Sulfonated poly(ether ether ketone)/s–TiO2 composite membrane for a vanadium redox flow battery

The SPEEK/s-TiO₂ composite membrane was prepared by blending sulfonated poly(ether ether ketone) (SPEEK) and sulfonated titanium dioxide (s-TiO₂) nanoparticles. The important physiochemical parameters such as proton conductivity, water uptake, swelling degree and ion exchange capacity of the composite membrane were measured. The thermal stability and chemical stability were also tested. It was observed that the SPEEK/s-TiO₂ composite membrane exhibited the best selectivity (7.13 × 10⁴ S·min·cm⁻³) accompanying high proton conductivity (0.061 S·cm⁻¹) and low tetravalent vanadium ion (VO²⁺) permeability (8.55 × 10⁻⁷ cm²·min⁻¹) compared with Nafion117, SPEEK and SPEEK/TiO₂ membranes. The battery performance with these membranes was characterized by charge–discharge cycling tests and it was found that the SPEEK/s-TiO₂ composite membrane showed the highest energy efficiency (EE) up to 82.3%, indicating the SPEEK/s-TiO₂ composite membrane is a candidate for vanadium redox flow battery (VRFB) application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48830.     

Synthesis and characterization of multiblock semi-crystalline hydrophobic poly(ether ether ketone)–hydrophilic disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes

Multiblock copolymers based on alternating segments of telechelic phenoxide terminated hydrophilic fully disulfonated poly(arylene ether sulfone) (BPS100) and decafluorobiphenyl (DFBP) terminated hydrophobic poly(arylene ether ketimine) (PEEKt), were synthesized from the hydrophilic and ketimine-protected amorphous hydrophobic telechelic oligomers by nucleophilic coupling reactions. After film formation from DMSO, the copolymer was acidified, which converted the ketimine to semi-crystalline ketone segments and the sulfonate salts to disulfonic acids. A semi-crystalline phase with a T_m of 325 °C was confirmed. The semi-crystalline multiblock copolymer membranes were tough, ductile and solvent resistant. Fundamental properties as proton exchange membranes (PEMs) showed enhanced conductivities under fully hydrated and reduced humidity conditions. These multiblock copolymers exhibited low in-plane anisotropic swelling behavior, in contrast to the random copolymers.     

Methanol permeability and proton conductivity of direct methanol fuel cell membranes based on sulfonated poly(vinyl alcohol)–layered silicate nanocomposites

Layered silicate nanocomposite membranes to be used as electrolyte polymeric membranes in a direct methanol fuel cell were prepared through the mixing of poly(vinyl alcohol) (PVA) with various amounts (2, 4, and 5% w/w) of sodium montmorillonite layered silicate nanoclay. The proton conductivity of the polymer was induced by the reaction of the polymer with sulfosuccinic acid. After that, a solution of the sulfonated PVA–layered silicate nanocomposite was cast into membranes. The proton conductivity and methanol permeability of the membranes were determined with a four-point probe technique and a gas chromatography technique, respectively. In addition, structures of the nanocomposite membranes were characterized with X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared techniques. The mechanical properties of the nanocomposite membranes were also determined with a universal testing machine. From the results, it was found that the water uptake, proton conductivity, and methanol permeability of the membranes initially decreased after a 2% (w/w) concentration of the layered silicate was added. Above this nanoclay loading, the water uptake of the membranes increased again. The results were examined in the light of the interaction between the clay and sulfonated polymer, and the steric effect provided the exfoliation of the nanoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The preparation and characteristics of poly(methyl methacrylate–methylacrylate acid)/nano-ZnO composite latex particles

In this work, poly(methyl methacrylate-co-methylacrylate acid)/ZnO (poly(MMA–MAA)/ZnO) composite latex particle was synthesized by three steps The first step was to synthesize poly(MMA–MAA) copolymer latex particles by soapless emulsion polymerization. Following the first step, the second step was to polymerize MMA, MAA and 3,3-(trimethoxysilyl) propyl methacrylate (MPS) in the presence of poly(MMA–MAA) seed latex particles to form the poly(MMA–MAA)/poly(MMA–MAA–MPS) core–shell latex particles. In the third step, the poly(MMA–MAA)/poly(MMA–MAA–MPS) latex particles reacted with ZnO nanoparticles, which were synthesized by a traditional sol gel method, to form the polymer/inorganic poly(MMA–MAA)/poly(MMA–MAA–MPS)/ZnO composite latex. In this study, MPS with silanol groups essentially was used as the coupling agent to couple with ZnO nanoparticles, while the results of the study showed that there was not covalent bond existed between ZnO particles and polymer latex. The ZnO particles were adsorbed on the surface of polymer latex by electrostatic interaction. Besides, the linear poly(MMA–MAA)/crosslinking poly(MMA–MAA–MPS) core–shell latex particles which were synthesized in the second step were heated in the presence of ammonia to form the hollow poly(MMA–MAA–MPS) latex particles. The factors of heating time and concentration of crosslinking agent significantly influenced the morphology of hollow poly(MMA–MAA–MPS) latex particles.     

