Enhanced Thermal Oxidation Stability of Reduced Graphene Oxide by Nitrogen Doping

Nitrogen‐doped reduced graphene oxide (N‐doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present.     

Irradiation effects in CaF2 probed by Raman scattering

The formation conditions and dynamics of Ca colloids and point defects that appear in irradiated single crystals of CaF₂ were investigated by Raman spectroscopy. The intensity changes in the Raman spectra because of the presence of different concentrations of point defects and Ca colloids that emerged in CaF₂ after irradiation with 2.2 GeV Au ions were used to study their distribution and stability under illumination with three laser wavelengths (473, 532 and 633 nm) at different output powers (2 to 200 mW). A damage saturation at a fluence of 6 × 10¹¹ ion cm⁻² was observed. The dependence of the spectral changes on the ion fluence can be described by a core/halo damage cross‐section model. A radius of 13–18 nm was obtained for the outer (halo) cylinder, in agreement with previous swelling studies. Illuminations of irradiated samples with blue (473 nm) and green (532 nm) lasers were found to be extremely efficient in bleaching the samples, while illumination with a red (633 nm) laser did not lead to a sample recovery. This indicates that the bleaching process is governed by recombination of point defects that have to overcome an energy barrier. Typical time constants for the processes involved are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Control of crystalline phases in magnetic Fe nanoparticles inserted inside a matrix of porous carbon

Two magnetic composites made up of Fe nanoparticles (Fe-NPs) embedded in a porous amorphous carbon matrix are presented. One of the samples, Fe-S-AC, was obtained with the aid of sucrose and the other, Fe-AC, in the absence of this substance. The XRD patterns show Bragg diffraction peaks associated with α-Fe and γ-Fe crystalline phases in the Fe-AC sample, while only peaks corresponding to the α-Fe phase are observed for Fe-S-AC powders. The Fe-NPs exhibit broad particle-size distributions for both samples, 5–50 nm for Fe-AC, whereas two populations (2–8 and 10–70 nm) for the Fe-S-AC composite are found. This fact gives rise to poorly defined blocking temperatures, as it can be deduced from the broad maxima observed in M_ZFC(T) variations. In addition, M(H) curves for both Fe-AC and Fe-S-AC samples reveal the existence of exchange-bias effect for T<60 K, probably due to a magnetic coupling within a core/shell structure of the Fe-NPs, although this effect was observed to be less significant for Fe-S-AC.     

Resistive switching in Ag–TiO2 contacts

We study the electric pulse induced resistance switching of TiO₂–Ag contacts at room temperature, exploring both unipolar and bipolar switching modes. Initially we observed unipolar response. After hundred pulsing cycles the unipolar switching response vanishes but the device can still be operated in bipolar switching regime. The underlying mechanism for resistance switching is modeled in terms of formation and rupture of filament, and movement of oxygen vacancies.     

Alkynyl Fischer carbene complex as a traceless directing group for the regioselective cycloaddition of dithiolethiones to arylacetylene: synthesis of E-dithiafulvene thione and dithioesters

A phenylethynyl Fischer carbene complex was used as a traceless directing group for the regioselective cycloaddition of dithiolethiones to arylacetylene, which constitutes the first synthesis of E-dithiafulvene thione or dithioesters.     

Subextensive entropies and open order in perovskite oxynitrides

Unusual subextensive configurational entropies that vary with particle size and tend to zero per atom in macroscopic samples are predicted for AMO(3-z)N(z) oxynitrides with perovskite type crystal structures. These materials are crystallographically disordered on the atomic scale, but local anion order produces chains of M-N-M bonds that undergo a 90° turn at each M cation, giving rise to subextensive entropies in materials such as SrTaO(2)N, LaNbON(2), and EuWO(1.5)N(1.5). A general Pauling ice-rules formula is used to calculate the extensive molar entropies for other cases such as SrMoO(2.5)N(0.5) and BaTaO(2)N. The subextensive oxynitrides are usefully classified as showing an "open order", related to the correlated order of displacements in ferroelectric perovskites such as BaTiO(3). This raises the possibility that further open-ordered oxynitride or molecular structures may be accessible, and other states such as spins and charges may also show novel open orders.     

Synthesis of thiadiazole, dithietane, and imine derivatives of the [1,2]dithiolo[1,4]thiazine ring system

We report the synthesis of some new polysulfur-nitrogen heterocyclics by cycloaddition reactions to the thioketo group of readily available tricyclic 1,2-dithiole-3-thiones. Thus treatment of bis[1,2]dithiolo[1,4]thiazine ketothione 1 with diaryl nitrile imines generated from hydrazonoyl chlorides 2a-g gave [1,3,4]thiadiazolylidenyl[1,2]dithiolo[1,4]thiazines 4a-g in high yield. Compounds 4a-f, bearing the same substituents in both aryl groups, were stable but the analogous 4g,h with a p-nitrophenyl group on carbon gave the bis[1,2]dithiolo[1,4]thiazine dione 9, probably by cycloreversion and hydrolysis during chromatography. Treatment of 1, the bis[1,2]dithiolopyrrole ketothione 13, and dithione 12 with ethoxycarbonyl azide 11 gave imines 12 and 15 and bisimine 16, respectively, by an alternative fragmentation of the initial cycloadduct in which the 1,2-dithiole ring is retained. Reaction of 1 with TosMIC gave the imino-1,3-dithietane 17.     

Solid-phase synthesis of graphitic carbon nanostructures from iron and cobalt gluconates and their utilization as electrocatalyst supports

We present a novel and facile synthesis methodology for obtaining graphitic carbon structures from Fe(II) and Co(II) gluconates. The formation of graphitic carbon can be carried out in only one step by means of heat treatment of these organic salts at a temperature of 900 degrees C or 1000 degrees C under inert atmosphere. This process consists of the following steps: (a) pyrolysis of the organic gluconate and its transformation to amorphous carbon, (b) conversion of Fe(2+) and Co(2+) ions to Fe(2)O(3) and CoO and their subsequent reduction to metallic nanoparticles by the carbon and (c) conversion of a fraction of formed amorphous carbon to graphitic structures by Fe and Co nanoparticles that act as catalysts in the graphitization process. The removal of the amorphous carbon and metallic nanoparticles by means of oxidative treatment (KMnO(4) in an acid solution) allows graphitic carbon nanostructures (GCNs) to be selectively recovered. The GCNs thus obtained (i.e. nanocapsules and nanopipes) have a high crystallinity as evidenced by TEM/SAED, XRD and Raman analysis. In addition, we used these GCNs as supports for platinum nanoparticles, which were well dispersed (mean Pt size approximately 2.5-3.2 nm). Most electrocatalysts prepared in this way have a high electrocatalytical surface area, up to 90 m(2) g(-1) Pt, and exhibit high catalytic activities toward methanol electrooxidation.     

Heterocyclic N-glycosyl derivatives. XIV. Preparation of some N-(2,3-dideoxyglycopyranosyl)benzotriazoles by hydrogenation of N-(pent- and hex-2-enopyranosyl)benzotriazoles

Catalytic hydrogenation of a series of N-(pent- and hex-2-enopyranosyl)benzotriazoles afforded the corresponding saturated N-glycosyl derivatives having the same anomeric configuration as the starting compounds. The conformations of all compounds obtained were determined by nmr spectroscopy. The hexopyranosyl nucleosides in solution adopt the Cl conformation. On the other hand, pentopyranosyl nucleosides exist as a mixture of the two chair conformers in equilibrium, with the IC or CI ( L ) form predominating.