Pebax–polydopamine microsphere mixed‐matrix membranes for efficient CO2 separation

Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO₂–CH₄ gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO₂–CH₄ selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO₂ separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO₂ permeability and CO₂–CH₄ selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.     

Synthesis and characterization of poly(ether-<Emphasis Type="Italic">block</Emphasis>-amide) copolymers/multi-walled carbon nanotube nanocomposite membranes for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

One of the effective techniques for improving separation properties of polymeric membranes is incorporation of suitable nanoparticles into their matrices. This study presents the preparation of three types of nanocomposite membranes comprising three grades of poly (ether-block-amide) (Pebax 1074, Pebax 1657 and Pebax 2533) and modified multi-walled carbon nanotubes (MWCNTs) with different loadings (1, 1.5, 2 and 2.5 wt%). The prepared membranes were characterized by field emission scanning electron microscopy (FESEM), attenuated total reflection-Fourier transfer infrared spectroscopy (ATR-FTIR) and X-ray diffraction (XRD). Permeation of CO₂ and CH₄ gases through the prepared membranes was measured at the pressure range of 2-8 bars and 25 °C. The results showed that the incorporation of MWCNTs into the polymers matrices improves CO₂/CH₄ selectivity. Further, Pebax 1074/MWCNT nanocomposite membrane exhibits better performance for CO₂/CH₄ separation compared to the neat Pebax and the two other nanocomposite membranes.     

High speed spin coating in fabrication of Pebax 1657 based mixed matrix membrane filled with ultra-porous ZIF-8 particles for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

Modified ultra-porous ZIF-8 particles were used to prepare novel ZIF-8/Pebax 1657 mixed matrix membranes (MMMs) on PES support for separation of CO₂ from CH₄ using spin coating method. TEM and SEM were used to characterize modified ZIF-8 particles. SEM was also used to investigate the morphology of synthesized MMMs. The MMMs with thinner selective layer showed higher CO₂ permeability and lower CO₂/CH₄ selectivity in permeation tests compared to MMMs with thicker selective layer. The plasticization was recognized as the main reason for rise in CO₂ permeability and drop in CO₂/CH₄ selectivity of thinner MMMs. The gas sorption results showed that the high permeability of CO₂ in MMMs is mainly due to the high solubility of this gas in MMMs, leading to high CO₂/CH₄ solubility selectivity for MMMs. The fractional free volume and void volume fraction of MMMs increased as the thickness of membrane decreased. Applying higher mixed feed pressures and permeation tests temperatures resulted in increase in CO₂ permeability and decrease in CO₂/CH₄ selectivity. At highest testing temperature (60 °C), the CO₂ permeability of synthesized MMMs with thinner selective layer remarkably increased.     

Pebax membrane for CO2/CH4 separation: Effects of various solvents on morphology and performance

In this study, the effects of different solvents on the morphology and permeation of poly(ether‐block‐amide) (Pebax‐1657) membranes were investigated. Pebax membranes were fabricated via a solution casting method with five different solvents, that is, N,N‐dimethyl formamide (DMF), N,N‐dimethyl acetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), formic acid, and a mixture of ethanol (EtOH) with water (H₂O). Cross‐sectional scanning electron microscopy analysis of the membranes was performed to investigate the morphology of the prepared membranes. X‐ray diffraction and Fourier transform infrared analysis were also carried out to characterize the membranes. The interactions of the polymer and various solvents were evaluated with Hansen solubility parameters. Permeation experiments for CO₂ and CH₄ gases were performed to study the effects of the solvents on the permeation properties of the membranes. The solvent properties, such as the molar volume, boiling point, and solubility parameters, were investigated as were the membranes characteristics, such as the crystallinity, d‐spacing, and fractional free volume. The results obtained from the experiments show that the CO₂ permeability for the membranes prepared with different solvents followed this order: NMP > DMF > Formic acid > DMAc > H₂O/EtOH mixture. With increasing molar volume, the gas permeability increased for all of the membranes, except for DMAc, which showed a lower permeability because of its highly crystalline structure. DMF showed a higher CO₂/CH₄ ideal selectivity compared to the other membranes and, consequently, could be introduced as the best solvent from all aspects for the Pebax‐1657 membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44531.     

Synthesis of High‐Performance Pebax®‐1074/DD3R Mixed‐Matrix Membranes for CO2/CH4 Separation

This work deals with the incorporation of deca‐dodecasil 3 rhombohedral (DD3R) zeolite as an inorganic filler into the Pebax®‐1074‐based polymer matrix to enhance the performance of the pure polymeric membrane in CO₂/CH₄ separation. The membranes were fabricated with different concentrations of DD3R. Separation performances of the membranes were investigated at various feed pressures and temperatures. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) analysis of the prepared membranes were performed. In the best case, selectivity for CO₂/CH₄ separation was improved, while the permeability decreased. Membranes with 1 and 5 wt % DD3R were located in the acceptable region beyond the Robeson plot (1991) for CO₂/CH₄ gas pairs.     