Synthesis and characterization of soluble aromatic poly(ether amide amide ether ketone ketone)s by electrophilic Friedel–Crafts solution polycondensation

A new monomer, N,N′-bis(4-phenoxybenzoyl)-m-phenylenediamine (BPBMPD), was prepared by condensation of m-phenylenediamine with 4-phenoxybenzoyl chloride in N,N-dimethylacetamide (DMAc). Novel soluble aromatic poly(ether amide amide ether ketone ketone)s (PEAAEKKs) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of BPBMPD with a mixture of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) in the presence of anhydrous aluminum chloride and N-methylpyrrolidone (NMP) in 1,2-dichloroethane (DCE). The influences of reaction conditions on the preparation of polymers were examined. The polymers obtained were characterized by different physico-chemical techniques such as FT-IR, DSC, TGA, and wide-angle X-ray diffraction (WAXD). All the polymers were amorphous and the solubility of the polymers was improved by the incorporation of 1,3-dibenzoylaminobenzene moieties in the main chain. Thermal analyses showed that the polymers had high T_gs of 220–231 °C and exhibited high thermal stability. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 102.9–108.5 MPa, Young’s moduli of 2.44–2.86 GPa, and elongations at break of 9.8–13.7%.     

Synthesis and characteristics of poly(methacrylic acid–co–N-isopropylacrylamide)/Nano ZnO thermosensitive composite hollow latex particles

In this work, the poly(methacrylic acid–co–N-isopropylacrylamide)/Nano ZnO thermosensitive composite hollow latex particles was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate-co- methacrylic acid) (poly(MMA–MAA)) copolymer latex particles by the method of soapless emulsion polymerization. The second process was to polymerize MAA, N-isopropylacrylamide (NIPAAm) and N,N′-Methylenebisacrylamide (MBA) in the presence of poly(MMA–MAA) latex particles to form the linear poly(MMA–MAA)/crosslinking poly(MAA-NIPAAm) core–shell latex particles, and then the core–shell latex particles were heated in the presence of ammonia solution to form the poly(MAA-NIPAAm) thermosensitive hollow latex particles. In the third process, the poly(MAA-NIPAAm) hollow latex particles reacted with ZnO nanoparticles to form the poly(MAA-NIPAAm)/ZnO thermosensitive composite hollow latex particles on which the ZnO nanoparticles were adsorbed. Besides, a novel process was used to synthesize the poly(MAA-NIPAAm)/ZnO composite latex particles in which the ZnO nanoparticles were encapsulated. The effects of various variables on the morphology of poly(MAA-NIPAAm)/ZnO composite hollow latex particle were studied.     

Electrocatalytic Activity of Carbon Nanotube-Supported Pt–Cr–Co Tri-Metallic Nanoparticles for Methanol and Ethanol Oxidations

In this work, platinum (Pt), Pt–Cr, Pt–Co, and Pt–Cr–Co nanoparticles were synthesized on single-walled carbon nanotubes, and their effects on electrocatalytic activity for methanol and ethanol oxidations were investigated using cyclic voltammetry and electrochemical impedance spectroscopy. In comparison to Pt, Pt–Cr, and Pt–Co, Pt–Cr–Co nanoparticles demonstrate better catalytic characteristics for methanol and ethanol oxidations, such as forward peak current density, resistance to carbon monoxide poisoning, peak potential for oxidation, and charge transfer resistance. This study indicates that Pt-trimetallic nanoparticles could be desirable catalyst candidates for both direct methanol and ethanol fuel cells.     

