Fabrication and characterization of poly(phenylene oxide)/SBA-15/carbon molecule sieve multilayer mixed matrix membrane for gas separation

A novel multilayer mixed matrix membrane (MMM), consisting of poly(phenylene oxide) (PPO), large-pore mesoporous silica molecular sieve zeolite SBA-15, and a carbon molecular sieve (CMS)/Al₂O₃ substrate, was successfully fabricated using the procedure outlined in this paper. The membranes were cast by spin coating and exposed to different gases for the purpose of determining and comparing the permeability and selectivity of PPO/SBA-15 membranes to H₂, CO₂, N₂, and CH₄. PPO/SBA-15/CMS/Al₂O₃ MMMs with different loading weights of zeolite SBA-15 were also studied. This new class of PPO/SBA-15/CMS/Al₂O₃ multilayer MMMs showed higher levels of gas permeability compared to PPO/SBA-15 membranes. The permselectivity of H₂/N₂ and H₂/CH₄ combinations increased remarkably, with values at 38.9 and 50.9, respectively, at 10 wt% zeolite loading. Field emission scanning electron microscopy results showed that the interface between the polymer and the zeolite in MMMs was better at a 10 wt% loading than other loading levels. The increments of the glass transition temperature of MMMs with zeolite confirm that zeolite causes polymer chains to become rigid.     

Gas sorption in H2-selective mixed matrix membranes: Experimental and neural network modeling

Robust artificial neural network (ANN) was developed to forecast sorption of gases in membranes comprised of porous nanoparticles dispersed homogenously within polymer matrix. The main purpose of this study was to predict sorption of light gases (H₂, CH₄, CO₂) within mixed matrix membranes (MMMs) as function of critical temperature, nanoparticles loading and upstream pressure. Collected data were distributed into three portions of training (70%), validation (19%), and testing (11%). The optimum network structure was determined by trial-error method (4:6:2:1) and was applied for modeling the gas sorption. The prediction results were remarkably agreed with the experimental data with MSE of 0.00005 and correlation coefficient of 0.9994.     

Preparation of mixed matrix composite membrane for hydrogen purification by incorporating ZIF-8 nanoparticles modified with tannic acid

The incompatibility between nanofillers and polymer, caused by the agglomeration of nanoparticles and their weak interaction with each other, is still a challenge to develop mixed matrix composite membrane. Herein, we introduced the ZIF-8-TA nanoparticles synthesized by in situ hydrophilic modification into the hydrophilic poly(vinylamine) (PVAm) matrix to prepare composite membranes for H₂ purification. The dispersion of ZIF-8 in water was improved by tannic acid modification, and the compatibility between ZIF-8 particles and PVAm matrix was enhanced by chemical crosslinking between the quinone groups in oxidized tannic acid (TA) and the amino groups in PVAm. Moreover, the compatibility between hydrophobic polydimethylsiloxane (PDMS) gutter layer and hydrophilic separation layer was achieved by the adhesion of TA-Fe³⁺ complex to the surface of PDMS layer during membrane preparation. The interlayer hydrophilic modification and the formation of separation layer were accomplished in one step, which simplified the preparation process. The experimental results indicated that when the TA addition used for modification was 0.5 g and the ZIF-8-TA_0.5 content in membrane was 12 wt%, the prepared membrane showed the best separation performance with the CO₂ permeance of 987 GPU and the CO₂/H₂ selectivity of 31, under the feed gas pressure of 0.12 MPa.     

A novel organic/inorganic polymer membrane based on poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid/3-glycidyloxypropyl trimethoxysilane polymer electrolyte membrane for direct methanol fuel cells

Poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS)/3-glycidyloxypropyl)trimethoxysilane (PVA/PAMPS/GPTMS) organic/inorganic proton-conducting polymer membranes are prepared by a solution casting method. PAMPS is a polymeric acid commonly used as a primary proton donor, while 3-(glycidyloxypropyl)trimethoxysilane (GPTMS) is an inorganic precursor forming a semi-interpenetrating network (SIPN). Varying amounts of sulfosuccinic acid (SSA) are used as the cross-linker and secondary proton source. The characteristic properties of PVA/PAMPS/GPTMS composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. Direct methanol fuel cells (DMFCs) made of PVA/PAMPS/GPTMS composite membranes are assembled and examined. Experimental results indicate that DMFCs employing an inexpensive, non-perfluorinated, organic/inorganic SIPN membrane achieve good electrochemical performance. The highest peak power density of a DMFC using PVA/PAMPS/GPTMS composite membrane with 2 M CH₃OH solution fuel at ambient temperature is 23.63 mW cm⁻². The proposed organic/inorganic proton-conducting membrane based on PVA/PAMPS/GPTMS appears to be a viable candidate for future DMFC applications.     