Application of poly (amide-<Emphasis Type="Italic">b</Emphasis>-ethylene oxide)/zeolitic imidazolate framework nanocomposite membrane in gas separation

Mixed matrix membranes (MMMs) are gaining increasing interest in academic and industrial research due to their combined, desirable properties of both polymers and organic/inorganic filler as important materials. In this work, synthesized zeolitic imidazolate framework (ZIF-8) suspension (10–50 wt%) was directly incorporated into a [poly (amide-b-ethylene oxide) Pebax^® 1657] matrix in order to improve the gas separation performance of the membrane. Dynamic light scattering (DLS) analysis showed an average diameter of 77.4 nm for the prepared nanoparticles. The transparent membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffractometry (XRD). These indicated excellent dispersion of nanoparticles, which was achieved by ultrasonication before casting the solution. Incorporation of ZIF-8 as filler in the polymer matrix led to improved thermal and mechanical stability of the membranes. This was confirmed by TGA and tensile analyses, indicating good contacts provided at the polymer/filler interfaces. The effect of ZIF-8 loading (up to 50 wt%) on membrane performance was investigated and it showed an optimum loading of 30 %. Single gas (CO₂, N₂ and CH₄) permeation tests revealed rapid, enhanced permeability of the nanocomposite membranes without significant changes in selectivity (compared to those of the pristine polymeric membrane). The permeability increases for CO₂, CH₄ and N₂ in the optimum Pebax^® 1657/ZIF-8 (30 wt%) membrane were found in the stated order as 111, 88 and 99 %. The study revealed that Pebax^® 1657/ZIF-8 membranes displayed better gas permeation properties compared to those of Pebax^® 1657.     

Performance evaluation of a synthesized and characterized Pebax1657/PEG1000/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> membrane for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation using response surface methodology

In this work, the response surface methodology (RSM) based on the central composite design (CCD) was used to examine effects of different gamma alumina (γ-Al₂O₃) loadings (0 to 8 wt.%) and various polyethylene glycol 1000 (PEG1000) contents (0 to 40 wt.%) as parameters on membrane preparation. Accordingly, pure carbon dioxide (CO₂) and methane (CH₄) gasses permeability and ideal CO₂/CH₄ selectivity values were considered as responses. Poly (ether block amide) 1657 (Pebax1657) was used as the base polymer matrix for the membranes fabrication. The neat Pebax1657 membrane was prepared via solution casting-solvent evaporation method and the other membranes were prepared via solution blending technique. Analysis of variance (ANOVA) was used to analyze the experiments statistically and the results indicated that the optimized amounts of γ-Al₂O₃ nanoparticles and PEG1000 in order to enhance both CO₂ permeability and ideal CO₂/CH₄ selectivity were 8 wt.% and 10 wt.%, respectively. Additionally, a comparison between the separation performance of the neat membrane, the nanocomposite membrane with the optimum amount of γ-Al₂O₃ nanoparticles, the blended membrane with optimum amounts of PEG1000, and the blended nanocomposite membrane with optimum amounts of γ-Al₂O₃ nanoparticles and PEG1000 was presented. The obtained gas permeation results showed that the blended nanocomposite membrane exhibits the highest CO₂/CH₄ separation performance compared to the neat Pebax membrane.     

Effect of graphene oxide on the behavior of poly(amide‐6‐b‐ethylene oxide)/graphene oxide mixed‐matrix membranes in the permeation process

Polyether‐block‐amide (Pebax)/graphene oxide (GO) mixed‐matrix membranes (MMMs) were prepared with a solution casting method, and their gas‐separation performance and mechanical properties were investigated. Compared with the pristine Pebax membrane, the crystallinity of the Pebax/GO MMMs showed a little increase. The incorporation of GO induced an increase in the elastic modulus, whereas the strain at break and tensile strength decreased. The apparent activation energies (E_p) of CO₂, N₂, H₂, and CH₄ permeation through the Pebax/GO MMMs increased because of the greater difficulty of polymer chain rotation. The E_p value of CO₂ changed from 16.5 kJ/mol of the pristine Pebax to 23.7 kJ/mol of the Pebax/GO MMMs with 3.85 vol % GO. Because of the impermeable nature of GO, the gas permeabilities of the Pebax/GO MMMs decreased remarkably with increasing GO content, in particular for the larger gases. The CO₂ permeability of the Pebax/GO MMMs with 3.85 vol % GO decreased by about 70% of that of the pristine Pebax membrane. Rather than the Maxwell model, the permeation properties of the Pebax/GO MMMs could be described successfully with the Lape model, which considered the influence of the geometrical shape and arrangement pattern of GO on the gas transport. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42624.     

