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The use of immiscible polymer blends in gas separations is limited due to uncontrollable phase separation. In contrast, compatibilized immiscible polymer blends can be used as precursors with controlled morphologies that allow for a unique pore architecture. Herein, an immiscible polymer blend (1:1) comprising polybenzimidazole (PBI) and the copolyimide 6FDA-DAM:DABA [3:2], derived from reacting 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,4,6-trimethyl-1,3-phenylenediamine (DAM) and 3,5-diaminobenzoic acid (DABA), were combined with durene diamine as a compatibilizer. The compatibilizer helped reduce the 6FDD domain sizes from 5.6 µm down to 0.77 µm and induced a more even 6FDA distribution and the formation of continuous thin-selective PBI layers. The carbon–carbon composite membranes derived from the compatibilized immiscible polymer blends showed a 3-fold increase in both H2 permeability and H2/CO2 selectivity compared to the membranes derived from non-compatibilized polymer blends. The H2 permeability of the compatibilized immiscible polymer blends increased from 3.6 to 27 Barrer, and their H2/CO2 selectivity increased from 7.2 to 20. The graphitic domain size of the carbon–carbon composite membranes derived from the polymer blends also increased from 6.3 nm for the non-compatibilized blend to 10.0 nm for the compatibilized blend. [ABSTRACT FROM AUTHOR]

This study explores a simple method of fabricating hybrid supercapacitor electrodes, which could potentially broaden the application of this technology. The method involves electrospinning a uniform solution of Matrimid/Metal−Organic Polyhedra 18 (MOP−18) followed by carbonization at a relatively low temperature of 700 °C in air, rather than in an inert atmosphere, to create free−standing, redox−active hybrid supercapacitor electrodes. Additionally, the synthesis procedure requires no stabilization or activation steps, which enhances the cost effectiveness of the synthesized electrode materials. The resulting C/CuO composite was used as the working electrode, with a polyacrylonitrile (PAN)/Poly(methyl methacrylate) (PMMA) carbon nanofiber (CNF) electrode as the counter and 6 M KOH as the electrolyte in a T−cell configuration. The cell performance and redox activity were evaluated using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), electrochemical impedance spectroscopy (EIS) and cycling stability tests. Additionally, the physical and chemical structures of the electrode materials were assessed using X−ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron spectroscopy (TEM), X−ray diffractometry (PXRD), surface area analysis and other characterization techniques. The electrode material demonstrated a specific capacitance of up to 206 F/g. Supercapacitors utilizing this material display an energy density of 10.3 Wh/kg (active material) at a current density of 1 A/g in electrochemical testing. [ABSTRACT FROM AUTHOR]

Vanadium sesquioxide/vanadium nitride nanoparticles were prepared in carbon fibers by electrospinning, followed by carbonization. Polyacrylonitrile was used as the carbon precursor, poly-(methyl methacrylate) as the porogen, and V2O5 nanowires as the vanadium source. During the high temperature carbonization, V2O5 was reduced in situ by carbon and converted into V2O3 and further transformed into VN by NH3 released from polyacrylonitrile. The composite was used as electrodes and fabricated into a symmetric coin cell-type supercapacitor using 1 M lithium bis-(trifluoromethanesulfonyl)-imide in propylene carbonate as the electrolyte. The resulting supercapacitor showed a specific capacitance of 369 F g–1 at 5 mV/s, an energy density of 107 Wh kg–1 at 0.05 A g–1, and a high power density of 5154 W kg–1 at 5 A g–1. [ABSTRACT FROM AUTHOR]

Carbon molecular sieve membranes (CMSMs) were prepared by carbonizing the high free volume polyimide BTDA-BAF that is obtained from the reaction of benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA) and 9,9-bis(4-aminophenyl) fluorene (BAF). The bulky cardo groups prevented a tight packing and rotation of the chains that leads to high permeabilities of their CMSMs. The incorporation of metal–organic polyhedra 18 (MOP-18, a copper-based MOP) in the BTDA-BAF polymer before pyrolysis at 550 °C prevented the collapse of the pores and the aging of the CMSMs. It was found that upon decomposition of MOP-18, a distribution of copper nanoparticles minimized the collapse of the graphitic sheets that formed the micropores and mesopores in the CMSM. The pillared CMSMs displayed CO2 and CH4 permeabilities of 12,729 and 659 Barrer, respectively, with a CO2/CH4 selectivity of 19.3 after 3 weeks of aging. The permselectivity properties of these membranes was determined to be at the 2019 Robeson upper bound. In contrast, the CMSMs from pure BTDA-BAF aged three times faster than the CMSMs from MOP-18/BTDA-BAF and exhibited lower CO2 and CH4 permeabilities of 5337 and 573 Barrer, respectively, with a CO2/CH4 selectivity of 9.3. The non-pillared CMSMs performed below the upper bound. [ABSTRACT FROM AUTHOR]

