Highly selective sulfonated Poly (arylene ether nitrile) composite membranes containing copper phthalocyanine grafted graphene oxide for direct methanol fuel cell

To improve the performances of sulfonated poly (arylene ether nitrile) (SPEN)–based proton exchange membranes (PEMs) in direct methanol fuel cells (DMFCs), the copper phthalocyanine grafted graphene oxide (CP-GO) was successfully prepared via in situ polymerization and subsequently incorporated into SPEN as filler to fabricate a series of SPEN/CP-GO-X (X represents for the mass ratio of CP-GO) composite membranes. The water absorption, swelling ratio, mechanical properties, proton conductivity, and methanol permeability of the membranes were systematically studied. CP-GO possesses good dispersion and compatibility with SPEN matrix, which is propitious to the formation of strong interfacial interactions with the SPEN, so as to provide more efficient transport channels for proton transfer in the composite membranes and significantly improve the proton conductivity of the membranes. Besides, the strong π–π conjugation interactions between CP-GO and SPEN matrix can make the composite membranes more compact, blocking the methanol transfer in the membranes, and significantly reducing the methanol permeability. Consequently, the SPEN/CP-GO-1 composite membrane displayed outstanding tensile strength (58 MPa at 100% RH and 25°C), excellent proton conductivity (0.178 S cm−1 at 60°C), and superior selectivity (5.552 × 105 S·cm−3·s). This study proposed a new method and strategy for the preparation of high performance PEMs.

Promising Potential of Eugenol (Clove) Based Organic Membrane for Polymer Electrolyte Membrane Fuel Cell

Fuel cell is one of alternative method to replace fossil fuel energy. The important component of fuel cell is a membrane that used for separating cathode and anode also as a proton conductor. The purpose of this research is to produce polymer electrolyte membrane from poly (eugenol sulfonate) (PES) as polymer matrix, characterize the resulting membrane analysis using ionic properties analysis by calculating ionic conductivity using impedance spectroscopy, ion exchange capacity (IEC), solvent absorption analysis by calculating water uptake and methanol permeability, and studying mechanism Proton transport that occurs on the membrane. This research was initiated by making polymer of PES, and then fabrication and characterization of electrolytic polymer membrane. The formed membrane has an optimal proton conductivity of 0.00095 S.cm-1 with PES composition of 22% (wt).

Fabrication of Polyelectrolyte Membranes of Pectin Graft-Copolymers with PVA and Their Composites with Phosphomolybdic Acid for Drug Delivery, Toxic Metal Ion Removal, and Fuel Cell Applications

In this study, a simple method for the fabrication of highly diffusive, adsorptive and conductive eco-friendly polyelectrolyte membranes (PEMs) with sulfonate functionalized pectin and poly(vinyl alcohol)(PVA) was established. The graft-copolymers were synthesized by employing the use of potassium persulfate as a free radical initiator from pectin (PC), a carbohydrate polymer with 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS) and sodium 4-vinylbenzene sulphonate (SVBS). The PEMs were fabricated from the blends of pectin graft-copolymers (PC-g-AMPS and PC-g-SVBS) and PVA by using a solution casting method, followed by chemical crosslinking with glutaraldehyde. The composite PEMs were fabricated by mixing phosphomolybdic acid with the aforementioned blends. The PEMs were successfully characterized by FTIR, XRD, SEM, and EDAX studies. They were assessed for the controlled release of an anti-cancer drug (5-fluorouracil) and the removal of toxic metal ions (Cu2+) from aqueous media. Furthermore, the composite PEMs were evaluated for fuel cell application. The 5-fluorouracil release capacity of the PEMs was found to be 93% and 99.1% at 300 min in a phosphate buffer solution (pH = 7.4). The highest Cu2+ removal was observed at 206.7 and 190.1 mg/g. The phosphomolybdic acid-embedded PEMs showed superior methanol permeability, i.e., 6.83 × 10−5, and 5.94 × 10−5, compared to the pristine PEMs. Furthermore, the same trend was observed for the proton conductivities, i.e., 13.77 × 10−3, and 18.6 × 10−3 S/cm at 30 °C.

Fabrication of Eco-Friendly Polyelectrolyte Membranes Based on Sulfonate Grafted Sodium Alginate for Drug Delivery, Toxic Metal Ion Removal and Fuel Cell Applications

Polyelectrolyte membranes (PEMs) are a novel type of material that is in high demand in health, energy and environmental sectors. If environmentally benign materials are created with biodegradable ones, PEMs can evolve into practical technology. In this work, we have fabricated environmentally safe and economic PEMs based on sulfonate grafted sodium alginate (SA) and poly(vinyl alcohol) (PVA). In the first step, 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS) and sodium 4-vinylbenzene sulfonate (SVBS) are grafted on to SA by utilizing the simple free radical polymerization technique. Graft copolymers (SA-g-AMPS and SA-g-SVBS) were characterized by 1H NMR, FTIR, XRD and DSC. In the second step, sulfonated SA was successfully blended with PVA to fabricate PEMs for the in vitro controlled release of 5-fluorouracil (anti-cancer drug) at pH 1.2 and 7.4 and to remove copper (II) ions from aqueous media. Moreover, phosphomolybdic acids (PMAs) incorporated with composite PEMs were developed to evaluate fuel cell characteristics, i.e., ion exchange capacity, oxidative stability, proton conductivity and methanol permeability. Fabricated PEMs are characterized by the FTIR, ATR-FTIR, XRD, SEM and EDAX. PMA was incorporated. PEMs demonstrated maximum encapsulation efficiency of 5FU, i.e., 78 ± 2.3%, and released the drug maximum in pH 7.4 buffer. The maximum Cu(II) removal was observed at 188.91 and 181.22 mg.g–1. PMA incorporated with PEMs exhibited significant proton conductivity (59.23 and 45.66 mS/cm) and low methanol permeability (2.19 and 2.04 × 10−6 cm2/s).