The effect of ZIF-90 particle in Pebax/Psf composite membrane on the transport properties of CO2, CH4 and N2 gases by Molecular Dynamics Simulation method

Nowadays, mixed matrix membranes (MMMs) have considered by many researchers to overcome the problems of polymeric membranes. In addition, molecular dynamics (MD) and Monte Carlo (MC) simulation Methods are suitable tools for studying transport properties and morphology in MMMs. For this purpose, in this study using material studio 2017 (MS) software, the transport properties of CO₂, CH₄ and N₂ in Pebax, Psf neat Pebax/Psf composite and Pebax/Psf composite filled with ZIF-90 particles have been investigated. By adding Psf to Pebax matrix, the selectivity of CO₂/CH₄ and CO₂/N₂ gases has significantly increased. In addition, adding ZIF-90 particles to the Pebax/Psf composite increased the permeability of CO₂, CH₄ and N₂ compared to neat and composite membranes. The morphological properties of the membranes, such as the fractional free volume (FFV), radial distribution function (RDF), glass transition temperature (T_G), X-ray diffraction (XRD) and equilibrium density have calculated and acceptable results have obtained.     

Improved CO2/CH4 separation performance of mixed-matrix membrane by adding ZIF-7-NH2 nanocrystals

Membrane-based technology is an attractive alternative in terms of CO₂ separation. Pebax-based membranes are regarded as potential candidates for CO₂ separation due to the favorable interaction between its poly (ethylene oxide) chains with CO₂ molecules and inorganic fillers. However, the separation performance for CO₂/CH₄ mixture is still suffered from the moderate gas permeability and selectivity. To overcome this problem, in this work, amino-functionalized zeolite imidazolate framework (ZIF-7-NH₂) nanocrystals were used as fillers to blend with Pebax 1657 for fabricating mixed-matrix membranes (MMMs). XRD, Brunauer–Emmett–Teller (BET), scanning electron microscope, and ¹H nuclear magnetic resonance characterization indicated that ZIF-7-NH₂ with the highest crystallinity was synthesized. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and Young's modulus showed that it has good interfacial interaction. Gas separation test results showed that both the CO₂ permeability and CO₂/CH₄ selectivity of the 31 wt% ZIF-7-NH₂/Pebax MMMs increased by 80 and 170%, respectively. The improved performance is attributed to the addition of ZIF-7-NH₂ nanocrystals and the favorable interfacial interactions between the polymer and ZIF-7-NH₂ nanocrystals. Furthermore, the polyvinylidene fluoride supported hollow fiber composite membranes also exhibit the long-term stability for CO₂/CH₄ separation.     

Fabrication of Homogenous Polymer‐Zeolite Nanocomposites as Mixed‐Matrix Membranes for Gas Separation

Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO₂/N₂ and CO₂/CH₄ selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO₂/CH₄ and CO₂/N₂ at the three examined feed pressures of 4, 8 and 12 atm.     

Effect of support layer on gas permeation properties of composite polymeric membranes

PES/Pebax and PEI/Pebax composite membranes were prepared by coating the porous PES and PEI substrate membranes with Pebax-1657. The morphology and performance of the prepared membranes were investigated by SEM and CO₂ and CH₄ permeation tests. The CO₂ permeances of 28 and 52 GPU were achieved for PES/Pebax and PEI/Pebax composite membranes, respectively, with CO₂/CH₄ selectivities almost equal to that of Pebax (26). The experimental data were further subjected to a theoretical analysis using the resistance model. It was found that the porosity and the thickness of the dense section of PES substrate were an order of magnitude higher than those of PEI substitute. The porosity/thickness ratio of PEI substrate was, however, higher than PES, explaining the higher permeance of PEI/Pebax composite membrane. Substrates with porosities much higher than the Henis-Tripodi gas separation membrane were used in this work, aiming to achieve the selectivity of Pebax, rather than those of the substrate membrane materials.     