Mechanism of CH4 Dry Reforming on Nanocrystalline Doped Ceria-Zirconia with Supported Pt, Ru, Ni, and Ni–Ru

Specificity of CH₄ dry reforming mechanism for Me-supported doped ceria-zirconia catalysts with high oxygen mobility was elucidated using a combination of transient kinetic methods (TAP, SSITKA) with pulse microcalorimetry and in situ FTIRS. Steady-state reaction of CH₄ dry reforming is described by a simple redox scheme with independent stages of CH₄ and CO₂ activation. This is provided by easy CO₂ dissociation on reduced sites of oxide supports followed by a fast oxygen transfer along the surface/domain boundaries to metal sites where CH₄ molecules are transformed to CO and H₂. The rate-limiting stage is irreversible transformation of CH₄ on metal sites, while CO₂ transformation proceeds much faster being reversible for steady-state surface. The oxygen forms responsible for CH₄ selective transformation into syngas correspond to strongly bound bridging oxygen species with heats of desorption ≈600–650 kJ/mol O₂, most probably bound with pairs of Pr and/or Ce cations able to change their oxidation state. Ni + Ru clusters could be involved in CO₂ activation via facilitating C–O bond breaking in the transition state, thus increasing the rate constant of the surface reoxidation by CO₂. Strongly bound carbonates are spectators.     

Electrocatalytic oxidation of methanol and formic acid on dispersed electrodes: Pt, Pt–Sn and Pt/M(upd) in poly(2-hydroxy-3-aminophenazine)

Platinum particles dispersed in a poly(2-hydroxy-3-aminophenazine) film (pHAPh/Pt) provide a better catalyst than smooth Pt for the electrooxidation of methanol and formic acid in perchloric acid aqueous solutions. The catalytic activity of the Pt particles is further enhanced when Sn is codeposited in the polymer film. In the case of formic acid oxidation, the activity of Pt nanoparticles is influenced by adatoms of Tl, Pb and Bi deposited undepotential conditions. The upd-modified Pt particles are much more active than bare Pt particles. The morphology and identity of the metallic dispersion were examined by transmission electron microscopy.     

Characterization and photodegradation characteristics of organic dye for Pt–titania combined multi-walled carbon nanotube composite catalysts

Multi-walled carbon nanotubes (MWCNTs), titanium(IV) isopropoxide (TIP) and potassium hexachloroplatinate(IV) (K₂PtCl₆) were used for the preparation of Pt/MWCNT/TiO₂ composites. The composites were comprehensively characterized by Brauer–Emett–Teller surface area, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray and UV–vis absorption spectroscopy. The photoactivity of the prepared materials under UV irradiation was tested using the conversion of methylene blue (MB) in aqueous solution. According to the results of MB removal experiment, it can be considered that the MB removal effect of the Pt/MWCNT/TiO₂ composites is affected by two kinds of effects: adsorption effect by MWCNTs and photocatalytic effect by TiO₂. Finally, the photocatalytic effect increases due to photo-induced-electron absorption effect by MWCNTs and electron trap effect by Pt metal.     

Modification of poly(vinylidene fluoride) membranes with aluminum oxide nanowires and graphene oxide nanosheets for oil–water separation

To improve the hydrophilic and oleophobic properties of membrane, we adopted aluminum oxide (Al₂O₃) nanowires and graphene oxide (GO) nanosheets to modify poly(vinylidene fluoride) (PVDF) membranes. The experimental results show that the intercalation of Al₂O₃ nanowires between GO nanosheets effectively improved the roughness of the GO–Al₂O₃–PVDF membrane, and the permeability of the membrane with an optimal mass ratio of Al₂O₃ to GO of 7.5 was 31 times that of the GO–PVDF membrane. Furthermore, the addition of Al₂O₃ nanowires significantly enhanced both the hydrophilic and oleophobic properties of the GO–Al₂O₃–PVDF membrane. On the basis of the extended Derjaguin–Landau–Verwey–Overbeek theory, the energy barriers between the oil droplets and GO–PVDF and GO–Al₂O₃–PVDF membranes were 0.63 and 0.9 KT, respectively; this indicated improvements in the anti-oil-fouling ability of the GO–Al₂O₃–PVDF membranes. We also found that both the GO–PVDF and GO–Al₂O₃–PVDF membranes had great oil–water separation rates (97.9 and 99.4%, respectively) with an initial oil concentration of 200 mg/L. The findings of this study show that the GO–Al₂O₃–PVDF membrane is a promising oil–water separation membrane, and further investigation of the cleaning procedure is needed to promote its practical application in oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47493.     

