Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Thermal behaviour and phases evolution during the sintering of porous inorganic membranes

Anorthite-based highly porous membranes were successfully produced using calcined oyster shell to enhance the pore network. The calcined oyster shells produce CaO responsible for the crystallisation of gehlenite and anorthite at relatively low temperature. While the crystallisation produced nano and meso size of intergranular pores, vitrification of feldspar is responsible for development of the capillary porosities. The increasing sintering temperature from 1200 °C to 1300 °C implies the increase in average pores radius from 1.2 μm to 14.3 μm due to the formation of spherical pores from vitrification. The combination of different class of porosities in the matrices results in the interconnection with improvement of the permeability of the porous network. Porosity, permeability and chemical stability were improved with 20 wt.% of calcined oyster shell addition allowing the possible development of high strength porous network which is promising for the membranes support and other applications including liquid separation as well as liquid filtration where high pressure is used.     

Crystal violet dye sorption and transport in/through biobased PVA cryogel membranes

Cryogels based on poly(vinyl alcohol) [PVA] and three types of bioinsertions such as scleroglucan, cellulose microfibers, and zein, respectively, have been prepared using capacity of PVA to crosslink by repeated freezing–thawing cycles. The effect of the incorporation of biopolymers on the properties of PVA cryogel has been studied by using several techniques such as: scanning electron microscopy, differential scanning calorimetry, and Fourier transform infrared studies. The obtained biobased cryogel membranes were subjected to sorption and to diffusion experiments using Crystal Violet (CV), a dye commonly used in the textile industry and in medicine. Image analysis with CIELAB system was used both to monitor the cryogels loading with CV and to gain insight in the dye state into the gel, in correlation with the bioinsertion type and gels morphology. Dye diffusion but also sorption capacity of the cryogels was found to be closely related to the type of biopolymer. In this article the equilibrium (sorption isotherms) and transport properties (diffusion and permeability coefficients) of CV, in/through physical cross‐linked PVA hydrogel membranes with bioinsertions has been reported. The highest efficiency for the CV removal from aqueous solutions was obtained for the PVA/Scl cryogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41838.     

Effect of cellulose acetate/cellulose triacetate ratio on reverse osmosis blend membrane performance

Surface functionalization and modification including the grafting process are effective approaches to improve and enhance the reverse osmosis (RO) membrane performance. This work is aimed to synthesize grafted/crosslinked cellulose acetate (CA)/cellulose triacetate (CTA) blend RO membranes using N-isopropylacrylamide (N-IPAAm) as a monomer and N,N-methylene bisacrylamide (MBAAm) as a crosslinker. The morphology of these membranes was analyzed by scanning electron microscopy and their surface roughness was characterized by atomic force microscopy. The performance of these membranes was evaluated through measuring two major parameters of salt rejection and water flux using RO unit at variable operating pressures. It was noted that the surface average roughness obviously decreased from 148 nm for the pure CA/CTA blend membrane with 2.5% CTA to 110 nm and 87 nm for the grafted N-IPAAm and grafted/crosslinked N-IPAAM/MBAAm/CA/CTA-RO membranes, respectively. Moreover, the contact angle decreased from 51.98° to 47.6° and 43.8° after the grafting and crosslinking process. The salt rejection of the grafted CA/CTA-RO membrane by 0.1% N-IPAAm produced the highest value of 98.12% and the water flux was 3.29 L/m²h at 10 bar.     

Enhanced graphitic domains of unreduced graphene oxide and the interplay of hydration behaviour and catalytic activity

Previous studies indicate that the properties of graphene oxide (GO) can be significantly improved by enhancing its graphitic domain size through thermal diffusion and clustering of functional groups. Remarkably, this transition takes place below the decomposition temperature of the functional groups and thus allows fine tuning of graphitic domains without compromising with the functionality of GO. By studying the transformation of GO under mild thermal treatment, we directly observe this size enhancement of graphitic domains from originally ≤40 nm² to >200 nm² through an extensive transmission electron microscopy (TEM) study. Additionally, we confirm the integrity of the functional groups during this process by a comprehensive chemical analysis. A closer look into the process confirms the theoretical predicted relevance for the room temperature stability of GO and the development of the composition of functional groups is explained with reaction pathways from theoretical calculations. We further investigate the influence of enlarged graphitic domains on the hydration behaviour of GO and the catalytic performance of single atom catalysts supported by GO. Additionally, we show that the sheet resistance of GO is reduced by several orders of magnitude during the mild thermal annealing process.     

A Multiscale-Porous Anion Exchange Membrane for Convenient and Scalable Electrokinetic Concentration of Cationic Species

A device able to electrokinetically concentrate cationic samples has many potential medical and industrial applications, but until now has remained undeveloped due to the lack of a commercial anion-permselective material leading to a prohibitively complex fabrication procedure. Herein, a novel multiscale-porous anion exchange membrane (MP-AEM) that enables the convenient and scalable electrokinetic concentration of cationic species is proposed. A mechanically enhanced multiscale-porous structure with a solid framework is realized by adopting polyester resin as an additive to overcome the intrinsic limitations of the AEM material. The scalable MP-AEM-embedded electrokinetic concentrator is devised based on the peculiar properties of the MP-AEM that for allow both ion and fluid transport. With the MP-AEM, the concentrator is fabricated in a highly streamlined manner consisting only of a simple insertion and assembly. The concentration performance of the MP-AEM-embedded electrokinetic concentrator is demonstrated with a positively charged fluorescent dye and a fluorescein-labeled protein, and the results show enrichment factors of 250 and 500, respectively. The MP-AEM makes cationic electrokinetic concentration more accessible and scalable, thereby enabling further progress in a wide range of fields.     