Hybrid supercapacitors (SCs) made of carbon–metal oxide composites are devices which combine the advantages of electric double layer capacitors and pseudocapacitors viz high energy density, high power density and high cyclability. This is best achieved when the pseudocapacitive components are uniform in size and distribution on the conducting carbon support. Electrodes mats, fabricated from carbonized electrospun fibers generated from solutions of polyacrylonitrile (PAN) as the carbon source, cobalt (III) acetylacetonate as a metal oxide precursor, and polymethacrylic acid (PMAA) as a metal oxide precursor carrier were utilized in coin cell SCs. Fibers without the PMMA carrier were prepared for comparison. XRD and TGA showed conversion of the cobalt precursor to a mixture of cobalt and cobalt oxide (Co3O4). When the PMAA carrier was used, specific capacitance increased from 68 F g−1 in PAN-Co3O4 to 125 F g−1 in PAN-PMAA-Co3O4. The addition of PMAA to the system results in better uniformity, accessibility and dispersion of metal and metal oxide particles. Due to the relatively low surface area of carbonized samples, Co3O4 nanoparticles are the primary contributors to charge storage. The fabricated fibers show an energy density of 8.9 at 750 W kg−1, which is twice that of the fibers made without PMAA. [ABSTRACT FROM AUTHOR]

For the first time, porous organic polymers (POPs) based on the smallest buckybowl, corannulene (BB-POPs) have been synthesized. Three POPs were synthesised via Sonogashira co-polymerization of 1,2,5,6-tetrabromocorannulene and alkyne linkers. BB-POP-3 exhibits the highest surface area (SABET = 560 m2 g−1) and CO2 adsorption of 11.7 wt%, while they retain the redox properties of corannulene. [ABSTRACT FROM AUTHOR]

Gas separation for industrial, energy, and environmental applications requires low energy consumption and small footprint technology to minimize operating and capital costs for the processing of large volumes of gases. Among the separation methods currently being used, like distillation, amine scrubbing, and pressure and temperature swing adsorption, membrane-based gas separation has the potential to meet these demands. The key component, the membrane, must then be engineered to allow for high gas flux, high selectivity, and chemical and mechanical stability at the operating conditions of feed composition, pressure, and temperature. Among the new type of membranes studied that show promising results are the inorganic-based and the metal-organic framework-based mixed-matrix membranes (MOF-MMMs). A MOF is a unique material that offers the possibility of tuning the porosity of a membrane by introducing diffusional channels and forming a compatible interface with the polymer. This review details the origins of these membranes and their evolution since the first inorganic/polymer and MOF/polymer MMMs were reported in the open literature. The most significant advancements made in terms of materials, properties, and testing conditions are described in a chronological fashion. [ABSTRACT FROM AUTHOR]

Electrochemical double layer capacitors (EDLCs) utilize electrodes with high surface area to achieve high-energy storage capability. In this study, flexible and freestanding carbon nanofibers derived from PIM-1, a microporous polymer with high free volume, were prepared by pyrolysis of the electrospun polymer. A BET surface area of 546 m2 g−1 was obtained upon carbonization of the electrospun PIM-1 fibers. After further heat treatments such as steam-activation and annealing, the surface area increased to 1162 m2 g−1. These carbon fibers were directly used as electrodes without the use of binders in a coin cell (CR2032) configuration and were characterized by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The activated and annealed fibers gave a specific capacitance of 120 F g−1 at a scan rate of 10 mV s−1 using 1,3-ethylmethylimidizaolium bis(trifluoromethanesulfonyl)imide as the ionic liquid electrolyte. From the galvanostatic charge–discharge test, the supercapacitor exhibited energy and power densities of 60 W h kg−1 (active material) and 1.7 kW kg−1, respectively, at a current density of 1 A g−1. High power application of this device was demonstrated by its 77% retention of the energy density (47 W h kg−1) at a higher discharge current density of 5 A g−1. [ABSTRACT FROM AUTHOR]