Preparation of poly(ether‐block‐amide)/poly(amide‐co‐poly(propylene glycol)) random copolymer blend membranes for CO2/N2 separation

A series of poly(amide‐co‐poly(propylene glycol)) (PA‐PPG) random copolymers with different content of PPG were designed by polycondensation reaction. These random copolymers were blended up to 60% with commercially available Pebax 2533. The blend membranes were characterized by Fourier‐transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning electron microscope (SEM). Gas permeation properties of these blend membranes were investigated using five single‐gases (CO₂, H₂, O₂, CH₄, and N₂) at different temperature of 25–55°C and 1.0 atm. The impacts of content of PA‐PPG with different PPG content and operating temperature on CO₂ separation properties of Pebax/PA‐PPG blend membranes were studied. The results showed that CO₂ permeability gradually increased with the increasing operating temperature, whereas CO₂ permeability gradually decreased with the increase in content of PA‐PPG. CO₂/N₂ selectivity gradually increased with the increase in content of PA‐PPG. In particular, Pebax/PA‐PPG (50)–60% displayed excellent CO₂ and O₂ separation properties (P_CO2 = 79.7 Barrer and P_O2 = 13.6 Barrer, CO₂/N₂ = 34.7 and O₂/N₂ = 5.9) at 25°C and 1.0 atm. POLYM. ENG. SCI., 59:E14–E23, 2019. © 2018 Society of Plastics Engineers     

Effects of halloysite nanotubes on the morphology and CO2/CH4 separation performance of Pebax/polyetherimide thin-film composite membranes

Enhancing the performance of gas separation membranes is one of the major concerns of membrane researchers. Thus, in this study, poly(ether-block-amide) (Pebax)/polyetherimide (PEI) thin-film composite membranes were prepared and their CO₂/CH₄ gas separation performance was investigated by means of pure and mixed gases permeation tests. To improve the properties of these membranes, halloysite nanotubes (HNT) were added to Pebax layer at different loadings of 0.5, 1, 2, and 5 wt % to form Pebax-HNT/PEI membranes. Scanning electron microscopy, gas sorption, X-ray diffraction, Fourier-transform infrared, and differential scanning calorimetry tests were also performed to investigate the impact of HNT on structure and properties of prepared membranes. Results showed that both CO₂/CH₄ selectivity and CO₂ permeance increased by adding HNT to Pebax layer up to 2 wt %. By increasing HNT loading to 5 wt %, the CO₂/CH₄ selectivity decreased from 32 to 18, while CO₂ permeance increased from 3.25 to 4.2 GPU. Pebax/PEI and Pebax-HNT/PEI membranes containing 2 wt % of HNT were tested using CO₂/CH₄ gas mixtures at different feed CO₂ concentrations and feed pressure of 4 bar. The results showed that with increasing CO₂ concentration from 20 to 80 vol %, CO₂/CH₄ selectivity of Pebax/PEI composite membranes increased by 19%, while, in Pebax-HNT/PEI membrane, CO₂/CH₄ selectivity decreased by 40%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48860.     

Crosslinking and stabilization of nanoparticle filled poly(1‐trimethylsilyl‐1‐propyne) nanocomposite membranes for gas separations

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) has been crosslinked using 4,4′‐diazidobenzophenone bisazide to improve its chemical and physical stability over time. Crosslinking PTMSP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PTMSP was due to decrease in diffusion coefficient. Compared with the pure PTMSP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (fumed silica, titanium dioxide), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O₂/N₂, H₂/N₂, CO₂/N₂, CO₂/CH and H₂/CH₄ using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PTMSP membranes and PTMSP/filler nanocomposites over time. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A high CO2 permselective mesoporous silica/carbon composite membrane for CO2 separation

Ordered mesoporous silica/carbon composite membranes with a high CO₂ permeability and selectivity were designed and prepared by incorporating SBA-15 or MCM-48 particles into polymeric precursors followed by heat treatment. The as-made composite membranes were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and N₂ adsorption, of which the gas separation performance in terms of gas permeability and selectivity were evaluated using the single gas (CO₂, N₂, CH₄) and gas mixtures (CO₂/N₂ and CO₂/CH₄, 50/50 mol.%). In comparison to the pure carbon membranes and microporous zeolite/C composite membranes, the as-made mesoporous silica/C composite membranes, and the MCM-48/C composite membrane in particular, exhibit an outstanding CO₂ gas permeability and selectivity for the separation of CO₂/CH₄ and CO₂/N₂ gas pairs owing to the smaller gas diffusive resistance through the membrane and additional gas permeation channels created by the incorporation of mesoporous silicas in carbon membrane matrix. The channel shape and dimension of mesoporous silicas are key parameters for governing the gas permeability of the as-made composite membranes. The gas separation mechanism and the functions of porous materials incorporated inside the composite membranes are addressed.     