Effect of Direct Fluorination on the Transport Properties and Swelling of Polymeric Materials: A Review

Fluorine-containing polymers occupy a peculiar niche among conventional polymers due to the unique combination of physicochemical properties. Direct surface fluorination of the polymeric materials is one of the approaches for the introduction of fluorine into the chemical structure that allows one to implement advantages of fluorinated polymers in a thin layer. Current review considers the influence of the surface interaction of the polymeric materials and membranes with elemental fluorine on gas, vapor and liquid transport as well as swelling and related phenomena. The increase in direct fluorination duration and concentration of fluorine in the fluorination mixture is shown to result mostly in a reduction of all penetrants permeability to a different extent, whereas selectivity of the selected gas pairs (He-H2, H2-CH4, He-CH4, CO2-CH4, O2-N2, etc.) increases. Separation parameters for the treated polymeric films approach Robeson’s upper bounds or overcome them. The most promising results were obtained for highly permeable polymer, polytrimethylsilylpropyne (PTMSP). The surface fluorination of rubbers in printing equipment leads to an improved chemical resistance of the materials towards organic solvents, moisturizing solutions and reduce diffusion of plasticizers, photosensitizers and other components of the polymeric blends. The direct fluorination technique can be also considered one of the approaches of fabrication of fuel cell membranes from non-fluorinated polymeric precursors that improves their methanol permeability, proton conductivity and oxidative stability.

Fabrication and Characterization of Chitosan/N-Phthaloyl Composite Membrane for DMFC Application

Modified chitosan membrane is one of the promising membranes for polymer electrolyte membrane. Chitosan/N-phthaloyl chitosan composite membranes were fabricated to obtain high proton conductivity and low methanol permeability. Membranes were fabricated by casting method and solvent evaporation. Surface morphology, mechanical analysis, methanol permeability, and proton conductivity were used to characterize the overall properties. FT-IR spectra exhibited the presence of interaction of chitosan and n-phthaloyl/chitosan. SEM analysis showed that the surface roughness of composite membrane increases as the n-phthaloyl loading increases. The highest proton conductivity of synthesized membrane is at 2.4 mS.cm-1 and is higher than pristine chitosan membrane at 1.6 mS.cm-1. Moreover, with n-phthaloyl/chitosan addition, the methanol permeability was also improved. The correlation between proton conductivity and methanol permeability in composite membranes suggests that the blend has its potential in DMFC application.

Highly Conductive Polyelectrolyte Membranes Poly(vinyl alcohol)/Poly(2-acrylamido-2-methyl propane sulfonic acid) (PVA/PAMPS) for Fuel Cell Application

In this study, chemically cross-linked PVA/PAMPS membranes have been prepared to be used in direct methanol fuel cells (DMFCs). The structural properties of the resultant membrane were characterized by use FTIR and SEM. Additionally, their thermal stability was assessed using TGA. Moreover, the mechanical properties and methanol and water uptake of membrane was studied. The obtained FTIR of PVA/PAMPS membranes revealed a noticeable increase in the intensity of adsorption peaks appearing at 1062 and 1220 cm−1, which correspond to sulfonic groups with the increasing proportion of PAMPS. The thermograms of these polyelectrolyte membranes showed that their thermal stability was lower than that of PVA membrane, and total weight loss gradually decreased with increasing the PAMPS. Additionally, the functional properties and efficiency of these polyelectrolyte membranes were significantly improved with increasing PAMPS proportion in these blends. The IEC of polymer blend membrane prepared using PVA/PAMPS ratio of 1:1 was 2.64 meq/g. The same membrane recorded also a methanol permeability coefficient of 2.5 × 10−8 cm2/s and thus, its efficiency factor was 4 × 105 greater than that previously reported for the commercial polyelectrolyte membrane, Nafion® (2.6 × 105). No significant increase in this efficiency factor was observed with a further amount of PAMPS. These results proved that the PVA:PAMPS ratio of 1:1 represents the optimum mass ratio to develop the cost-effective and efficient PVA/PAMPS blend membranes for DMFCs applications.

Organic-Inorganic Novel Green Cation Exchange Membranes for Direct Methanol Fuel Cells

Commercializing direct methanol fuel cells (DMFC) demands cost-effective cation exchange membranes. Herein, a polymeric blend is prepared from low-cost and eco-friendly polymers (i.e., iota carrageenan (IC) and polyvinyl alcohol (PVA)). Zirconium phosphate (ZrPO4) was prepared from the impregnation–calcination method and characterized by energy dispersive X-ray analysis (EDX map), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM), then incorporated as a bonding and doping agent into the polymer blend with different concentrations. The new fabricated membranes were characterized by SEM, FTIR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and XRD. The results revealed that the membranes’ physicochemical properties (oxidative stability, tensile strength) are enhanced with increasing doping addition, and they realized higher results than Nafion 117 because of increasing numbers of hydrogen bonds fabricated between the polymers and zirconium phosphate. Additionally, the methanol permeability was decreased in the membranes with increasing zirconium phosphate content. The optimum membrane with IC/SPVA/ZrPO4-7.5 provided higher selectivity than Nafion 117. Therefore, it can be an effective cation exchange membrane for DMFCs applications.