Effect of oxygen and titanium contents on the stability of nanocrystalline Ti–Ru–Fe–O cathode materials for chlorate electrolysis

Electrodes made from nanocrystalline Ti:Ru:Fe (2–y:1+y/2:1+y/2), with y varying from 0 to 1 by step of 0.25, and Ti:Ru:Fe:O (2:1:1:w), with w varying from 0 to 2 by step of 0.5, were prepared and tested as activated cathodes for the hydrogen evolution reaction in typical chlorate electrolysis conditions. These electrodes were subjected to an accelerated aging test, consisting of a succession of cycles of hydrogen discharge (HER) and open-circuit (OCP) conditions. In addition to monitoring the cathodic overpotential value during the aging test, visual inspection and mass loss measurements were performed on the electrodes at the end of the test to assess their stability. In the case of Ti:Ru:Fe (2:1:1), a large increase of the cathodic overpotential value is observed after 20 cycles. Adding O to the formulation causes a remarkable improvement of the long-term stability of the electrodes. As little as [O] = 10 at.% in nanocrystalline Ti:Ru:Fe:O (2:1:1:w) materials is sufficient for the electrode to show absolutely no sign of degradation after 50 cycles of HER/OCP, the longest accelerated test conducted. Adding more O to the formulation of the material does not lead to further stability improvement. A better stability under the conditions of the accelerated aging test can also be observed for nanocrystalline Ti:Ru:Fe (2–y:1+y/2:1+y/2) materials with y > 0. In that case however, the level of improvement is dependent on the value of y. The best results are obtained for y = 0.75. A hypothesis is proposed to explain the improved stability obtained by lowering the Ti content and/or by adding O. The similarity and difference between both ways of improving the stability of the nanocrystalline Ti:Ru:Fe materials are also discussed.     

Preparation and properties of soapless poly(styrene–butyl acrylate–acrylic acid)/SiO2 composite emulsion

Soapless emulsion polymerization of styrene-butyl acrylate-acrylic acid was carried out using single or combined polymerizable emulsifiers, such as hydroxypropyl methacrylate sodium sulfate (HPMAS), sodium vinyl sulfate, and vinyl alkylphenol polyether sulfates (NRS-10), in the presence of colloidal nano-SiO₂ solution in order to obtain films with high degree of hardness and water-resistance. Monomer conversion, formation of coagulum, viscosity, particle size, size distribution, and surface tension of the emulsions, as well as the film properties, were determined and compared with those of an emulsion prepared with the conventional emulsifier sodium dodecyl sulfate and polyoxyethylene octylphenol ether. Emulsions prepared from a mixture of two polymerizable emulsifiers NRS-10 and HPMAS (1:1, weight ratio) have presented high monomer conversion, low coagulum, and small particle sizes. When the emulsifier level increased within a certain level, the monomer conversion increased but particles size decreased. Increased amounts of reactive emulsifiers led to low monomer conversion, large amount of coagulum and small particle sizes. With the increase of nano-SiO₂ the particle sizes and the viscosity of the emulsion also increased. The introduction of reactive emulsifiers improved the water-resistance of the resulting films, and the addition of nano-SiO₂ increased the hardness of the coatings. Under optimal conditions, the coatings made from emulsions produced from a combination of reactive emulsifiers such as NRS-10 and HPMAS (1:1, weight ratio) at 2?% level (based on monomer weight) exhibited remarkable hardness, adhesion force and water-resistance.     

Optimized structure and electrochemical properties of sulfonated carbon nanotubes/Co–Ni bimetallic layered hydroxide composites for high-performance supercapacitors

Technical development in electronic devices is frequently stifled by their insufficient capacity and cyclic stability of energy-storage devices. The nano-structured materials have sensational importance for providing novel and optimized combination to overcome exiting boundaries and provide efficient energy storage systems. Metal hydroxide materials with high capacity for pseudo-capacitance properties have grabbed special attention. Lately, the blend of nickel and cobalt hydroxides has been considered as a favorable class of metallic hydroxide materials owing to their comparatively high capacitance and exceptional redox reversibility. The sulfonated carbon nanotube fluid (SCNTF) was prepared by the ion exchange method to be utilized as the exceptional templates due to astonishing specific surface area, ensuring the maximum utilization of the active material. The CoNi-layered double hydroxides (LDHs)/SCNTF core-shell nanocomposite was prepared by the simple solvothermal method. Structural analysis showed that the composite material had the high conductance of carbon materials, the pseudo-capacitance characteristics of metal hydroxides, and porous structure, which facilitates the ion shuttle when the electrolyte reacts with the active material. Electrochemical analysis results showed that CoNi-LDHs/SCNTF had excellent rate performance, reversible charge-discharge properties and cycle stability. It exhibited an extreme specific capacity of 1190.5 F g^?1 at a current density of 1 A g^?1; whereas specific capacity remained 953.7 F g^?1 at the current density was 10 A g^?1. In addition, the capacity retention rate after 5000 charge-discharge cycles at a current density of 20 A g^?1 was 81.0%. The results indicated that the CoNi-LDHs/SCNTF core-shell nanocomposite material is cost efficient and an effective substitute in energy storage applications.     