Crosslinked quaternized poly(arylene ether sulfone) copolymer membrane applied in an electric double-layer capacitor for high energy density

The low energy density of supercapacitors, especially supercapacitors based on aqueous electrolytes, is the main factor limiting their application, and the energy density is closely related to the operating potential window of the supercapacitor. The polymer electrolyte is the main contributor to the safe operation and good ion conductivity of the supercapacitor. In this study, a crosslinked quaternized poly(arylene ether sulfone) (PAES) membrane was prepared via crosslinking during membrane formation with a thermal-only treatment and applied in an electric double-layer capacitor (EDLC). The pre-prepared PAES membrane formed a polymer electrolyte with 1 mol/L Li₂SO₄ and was then fabricated into an EDLC single cell. The properties of both the membrane and ELDC were investigated. The preferred cPAES-N-0.2 polymer electrolyte showed an ionic conductivity of 1.18 mS/cm. The optimized EDLC exhibited a single-electrode gravimetric capacitance of 104.92 F/g at a current density of 1.0 A/g and a high operating potential window (1.5 V); it, thereby, achieved a high energy density of 8.20 W h/kg. The EDLC also exhibited excellent cycling properties over 3000 charge–discharge cycles. The crosslinked structures promoted the tensile strength and thermal stability of the PAES membranes; this was accompanied by a slight decrease in the ionic conductivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47759.     

Oxidative degradation of polyamide reverse osmosis membranes: Studies of molecular model compounds and selected membranes

Selected aromatic amides were used to model the chemical reactivity of aromatic polyamides found in thin‐film composite reverse osmosis (RO) membranes. Chlorination and possible amide bond cleavage of aromatic amides upon exposure to aqueous chlorine, which can lead to membrane failure, were investigated. Correlations are made of the available chlorine concentration, pH, and exposure time with chemical changes in the model compounds. From the observed reactivity trends, insights are obtained into the mechanism of RO membrane performance loss upon chlorine exposure. Two chemical pathways for degradation are shown, one at constant pH and another that is pH‐history dependent. An alternative strategy is presented for the design of chlorine‐resistant RO membranes, and an initial performance study of RO membranes incorporating this strategy is reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1173–1184, 2003     

Selective Transport of Bismuth Ions through Supported Liquid Membrane

A new supported liquid membrane (SLM) system was prepared for the selective transport of bismuth ions from the aqueous feed into the aqueous permeate phase. The support of the SLM was a thin porous polypropylene or polyvinylidene fluoride membrane impregnated with diisooctyldithiophosphinic acid (Cyanex 301) as mobile carrier in 4‐chloroacetophenon as organic solvent. Cyanex 301 acts as a highly selective carrier for the uphill transport of bismuth ions through the SLM. In the presence of HNO₃ as a metal ion acceptor in the strip solution, the transport of bismuth ions into the strip side reached 70 % of the initial feed concentration after 3.5 hours. The selectivity and efficiency of bismuth transport from aqueous solutions containing different mixtures of cations were investigated. In the presence of P₂O₇^2– ions as suitable masking agent in the feed solution, the interfering effects of other cations were completely eliminated. The selective transport of bismuth through SLM is superior to liquid‐liquid extraction or through bulk liquid membranes. This is due to the high efficiency. The SLM reduces the solvent requirements, combines extraction and stripping operations in a single process and allows the use of highly selective extractants. The system may be applied to samples containing very low bismuth concentrations.     

Separation of propranolol enantiomers through membranes based on chiral derivatized polysulfone

The characterization of new synthesized chiral polymeric membranes, based in polysulfone polymer is here reported. Polysulfone was derivatized to chiral polysulfone, by bonding covalently the chiral carrier, N-dodecyl-4(R)-hydroxy-l-proline, to the polymer matrix. Two different chiral polysulfones, referred to as CPS_A and CPS_B, have been synthesized and used in the preparation of chiral polymeric membranes. However, as a consequence of the limited CPS_B solubility, only CPS_A resulted adequate to obtain useful membranes. Therefore, various chiral polysulfone membranes containing different amounts of CPS_A in unmodified polysulfone (PS) were prepared and properly characterized by scanning electron microscopy (SEM) and by enantioselective transport experiments of racemic propranolol. Dialysis transport experiments allowed us to determine the influence of the carrier content in the membrane on the transport rate and on enantiomer separation. Membranes containing a CPS_A/PS ratio of 1:3 showed an alpha value of 1.1 at 96 h of performance. Modelling of the propranolol transport rate is also performed.