Experimental investigation of natural polysaccharide-based mixed matrix membrane modified with graphene oxide and Pd-nanoparticles for enhanced gas separation performance

In this work, we proposed a mixed matrix membrane prepared by using a glycerol modified guar gum (GGP) polymer matrix incorporated with graphene oxide (GO). The influence of varying GO concentration on the gas separation performance was investigated and 2 wt% was found to be the optimum concentration for high performance. The 2 wt% GO mixed matrix membranes were further modified with Pd nanoparticles. When GO, and Pd nanoparticles were mixed, CO₂ permeability increased by 49.94%, while the permeability of H₂ gas molecules decreased by 98.11%, respectively, compared to the pristine GGP membrane. The selectivity of CO₂/H₂ was obtained as 18.27. The glass transition temperature of the membrane increased from 85 to 95.2 °C, tensile strength and elongation of the break were significantly improved by 29.09% and 84.37% through the addition of Pd and GO into the membrane. The scanning electron microscopy revealed a dense top surface after GO nanosheets incorporation. Further, the thermogravimetric analysis proposes that the modified membrane is thermally stable than GGP. Henceforth, the study suggests GO incorporation and Pd nanoparticles modification of guar gum membrane is a promising gas separation membrane with potentially high selectivity for CO₂ gas.     

Nafion/poly(1-vinyl-1,2,4-triazole) blends as proton conducting membranes for polymer electrolyte membrane fuel cells

In this study, proton conducting Nafion-poly(1-vinyl-1,2,4-triazole) blends are produced. Nafion/polymer blend membranes are prepared by means of film casting from the Nafion-PVTri solutions at several molar ratios of PVTri repeat unit to -SO₃H. The chemical structure of the homopolymer PVTri is confirmed by FT-IR and ¹³C NMR. Thermal properties are investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and the results illustrated that all these Nafion-PVTri electrolytes are thermally stable at least up to 300 °C. The membrane properties are further characterized for their morphology by scanning electron microscopy (SEM) and water uptake measurements. The methanol permeability of these membranes is measured and the results exhibited that they have quite lower methanol permeability compared to pristine Nafion112. The electrochemical properties of PVTri are investigated by cyclic voltammetry. The conductivity of Nafion-P(VTri)₁ blend membranes is measured to be 5.3 × 10⁻⁴ S cm⁻¹ at 220 °C, in anhydrous state. The conductivity of blend increased at least three orders of magnitude up on hydration, i.e., exceeding 10⁻³ S cm⁻¹ with RH = 50% at ambient temperature.     

Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety and poly(amic acid) for proton exchange membrane fuel cell application

Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety and poly(amic acid) with oligoaniline in the main chain have been prepared and immersed in H₃PO₄ to obtain acid-doped composite films. As expected, the water uptake values and methanol permeability of the composite membranes decrease with the increase of the weight fraction of PAA in the membrane matrix. Notably, the SPEEK-6F/PAA-15 shows a water uptake of 13.2% and a methanol permeability of 0.9 × 10⁻⁷ cm² s⁻¹, which are much lower than those of the Nafion (28.6% and 15.5 × 10⁻⁷ cm² s⁻¹, respectively). Although the proton conductivities decrease after the addition of PAA, higher selectivity values are obtained with the composite membranes. Therefore, the SPEEK-6F/PAA blend membranes, with the improved proton conductivity, methanol resistance and good thermal stability, can be used as a good alternative for proton conductive membranes with potential application in proton exchange membrane fuel cells (PEMFCs).     