Core–sheath nanofibrous membranes based on poly(acrylonitrile-butadiene-styrene), polyacrylonitrile,and zinc oxide nanoparticles for photoreduction of Cr(VI) ions in aqueous solutions

This investigation addresses the design of a series of poly(acrylonitrile-butadiene-styrene)/polyacrylonitrile–zinc oxide(ABS/PAN–ZnO) membranes by coaxial electrospinning. In the first instance, an optimization of ABS and PAN electrospinning was performed, thus establishing suitable compositional and processing parameters for obtaining homogenous fibers. Then, coaxial electrospinning of ABS and PAN solutions containing different amount of ZnO nanoparticles was carried out. The coaxial morphology of the nanofibers and ZnO distribution/dispersion were studied by the combination of several techniques such as scanning electron microscopy, X-ray energy dispersive analysis, contact angle, and thermogravimetric analysis. The performance of the obtained membranes for chromium (VI) ions removal from aqueous solutions was assessed by photoreduction using ultraviolet–visible spectroscopy. Electrospun mats composed of ABS (core)/PAN (sheath) embedded with 30 wt % of ZnO nanoparticles exhibited the highest chromium photoreduction (about 80%), suggesting the potential use of these membranes as filters for water purification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48429.     

Synthesis and evaluation of different adsorbents based on poly(methacrylic acid–trimethylolpropane trimethacrylate) and poly(vinylimidazole–trimethylolpropane trimethacrylate) for the adsorption of tebuthiuron from aqueous medium

In the present study a new cross-linked copolymer poly(methacrylic acid–trimethylolpropane trimethacrylate) (named PMA) and poly(vinylimidazole–trimethylolpropane trimethacrylate) (named PVI) was synthesized through precipitation polymerization and applied to the adsorption of tebuthiuron. Adsorbent materials were characterized by using FT-IR, SEM, TGA, textural data, and elemental analysis. Kinetic study showed that the tebuthiuron adsorption was very quick and the equilibrium time was achieved at 20 min for both polymers. Experimental kinetic data for both polymers were very well described by the second-order kinetic model, thus indicating that tebuthiuron adsorption involves chemical adsorption in different binding sites, which could control the reaction rate. Adsorption equilibrium data were better fitted to the dual-site Langmuir–Freundlich model, which recognizes the existence of two kinds of adsorption sites on the polymer surface ascribed to the presence of carboxyl and carbonyl groups from PMA and imidazole ring and carbonyl group from PVI. The maximum adsorption capacities of PMA and PVI were found to be 186.76 and 213.89 mg g^− 1, respectively, which are much higher than other adsorbents.     

Fabrication and cell morphology of a microcellular poly(ether imide)–carbon nanotube composite foam with a three-dimensional shape

The preparation of microcellular poly(ether imide) (PEI) based foams with three-dimensional geometry remains a great challenge worldwide. In this study, we fabricated microcellular PEI–carbon nanotube (CNT) bead foams with a batch rapid depressurization method in a self-designed mold with supercritical carbon dioxide (scCO₂) as a blowing agent. The effects of the saturation time, foaming temperature, foaming pressure, and depressurization rate on the microcellular structures of the PEI foam were analyzed by the Taguchi approach to determine the optimum foaming conditions, and the influence of the CNT content on the cell structure was analyzed. The results show that the depressurization rate and foaming temperature were the key factors influencing the cell size and cell density (N _f); that is, the high depressurization rate and low foaming temperature favored a small cell size and high N _f. The foaming temperature also influenced the foaming ratio (ϕ), and a high ϕ was obtained at a high foaming temperature. Under optimal foaming conditions, PEI with 2.0 wt % CNTs presented the best cell structure; N _f, cell size, and ϕ were 6.14 × 10¹⁰ cell/cm³, 2.43 μm, and 2.08, respectively. The mechanical properties of the final parts were related more to the foaming time and CNT concentration, and the maximum tensile and compression strength were reached at 3 h foaming time and 2.0 wt % CNT, that is, at 2.75 and 15.1 MPa (10% strain), respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47501.