The effects of formation and functionalization of graphene-based membranes on their gas and water vapor permeation properties.

The gas and water vapor permeabilities of graphene-based membranes can be affected by the presence of different functional groups directly bound to the graphene network. In this work, one type of carboxylated graphene oxide (GO-COOH) and two types of graphene oxide synthesized i) under strong oxidative conditions directly from graphite (GO-1) and ii) under mild oxidative conditions from exfoliated graphene (GO-2) were used as precursors of self-standing membranes prepared with thicknesses in the range of 12-55 µm via slow-vacuum filtration preparation method. It was observed that the permeabilities for all tested gases decreased in order GO-2 > GO-1 > GO-COOH and depended on both the arrangement of graphene sheets and their functionalization. The GO-1 membrane with a high content of oxygen-containing groups showed the best performance for water vapor permeability. The GO-2 membrane with a thickness of 43 µm exhibited a disordered GO sheet morphology and, therefore, unique gas-separation performance towards H2/CO2 gas pair, showing high hydrogen permeability while keeping extremely high H2/CO2 ideal selectivity that exceeds the Robeson 2008 upper bound of polymer membranes.

Intercalation of Ionic Liquids into LDH Structures for Microwave-Accelerated Polymerizations.

Microwave-accelerated ring-opening polymerization (ROP) of cyclic esters catalyzed by ionic liquid (IL) anions, intercalated into layered double hydroxides (LDHs), has been recently described as a fast and environmentally friendly synthetic way to prepare biodegradable polyester/LDH nanocomposites. However, to observe this synergistic catalytic effect between microwaves and IL anions and to achieve a homogeneous structure of the final polymer nanocomposite, the IL anions must be efficiently intercalated inside the LDH structure. Herein, we investigate the effects of various metal compositions of M2+/Al3+ LDHs (M = Mg, Co, and Ca) and different LDH synthetic routes (one-step direct coprecipitation, two-step coprecipitation/anion exchange, and two-step urea/anion exchange) on the intercalation efficiency of trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate IL. The most effective IL anion intercalation was observed for Ca2+/Al3+ LDH prepared using the two-step method consisting of coprecipitation and subsequent anion exchange. After optimization, this synthetic pathway led to the production of LDHs with intercalated IL anions and a reduced amount of intercalated water (<0.6 wt %). The catalytic ability of thus optimized LDH particles was demonstrated on the microwave-assisted ROP of ε-caprolactone, showing rapid progress of polymerization. Within minutes, the polycaprolactones with an average molecular mass in the range of 20 000-50 000 g/mol containing fully delaminated and exfoliated LDH nanoparticles were obtained.

Carbon and zeolite-based composites for radionuclide and heavy metal sorption.

Zeolites have been investigated as sorbents of heavy metals from water. Since graphene oxide was already reported as promising radionuclide sorbent, we developed composite materials containing both a synthetic zeolite (type A, P or Y) and graphene oxide to be multifunctional sorbents. The extension of multifunctionality of sorbents was done by presence of third component, exfoliated graphite, to have additional properties as conductivity. The changing sorption activities of a composite was studied depending on its composition and functional modification. The composites, characterized by X-ray powder diffraction, Raman, FTIR spectroscopy and scanning electron microscopy, were tested for sorption of selected radionuclides (134Cs+, 85Sr2+) and heavy metals (Pb2+, Cd2+). The dependency on composition was found in connection with a high sorption of Pb2+ and Cd2+. Finally, optimized multifunctional sorbents (Gr-GO-COOH-A in ratio 40:40:20 and Gr:GO:A in ratio 25:25:50) were found to keep interesting high sorption activities for heavy metals and radionuclides with good conductivity properties.

Influence of Inorganic Bases on the Structure of Titanium Dioxide-Based Microsheets.

Laboratory synthesis of microsheets of titanium dioxide from titanyl sulfate involves the use of ammonia solution, whereas another inorganic base is most likely to be employed at the industrial level, as ammonia is a toxic agent and therefore should be avoided according to European Union (EU) regulations. Selected nontoxic bases such as sodium, potassium, and lithium hydroxides have been tested as an alternative to ammonia solution to obtain amorphous and crystalline TiO2-based microsheets. The final products obtained at each step of the procedure (samples lyophilized and annealed at 230 and 800 °C) were analyzed with electron and atomic force microscopy, X-ray powder diffraction, thermal analysis, and Fourier transform infrared (FTIR) and Raman spectroscopies to determine their morphology and phase composition. The differences in the morphology of the obtained products were described in detail as well as phase and structural composition throughout the process. It was found that, in the last step of the synthesis, microsheets annealed at 800 °C were built of small rods and oval or platy crystalline particles depending on the base used. The temperature of formation of anatase, rutile, and alkali-metal titanates in correlation with the ionic radius of the alkali metal present in the sample was discussed.

Salt-washed graphene oxide and its cytotoxicity.

The carbon nanomaterials and congeners, e.g., graphene or graphene oxide (GO), dispose of numerous unique properties, which are not necessarily intrinsic but might be related to a content of impurities. The oxidation step of GO synthesis introduces a considerable amount of metallic species. Therefore, large-scale purification is an actual scientific challenge. Here we describe new purification technique (salt­washing), which is based on three consecutive steps: (a) aggregation of GO sheets with NaCl (b) washing of the aggregates and (c) removing of the salt to afford purified GO (swGO). The considerably improved purity of swGO was demonstrated by ICP and EPR spectroscopy. The microscopic methods (TEM with SEAD, AFM) proved that the salt-washing does not affect the morphology or concentration of defects, showing the aggregation of GO with NaCl is fully reversible. The eligibility of swGO for biomedical applications was tested using fibroblastic cell cultures. The determined IC50 values clearly show a strong correlation between the purity of samples and cytotoxicity. Although the purification decreases cytotoxicity of GO, the IC50 values are still low proving that cytotoxic effect is not only impurities-related but also an intrinsic property. These findings may represent a serious limitation for usage of GO in biomedical applications.

Ultrasound exfoliation of graphite in biphasic liquid systems containing ionic liquids: A study on the conditions for obtaining large few-layers graphene.

Herein we describe a successful protocol for graphite exfoliation using a biphasic liquid system (water/dichloromethane, DCM) containing ionic liquids (ILs; 1,3-dibenzylimidazolium benzoate- and 1-naphthoate). The use of (surface active) IL and sonication led to stable DCM/water (O/W) emulsion, which enhanced graphene formation, suppressed its re-aggregation and decreased shear/cavitation damage. The O/W emulsion stabilization by the ILs was studied by dynamic light scattering (DLS), whereas their interaction with the graphene sheets were described by Density Functional Theory (DFT) calculations. Moreover, a comprehensive investigation on cavitation-based exfoliation in the O/W systems was performed to assess the importance of operational parameters, including, the type of ultrasound processor, ultrasound power and insonation, and the influence of the exfoliation medium.