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Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 A) were obtained.

The facile fabrication of functionally graded all-graphene films using a single-step casting process is reported. The films consist of a self-assembled graphene oxide (GO) precursor that can be reduced to different levels on an active metal substrate. Control of processing conditions such as the underlying substrate metal and the film-drying environment results in an ability to tailor the internal architecture of the films as well as to functionally grade the reduction of GO. A gradient arrangement within each film, where one side is electrically conductive reduced GO (rGO) and the other side is insulating GO, was confirmed by scanning electron microscopy, Raman, X-ray diffraction, Fourier transform infrared, and X-ray photoelectron spectroscopy characterization studies. All-graphene-based freestanding films with selectively reduced GO were used in transient electronic applications such as flexible circuitry and RFID tag antennas, where their decommissioning is easily achieved by capitalizing on GO's ability to readily dissociate and create a stable suspension in water. Furthermore, the functionally graded structure was found to exhibit differential swelling behavior, and its potential applications in graphene-based actuators are outlined.

Carbon-based supercapacitors exhibit great rate capability, power density and cycle life, but suffer from relatively low energy density. Polyaniline provides high specific capacitance, but lacks cycling stability. By combining carbon-based materials with tetraaniline, an oligomer of polyaniline, a hybrid composite is formed that demonstrates improved supercapacitor performance relative to either material alone. In this study, the reduced graphene oxide-oligoaniline composites have been synthesized by a one-step hydrothermal process without the need for adding any oxidizing or reducing agents. FTIR, Raman spectroscopy, XPS, and MALDI-TOF mass spectroscopy indicate the successful reduction of GO to rGO and the formation of aniline oligomers. Unlike most polyaniline nanostructures for which charge storage kinetics are limited by slow diffusion-controlled reactions, the majority of oligoaniline in this composite is exposed to the electrolyte and stores charge through fast surface-controlled reactions. The unique microstructure of the rGO-oligoaniline composites facilitates transport of ions and electrons, leading to greater utilization of the active materials, high specific capacitance of 640 F/g at 0.2 mA/cm2 (corresponding to 707 C/g specific capacity), great rate capability and good cycle stability (91% retention after 2000 cycles).

Thin-film composite (TFC) membranes are favored for precise molecular sieving in liquid-phase separations; they possess high permeability due to the minimal thickness of the active layer and the high porosity of the support layer. However, current TFC membrane fabrication techniques are limited by the available materials for the selective layer and do not demonstrate the level of structural control needed to substantially advance organic solvent nanofiltration (OSN) membrane technology. In this work, we employ the newly developed thin-film lift-off (T-FLO) technique to fabricate polybenzimidazole (PBI) TFC membranes with porous support layers uniquely tailored to OSN. The drop-cast dense PBI selective layers endow the membranes with an almost complete rejection of common small dye molecules. The polymeric support layer is optimized by a combinatorial approach using four different monomers that alter the cross-linking density and polymer chain flexibility of the final composite. These two properties substantially affect the porogen holding capacity of the reticular polymer network, leading to the formation of different macropore structures. With a 150 nm thick PBI selective layer and fine-tuning of the support layer, the resulting membrane achieves stable and superior permeance of 14.0, 11.7, 16.4, 11.4, 17.1, and 19.7 L m-2 h-1 bar-1 for water, ethanol, methanol, isopropanol, tetrahydrofuran (THF), and acetonitrile, respectively.

Modified polyolefin separators fabricated via a roll-to-roll system exhibit markedly improved compatibility with lithium ion battery electrolytes. Zwitterionic molecules containing a perfluorophenyl azide functional group were synthesized and covalently bound to the surface of commercial polyolefin separators via UV-activated photochemistry. A roll-to-roll prototype system was constructed allowing for the functionalization of large areas of separator under ambient conditions at low cost. Lithium-ion battery cells containing the modified separators exhibit superior electrochemical performance using a common commercial electrolyte. The modified separators, both monolayer PE and trilayer PP/PE/PP, are wetted instantly upon contact with liquid electrolytes lacking linear carbonates. These electrolytes have been designed for use in batteries with advanced thermal stability properties and/or higher voltage windows, which have previously been hindered by incompatibility with commercial trilayer polyolefin separa...

