CO2-Derived Nanocarbons with Controlled Morphology and High Specific Capacitance.

The conversion of CO2 to nanocarbons addresses a dual goal of harmful CO2 elimination from the atmosphere along with the production of valuable nanocarbon materials. In the present study, a simple one-step metallothermic CO2 reduction to nanocarbons was performed at 675 °C with the usage of a Mg reductant. The latter was employed alone and in its mixture with ferrocene, which was found to control the morphology of the produced nanocarbons. Scanning electron microscopy (SEM) analysis reveals a gradual increase in the amount of nanoparticles with different shapes and a decrease in tubular nanostructures with the increase of ferrocene content in the mixture. A possible mechanism for such morphological alterations is discussed. Transmission electron microscopy (TEM) analysis elucidates that the nanotubes and nanoparticles gain mainly amorphous structures, while sheet- and cloud-like morphologies also present in the materials possess significantly improved crystallinity. As a result, the overall crystallinity was preserved constant for all of the samples, which was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. Finally, electrochemical tests demonstrated that the prepared nanocarbons retained high specific capacitance values in the range of 200-310 F/g (at 0.1 V/s), which can be explained by the measured high specific surface area (650-810 m2/g), total pore volume (1.20-1.55 cm3/g), and the degree of crystallinity. The obtained results demonstrate the suitability of ferrocene for managing the nanocarbons' morphology and open perspectives for the preparation of efficient "green" nanocarbon materials for energy storage applications and beyond.

Direct versus reverse vertical two-dimensional Mo2C/graphene heterostructures for enhanced hydrogen evolution reaction electrocatalysis.

Mo2C/graphene heterostructures prepared by chemical vapor deposition have demonstrated excellent electrocatalytic activity in a hydrogen evolution reaction (HER). This is attributed to the high catalytic activity of Mo2C while the high electrical conductivity of graphene facilitates charge transfer. In the as-grown direct vertical order, graphene is placed above the Mo2C film. This reduces the catalytic activity of the heterostructure, since graphene in chemically inert. Here, a simple transfer method is proposed that results in the reverse order deposition of the heterostructure on the electrode. This method places graphene at the interface between Mo2C and the electrode, enhancing charge transfer between them, which results in an overpotential of 440 mV at 10 mA cm-2 and corresponds to ∼65 mV overpotential reduction as compared to the direct heterostructure. At the same time, when a direct Cu/Mo2C/graphene junction with a Cu catalyst substrate is used as a working electrode, the improvement of the heterostructure HER activity is observed which is manifested in an overpotential of 275 mV at 10 mA cm-2 with a correspondent ∼230 mV reduction. All above performances are accompanied with excellent endurance.

Mo2C/graphene heterostructures: low temperature chemical vapor deposition on liquid bimetallic Sn-Cu and hydrogen evolution reaction electrocatalytic properties.

Thin 2D Mo2C/graphene vertical heterostructures have attracted significant attention due to their potential application as electrodes in the hydrogen evolution reaction (HER) and energy storage. A common drawback in the chemical vapor deposition synthesis of these structures is the demand for high temperature growth, which should be higher than the melting temperature of the metal catalyst. The most common metallic catalyst is Cu, which has a melting temperature of 1084 °C. Here, we report the growth of thin, ∼200 nm in thickness, semitransparent micrometer-sized Mo2C domains and Mo2C/graphene heterostructures at lower temperatures using liquid Sn-Cu alloys. No Sn-associated defects are observed, making the alloy an appealing growth substrate. Raman spectroscopy reveals the vertical interaction between graphene and Mo2C, as shown by the variation in the strain of the graphene film. The results demonstrate the capability to grow continuous nanometer-thin Mo2C films at temperatures as low as 880 °C, without sacrificing the growth rate. Mo2C films are proven to be efficient electrocatalysts for the HER. Moreover, we demonstrate the beneficial role of graphene overgrown on Mo2C in reducing the HER overpotential values, which is attributed to more efficient charge transfer kinetics, compared to pure Mo2C films.

Physical Properties of Photo-Aged Graphene/Polypropylene Nanocomposites.

In the present research, graphene nanoplatelets/polypropylene (GNP/PP) nanocomposites were prepared by melt mixing and were subjected to accelerated ageing. The effect of graphene on the morphology and physical properties of aged GNP/PP nanocomposites was investigated. The incorporation of graphene to non-aged PP matrix led to changes in its crystal conformation, decreased the ultraviolet-visible (UV-Vis) transmittance and tensile strain and increased the elastic modulus. The ageing of non-reinforced PP increased the ß-phase of PP and caused the formation of cracks on its surface, while voids were observed in its cross-section. The aged PP was also characterized by significantly lower UV-Vis transmittance, thermal stability and tensile strain, but increased elastic modulus compared to non-aged PP. Graphene retarded the ageing of PP matrix, according to Fourier Transform Infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) results. In the aged GNP/PP nanocomposite, the morphology did not present any changes and the examined properties were maintained to similar values with that of non-aged GNP/PP nanocomposite.

Recycling of typical supercapacitor materials.

A simple, facile and low-cost method for recycling of supercapacitor materials is proposed. This process aims to recover some fundamental components of a used supercapacitor, namely the electrolyte salt tetraethyl ammonium tetrafluoroborate (TEABF4) dissolved in an aprotic organic solvent such as acetonitrile (ACN), the carbonaceous material (activated charcoal, carbon nanotubes) purified, the current collector (aluminium foil) and the separator (paper) for further utilization. The method includes mechanical shredding of the supercapacitor in order to reduce its size, and separation of aluminium foil and paper from the carbonaceous resources containing TEABF4 by sieving. The extraction of TEABF4 from the carbonaceous material was based on its solubility in water and subsequent separation through filtering and distillation. A cyclic voltammetry curve of the recycled carbonaceous material revealed supercapacitor behaviour allowing a potential reutilization. Furthermore, as BF4(-) stemming from TEABF4 can be slowly hydrolysed in an aqueous environment, thus releasing F(-) anions, which are hazardous, we went on to their gradual trapping with calcium acetate and conversion to non-hazardous CaF2.

Photocatalytic degradation of mecoprop and clopyralid in aqueous suspensions of nanostructured N-doped TiO2.

The work describes a study of the oxidation power of N-doped and undoped anatase TiO(2), as well as TiO(2) Degussa P25 suspensions for photocatalytic degradation of the herbicides RS-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop) and 3,6-dichloro-pyridine-2-carboxylic acid (clopyralid) using visible and UV light. Undoped nanostructured TiO(2) powder in the form of anatase was prepared by a sol-gel route. The synthesized TiO(2), as well as TiO(2) Degussa P25 powder, were modified with urea to introduce nitrogen into the structure. N-doped TiO(2) appeared to be somewhat more efficient than the starting TiO(2) (anatase) powder when visible light was used for mecoprop degradation. N-doped TiO(2) Degussa P25 was also slightly more efficient than TiO(2) Degussa P25. However, under the same experimental conditions, no degradation of clopyralid was observed in the presence of any of the mentioned catalysts. When the kinetics of mecoprop degradation was studied using UV light, more efficient were the undoped powders, while in the case of clopyralid, N-doped TiO(2) Degussa P25 powder was most efficient, which is probably a consequence of the difference in the molecular structure of the two herbicides.