes with different cross-link densities are constructed by MD simulations to conceptually determine how the fractional free volume of polyamide affects the gas separation performance of the membrane. The PA membrane with a lower cross-link density (LCPA) shows a higher gas diffusion coefficient, a lower gas solubility coefficient, and a higher gas permeability than the PA membrane with a higher cross-link density (HCPA). Moreover, the pristine and modified silicate nanotubes (SNTs) as the fast gas transport channels are incorporated into the polyamide membranes to assess the effect of the SNT/PA interface chemistry on the CO2 separation properties of the membranes. SNTs are systematically modified by three modifying agents with different CO2-philic groups and different interfacial interaction energies with the polyamide matrix. The results of MD simulations demonstrate that the incorporation of silicate nanotubes into the PA matrix increases the gas diffusivity and permeability and decreases the CO2/gas selectivity. Moreover, the membranes containing modified SNTs possessing high CO2-philicity and high SNTs/PA interfacial interactions show a high CO2 separation performance.

Tuning MOF/polymer interfacial pore geometry in mixed matrix membrane for upgrading CO2 separation performance.

The current paradigm considers the control of the MOF/polymer interface mostly for achieving a good compatibility between the two components to ensure the fabrication of continuous mixed-matrix metal-organic framework (MMMOF) membranes. Here, we unravel that the interfacial pore shape nanostructure plays a key role for an optimum molecular transport. The prototypical ultrasmall pore AlFFIVE-1-Ni MOF was assembled with the polymer PIM-1 to design a composite with gradually expanding pore from the MOF entrance to the MOF/polymer interfacial region. Concentration gradient-driven molecular dynamics simulations demonstrated that this pore nanostructuring enables an optimum guided path for the gas molecules at the MOF/polymer interface that decisively leads to an acceleration of the molecular transport all along the MMMOF membrane. This numerical prediction resulted in the successful fabrication of a [001]-oriented nanosheets AlFFIVE-1-Ni/PIM-1 MMMOF membrane exhibiting an excellent CO2 permeability, better than many MMMs, and ideally associated with a sufficiently high CO2/CH4 selectivity that makes this membrane very promising for natural gas/biogas purification.

Polymer-incorporated modified halloysite nanotubes for efficient CO2/N2 separation

Mixed-matrix membranes (MMMs) as one of solid sorbents for carbon dioxide (CO2) separation face the challenge of merging efficient separation with economical preparation process using scalable raw material. Halloysite nanotubes (Hal) with unique one-dimensional gas transmission channels have great prospect in MMMs for gas separation. However, the insufficient porosity of Hal has restricted further development of CO2 separation performances. Herein, a facile and efficient modification approach was carried out, involving successive treatments of calcination and selective leaching. The resulting nanotubes with continuous channel systems (CA-Hal) are embedded in poly(ether-block-amide) for the preparation of mixed-matrix membranes with enhanced gas transport. The performances of MMMs with modified nanotubes as inorganic fillers obtained by different modification methods (calcination, selective leaching, and a combination of calcination and selective leaching) were specifically discussed. CA-Hal with the highest specific surface area and certain surface energy has an excellent potential as inorganic fillers, which can be uniformly dispersed in the polymer matrix to form interfacial channels, preventing the particle agglomeration and producing non-selective interfacial defects. The hierarchical porous structure of CA-Hal can serve as fast gas transport channels in MMMs for efficient CO2 diffusion and enhanced separation. The MMMs containing 5 wt% CA-Hal have demonstrated excellent CO2 permeability (179.5 Barrer), CO2 diffusivity (17.56 10−7 cm2·S−1) and CO2/N2 selectivity (98.7). In addition, the prepared MMMs exhibits improved mechanical properties compared with the pure membrane without inorganic fillers.

La0.8Sr0.2Ga0.8Mg0.2O3−δ − molten carbonate membrane for high − temperature CO2 separation

A perovskite structure La0.8Sr0.2Ga0.8Mg0.2O3−δ (LSGM), is a promising support material for dual − phase membrane for high − temperature CO2 separation owing to its high oxygen ion conductivity. The microstructure plays an important role in CO2 separation performance of the membrane. The result shows that effective particle − to − particle contact is a crucial guarantee for improving CO2 permeability. The uniformly distributed small pores of the support can greatly reduce the leakage. The Al2O3 coating on the porous support can improve the wettability between LSGM and molten carbonate, simultaneously increasing CO2 permeation flux while reducing leakage. The Al2O3 coated LSGM − based dual − phase membrane achieves a CO2 permeation flux of 0.34 mL min−1 cm−2 at 750 °C, with no detectable leakage. Above 750 °C, a reaction occurs between LSGM and molten carbonate, leading to a decline in membrane performance. For LSGM − carbonate dual − phase membranes, it is recommended to operate at temperatures not exceeding 750 °C.