Supercapacitors are energy storage and conversion devices that display high power. In order to increase energy density, redox-active materials can be incorporated into the carbonaceous electrode(s). Although in recent years many studies have offered different redox-active candidates and composite methods, there is a constant search for an effective, easily producible and stable composite material. Here, we present a graphene/ferrocene composition as a redox active 3-D supercapacitor electrode material. The combination of highly reversible, conductive and strongly attached ferrocene with the high surface area and open porous structure of graphene results in high-power, high-energy density supercapacitors. The graphene scaffold is converted from graphene-oxide (GO) by laser irradiation, a facile, fast and eco-friendly method. The ferrocene is chemically bonded to the graphene by two different approaches that take advantage of the strong and stable pi–pi interactions between the carbon and the aromatic ligands. The excellent bonding between the components results in low internal resistance and high reversibility of the redox reaction. The composite demonstrated a 205% increase in specific capacitance from 87 F g−1 for pure laser reduced graphene oxide to 178 F g−1 for the composite with ferrocene. This is equivalent to an energy density of 6.19 W h kg−1 while maintaining a power density of 26.0 kW kg−1.

Dicarboxylic acids play a key role in atmospheric particle nucleation. Though long assumed to originate from primary sources, little experimental evidence exists directly linking combustion to their emissions. In this work, we sought definitive proof that dicarboxylic acids are produced in diesel engines and that they can slip through a modern aftertreatment system (ATS) at low exhaust temperatures. One difficulty in measuring dicarboxylic acid emissions is that they cannot be identified using conventional mass spectroscopy techniques. In this work, we refined a derivatization gas chromatography-mass spectroscopy technique to measure 11 mono- and dicarboxylic acids from plain and KOH impregnated quartz filters. Filters were loaded with exhaust from a modern passenger car diesel engine on a dynamometer sampled before and after an ATS consisting of an oxidation catalyst and diesel particulate filter. Our findings confirm that dicarboxylic acids are produced in diesel engine combustion, especially during low temperature combustion modes that emit significant concentrations of partially combusted hydrocarbons. Exhaust acids were largely removed by a fully warmed-up ATS, mitigating their environmental impact. Our results also suggest that dicarboxylic acids do not participate in primary particle formation in dilute engine exhaust as low quantities were collected on unimpregnated filters.

Solid solutions of tungsten diboride (WB2) with increasing substitution of tungsten (W) by tantalum (Ta) and niobium (Nb)—ranging from 0 to 50 at. % on a metals basis—were synthesized through resis...

High degrees of dispersion are a prerequisite for functional composite materials for applications in electronics such as sensors, charge and data storage, and catalysis. The use of small precursor materials can be a decisive factor in achieving a high degree of dispersion. In this study, carbon nanodots are used to fabricate a homogeneous, finely dispersed Fe2 O3 -graphene composite aerogel in a one-step conversion process from a precursor mixture. The laser-assisted conversion of small size carbon nanodots enables a uniform distribution of 6.5 nm Fe2 O3 nanoparticles during the formation of a highly conductive carbon matrix. Structural and electrochemical characterization shows that the features of both material entities are maintained and successfully integrated. The presence of Fe2 O3 nanoparticles has a positive effect on the active surface area of the carbon aerogel and thus on the capacitance of the material. This is demonstrated by testing the performance of the composite in supercapacitors. Faradaic reactions are exploited in an aqueous electrolyte through the high accessible surface of the incorporated small Fe2 O3 nanoparticles boosting the specific capacitance of the 3D turbostratic graphene network significantly.

We have recently reported a potentially useful application for conjugated polymer films in the field of gas separations (Science, 252, 1412, 1991). Here we report additional findings which show how selective control of gas permeability is facilitated by the doping, undoping and redoping (cycling) process of emeraldine films. Specifically, permeability data for H2, He, CH4, CO2, O2, N2, and CH4 are given for films treated with perchloric acid. There is a large increase in permeability to all gases following the doping and undoping film treatment cycle. Moreover, controlled redoping (of the undoped films) results in large separation factors for industrially important gas pairs. These results are consistent with the model based on dopant occupation of free-volume of the “pin-hole free” film. This cycling phenomenon is also found in other conjugated polymers such as poly-dimethoxy-para-phenylene-vinylene (DMPPV). Another important variable for gas transport properties of polyaniline films is the film curing time. Permeability data for films cured at 125° C for 2, 3, and 6 hours, and then cycled, indicate that a three hour cure time produces the most fully dense films. We also present preliminary gas permeability data for a polyimide thin film by itself and, a polyimide blend containing polyaniline.

Gas permeability values are reported for films of the conducting polymer polyaniline in the emeraldine oxidation state. Substantial improvements in gas selectivity, when compared to literature values, were observed for all gas pairs studied (He/N2, H2/N2, O2/N2, CO2/CH4). The doping procedure which enables conductivity in the film was found to cause significant concurrent changes in the film morphology which resulted in improved gas separations. These morphological changes primarily influence the permeant diffusivity as shown by comparison to the kinetic diameter of the permeant. The potential for development of conducting polymer membranes with precisely controlled morphology is clearly indicated, allowing optimization of films for any gas separation.