Preparation and characterization of CO2-selective Pebax/NaY mixed matrix membranes

CO₂-selective Pebax/NaY mixed matrix membranes (MMMs) were prepared by incorporating NaY zeolite into Pebax matrix. The morphology, chemical groups, thermal stability, and microstructure of the MMMs were investigated by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction, respectively. The effects of zeolite loading amount, permeation temperature and pressure on the CO₂/N₂ separation performance of the resultant membranes were studied. The as-prepared MMMs are much superior to the pristine Pebax membranes in terms of permeability and selectivity. The CO₂ permeability and CO₂/N₂ selectivity can respectively reach to 131.8 Barrer and 130.8 for MMMs made by the starting materials containing 40 wt % NaY. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48398.     

Gas‐separation properties of amine‐crosslinked polyimide membranes modified by amine vapor

The modification of a polyimide (PI) membrane by aromatic amine vapor was performed in this work to increase the crosslinking of the membrane and to study the effect on gas permeability and the corresponding selectivity. The single‐gas permeability of the membranes at 35 °C was probed for H₂, O₂, N₂, CO₂, and CH₄. From the relationship between the combinations of gases and ideal permselectivities, this study showed that amine‐crosslinked PI membranes tended to increase gas permselectivities exponentially with the increasing difference in gas kinetic diameter. Moreover, this study illustrated that the permeability of the membranes was influenced by the formation rate of amine‐crosslinked networks or chemical structures after the reaction. The membranes had the highest level of permselectivities among crosslinked PI membranes for O₂/N₂, and the H₂/CH₄ permselectivity increased 26 times after vapor modification. Furthermore, the modification method that used aromatic amine vapor produced thin and strongly modified layers. These findings indicate that modification is an advantageous technique for improving gas‐separation performance, even considering thinning. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44569.     

Enhanced gas separation properties of metal organic frameworks/polyetherimide mixed matrix membranes

Metal organic frameworks (MOFs) are supposed to be ideal additives for mixed matrix membranes (MMMs). In this article one kind of MOFs, Cu₃(BTC)₂, is synthesized, then directly incorporated into a model polymer (Ultem®1000) using N,N‐dimethylacetamide as solvent. Cu₃(BTC)₂ particles are uniformly dispersed and there are no interfacial defects in the prepared MMMs when Cu₃(BTC)₂ loading is not more than 35 wt %, seen in SEM images. Pure gas permeation tests show that gas permeability increases obviously with Cu₃(BTC)₂ loading increase, while ideal selectivities of CO₂/N₂ and CO₂/CH₄ are almost unchanged. For MMM with the best separation property, CO₂ permeability increases about 2.6 times and CO₂/N₂ selectivity remains almost unchanged. Results about gas diffusivity and solubility indicate that gas diffusivity and solubility make contribution to gas permeability increase at the same time but in different ways. Gas permeation properties of MMMs are well predicted by Maxwell or Bruggeman model. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40719.     

Pebax-based mixed matrix membranes loaded with graphene oxide/core shell ZIF-8@ZIF-67 nanocomposites improved CO2 permeability and selectivity

In order to facilitate CO₂ transport in Pebax-based membranes, graphene oxide (GO)/core shell ZIF-8@ZIF-67 nanocomposites were loaded in Pebax copolymer to improve CO₂ permeability and selectivity. The 0.5 wt% GO doped core shell ZIF-8@ZIF-67, which gave highest CO₂ adsorption capacity of 1.12 mmol/g, was used as nanocomposite. The incorporated GO/core shell ZIF enhanced CO₂ adsorption via unsaturated metal sites (Zn-O or Co-O), because O atoms in GO substituted for N atoms coordinated with Zn and Co single atoms in core shell ZIF-8@ZIF-67. Positron annihilation lifetime spectroscopy indicated that GO-templated core shell ZIF nanocomposites generated extra free volume and provided low-resistance channels to facilitate CO₂ transport. Fourier transform infrared spectroscopy analysis revealed that hydrogen bonds were generated between Pebax polymer chains and GO-templated core shell ZIF which improved swelling resistance and reduced interface defects. Therefore, Pebax-based MMMs loaded with 5 wt% GO/core shell ZIF-8@ZIF-67 exhibited optimum CO₂ permeability (173.2 barrers) and ideal selectivity of CO₂/N₂ (61.9) and CO₂/H₂ (11.6), which were 99.7%, 66.4%, and 20.8% higher than Pebax membranes and surpass Robeson 2008 upper bound. The tensile strength increased by 17.6% to 28.8 MPa and elongation at break increased by 7.61%–554.6% when pure Pebax membranes were incorporated with 2.5 wt% GO/core shell ZIF-8@ZIF-67.