An instrument was built for the permeation testing of flat polymer membranes under pressures up to 3.0 MPa and temperatures up to 300 °C. The high pressure, high temperature cell uses aluminum tape and a graphite gasket to minimize the leak from the high pressure side to the low pressure side, making possible the permeability measurements of slow diffusing gases such as N2. A computer program developed on a LabVIEW platform fully controls the instrument and data acquisition. It incorporates algorithms to automatically adjust the downstream volume, repressurize the upstream volume, vent the downstream volume to prevent over pressurization, and change the temperature of the permeation cell. The percent relative standard deviation of the permeability measurements was <5.5%. Flat membranes of VTEC PI-1388 polymer were tested from 0.3 to 3.0 MPa and from 35 to 300 °C. The permeabilities and fluxes of H2, CO2, and N2 increased with increasing temperature, while the H2/CO2 ideal selectivity remained unchanged. The major contribution to increased flux arose from increments in temperature rather than pressure. [ABSTRACT FROM AUTHOR]

Novel polysilsesquioxane (R-Si-(O)1.5) PEMs with highly cross-linked Si-O backbones and pendant organic side chains comprising propylsulfonic or ethylphosphonic acid groups, were prepared via sol-gel polymerization. The inorganic component provides thermal/mechanical/chemical stability while the organic component gives flexibility and proton-conducting properties. The propylsulfonic acid membranes exhibited proton conductivities (σ) up to 10-2 S/cm at high relative humidities and temperatures, while the ethylphosphonic acid membranes showed lower proton conductivities but higher thermal stabilities. Preliminary results for the propylsulfonic acid membranes in direct methanol fuel cell (DMFC) performance are reported. [ABSTRACT FROM AUTHOR]

Colloidal silica spheres are usually used for making opal photonic crystals. With the aim to create tunable or otherwise functional opals we have coated colloidal SiO2 spheres with conjugated polymers, including: polyaniline sulfonic acid, polypyrrole and MEH-PPV (poly [2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene]). Spheres coated with MEH-PPV were dispersed in H2O and coated with polyelectrolytes that charged the colloidal surfaces allowing the polymer coated spheres to self-assemble by sedimentation under gravity into close packed structures with well ordered crystalline domains. Inverse MEH-PPV/polypropylene photonic crystals were fabricated and their photoluminescence was blue shifted compared to a uniform MEH-PPV film. [ABSTRACT FROM AUTHOR]

A new dialkylthio benzo[1,2-b:4,5-b′]dithiophene (S-BDT) was designed and synthesized and the polymer S-PBDT was prepared by a Stille coupling reaction. A high open-circuit voltage (Voc) of up to 0.99 V was achieved in polymer solar cells with PCBM. [ABSTRACT FROM AUTHOR]

Capacity degradation by phase changes and oxygen evolution has been the largest obstacle for the ultimate commercialization of high‐capacity LiNiO2‐based cathode materials. The ultimate thermodynamic and kinetic reasons of these limitations are not yet systematically studied, and the fundamental mechanisms are still poorly understood. In this work, both phenomena are studied by density functional theory simulations and validation experiments. It is found that during delithiation of LiNiO2, decreased oxygen reduction induces a strong thermodynamic driving force for oxygen evolution in bulk. However, oxygen evolution is kinetically prohibited in the bulk phase due to a large oxygen migration kinetic barrier (2.4 eV). In contrast, surface regions provide a larger space for oxygen migration leading to facile oxygen evolution. These theoretical results are validated by experimental studies, and the kinetic stability of bulk LiNiO2 is clearly confirmed. Based on these findings, a rational design strategy for protective surface coating is proposed. Thermodynamic and kinetic reasons for structural instability of LiNiO2‐based cathode materials are studied by combined first‐principle calculation and experiments. Deep battery charging decreases oxygen reduction and induces strong thermodynamic driving force for oxygen evolution from surface and grain boundary. In contrast, oxygen evolution is kinetically prohibited in bulk phase, implying a promising direction for stabilizing these materials. [ABSTRACT FROM AUTHOR]

The energy needed to rupture a fibre (its toughness) is five times higher for spider silk than for the same mass of steel wire, which has inspired efforts to produce spider silk commercially. Here we spin 100-metre-long carbon-nanotube composite fibres that are tougher than any natural or synthetic organic fibre described so far, and use these to make fibre supercapacitors that are suitable for weaving into textiles. [ABSTRACT FROM AUTHOR]