4-Aminopyridine grafted sulfonated poly(arylene ether ketone sulfone) proton exchange membrane with high relative selectivity for fuel cells

A series of sulfonated poly(arylene ether ketone sulfone)s polymer having a degree of sulfonation of 80% and a carboxyl group in the side chain (C-SPAEKS) were prepared by polycondensation. The 4-aminopyridine grafted sulfonated poly(arylene ether ketone sulfone)s polymer membranes (SPPs) were prepared by amidation reaction with the carboxyl group to immobilize 4-aminopyridine on the side chain. The ¹H NMR results and Fourier transform infrared of SPP membranes demonstrated the successful grafting of the 4-aminopyridine. Proton conductivity, water absorption, swelling ratio, and thermal stability of different proportions of SPP membranes were investigated under the different conditions. With the increase of pyridine grafting content, the methanol permeability coefficient of the membrane decreased significantly from 8.17 × 10⁻⁷ cm²s⁻¹ to 8.92 × 10⁻⁸ cm²s⁻¹ at 25 °C. And, the proton conductivity and relative selectivity of the membrane were positively correlated with the grafted pyridine content. Among them, the SPP-4 membrane exhibited the highest proton conductivity of 0.088 Scm⁻¹ at 100 °C. The relative selectivity increased from 4.73 × 10⁴ S scm⁻³ to 9.84 × 10⁴ S scm⁻³.     

Development and characterization of polymer electrolyte membranes based on ionical cross-linked poly(1-vinyl-1,2,4 triazole) and poly(vinylphosphonic acid)

The fabrication, thermal and proton conducting properties of complex polymer electrolytes based on poly(vinylphosphonic acid) (VPA) and poly(1-vinyl-1,2,4-triazole) (PVTri) were investigated throughout this work. The membrane materials were produced by complexation of PVPA with PVTri at various concentrations to get PVTriP(VPA)_x where x designates the molar ratio of the polymer repeating units and varied from 0.25 to 4. The complexed structure of the polymers was confirmed by FT-IR spectroscopy. The TGA results verified that the presence of PVTri in the complex polymer electrolytes suppressed the formation of phosphonic acid anhydrides up to 150 °C. The DSC and SEM results demonstrated the homogeneity of the materials. Proton conductivity, activation energy and water/methanol uptake of these membranes were also measured. PVTriP(VPA)₂ showed a proton conductivity of 2.5 × 10⁻⁵ S cm⁻¹ at 180 °C in the anhydrous state. After humidification (RH = 50%), PVTri-P(VPA)₄ and PVTri-P(VPA)₂ showed respective proton conductivities of 0.008 and 0.022 S cm⁻¹ at 100 °C, where the conductivity of the latter is close to Nafion 117 at the same humidity level.     

Direct methanol fuel cell based on poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) composite polymer membrane

The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO₂/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH₃OH fuels are 12.85, 23.72, and 10.99 mW cm⁻², respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO₂/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.     

HT-PEMs based on nitrogen-heterocycle decorated poly (arylene ether ketone) with enhanced proton conductivity and excellent stability

The proton transport can be enhanced by properly controlling the chemical structure of side chains. In this work, polyelectrolytes supported on poly (arylene ether ketone), decorated with four kinds of nitrogen-heterocycles, were prepared as alternative materials for high-temperature proton exchange membrane (HT-PEM) applications. Particularly, the “prominent basic” alongside backbone makes positive imidazole group more effective than other three to promote phosphoric acid doping, enhance proton conductivity and avoid phosphoric acid leakage. The obtained BrPAEK-MeIm1.6 membranes (1.6 imidazole/unit), with PA doping level of 19.2 in 1 h acid absorption process, exhibited the conductivity of 0.091 S cm^?1 at 170 °C. Under harsh experimental conditions, membrane with higher imidazole exhibited relatively higher phosphoric acid retention ability (27% enhancement). The stability of proton conductivity has also been demonstrated, which indicates that the PA/BrPAEK-MeIm1.6 come to an equilibrium state with 77.7% of initial conductivity after 5 h. Then, there is almost negligible conductivity loss within 30 h. These results provide a basic understanding of nitrogen-heterocyclic addition and PA absorption and open up avenues for further research in this area.     

Preparation and characterization of directional conducting and lower methanol permeable ultrathin membrane based on poly (vinyl alcohol) and imidazolium compounds

To produce directional conducting and lower methanol permeable ultrathin membrane for fuel cell, the imidazolium salt as both cross-linking agent and proton donor has been designed to build a directional proton conducting channel in a poly (vinyl alcohol)-based membrane. The methanol permeability of directional conducting membrane is very low, which is about twice smaller than that of Nafion₁₁₇. In addition, the membranes show a relatively high oxidative durability in H₂O₂ solutions, with only about 10% weight loss after the membrane being immersed in 3% H₂O₂ solution for 120 h. All the properties of prepared directional conducting membrane indicate their promising prospects in proton conducting membrane applications.