Simulated porosity and electronic structure of nanoporous carbons

Nanoporous carbon refers to a broad class of materials characterized by nanometer-size pores, densities lower than water, large specific surface areas, and high porosities. These materials find applications in nanocatalysis and gas adsorption, among others. The porosity structure, that determines the properties and functionalities of these materials, is still not characterized in detail. Here, we reveal the detail porosity structure and the electronic properties of a type of nanoporous carbons, the so called carbide derived carbons (CDCs), through a simulation scheme that combines large simulation cells and long time scales at the empirical level with first-principles density functional calculations. We show that the carbon network consists in one layer thick nanographenes interconnected among them. The presence of specific defects in the carbon layers (heptagons and octagons) yields to open pores. These defects are not completely removed through annealing at high temperatures. We also suggest that, in contrast with graphene which is a zero-gap semiconductor, these materials would have a metallic character, since they develop an electronic band around the Fermi level. This band arises from the electronic states localized at the edges of the nanographene layers.     

Complex wave patterns in an effective reaction-diffusion model for chemical reactions in microemulsions

An effective medium theory is employed to derive a simple qualitative model of a pattern forming chemical reaction in a microemulsion. This spatially heterogeneous system is composed of water nanodroplets randomly distributed in oil. While some steps of the reaction are performed only inside the droplets, the transport through the extended medium occurs by diffusion of intermediate chemical reactants as well as by collisions of the droplets. We start to model the system with heterogeneous reaction-diffusion equations and then derive an equivalent effective spatially homogeneous reaction-diffusion model by using earlier results on homogenization in heterogeneous reaction-diffusion systems [S.Alonso, M.Ba?r, and R.Kapral, J. Chem. Phys. 134, 214102 (2009)]. We study the linear stability of the spatially homogeneous state in the resulting effective model and obtain a phase diagram of pattern formation, that is qualitatively similar to earlier experimental results for the Belousov-Zhabotinsky reaction in an aerosol OT (AOT)-water-in-oil microemulsion [V.K.Vanag and I.R.Epstein, Phys. Rev. Lett. 87, 228301 (2001)]. Moreover, we reproduce many patterns that have been observed in experiments with the Belousov-Zhabotinsky reaction in an AOT oil-in-water microemulsion by direct numerical simulations.     

Stabilization and study of SrFe(1-x)Mn(x)O2 oxides with infinite-layer structure

A series of layered oxides of nominal composition SrFe(1-x)Mn(x)O(2) (x = 0, 0.1, 0.2, 0.3) have been prepared by the reduction of three-dimensional perovskites SrFe(1-x)Mn(x)O(3-δ) with CaH(2) under mild temperature conditions of 583 K for 2 days. The samples with x = 0, 0.1, and 0.2 exhibit an infinite-layer crystal structure where all of the apical O atoms have been selectively removed upon reduction. A selected sample (x = 0.2) has been studied by neutron powder diffraction (NPD) and X-ray absorption spectroscopy. Both techniques indicate that Fe and Mn adopt a divalent oxidation state, although Fe(2+) ions are under tensile stress whereas Mn(2+) ions undergo compressive stress in the structure. The unit-cell parameters progressively evolve from a = 3.9932(4) ? and c = 3.4790(4) ? for x = 0 to a = 4.00861(15) ? and c = 3.46769(16) ? for x = 0.2; the cell volume presents an expansion across the series from V = 55.47(1) to 55.722(4) ?(3) for x = 0 and 0.2, respectively, because of the larger effective ionic radius of Mn(2+) versus Fe(2+) in four-fold coordination. Attempts to prepare Mn-rich compositions beyond x = 0.2 were unsuccessful. For SrFe(0.8)Mn(0.2)O(2), the magnetic properties indicate a strong magnetic coupling between Fe(2+) and Mn(2+) magnetic moments, with an antiferromagnetic temperature T(N) above room temperature, between 453 and 523 K, according to temperature-dependent NPD data. The NPD data include Bragg reflections of magnetic origin, accounted for with a propagation vector k = ((1)/(2), (1)/(2), (1)/(2)). A G-type antiferromagnetic structure was modeled with magnetic moments at the Fe/Mn position. The refined ordered magnetic moment at this position is 1.71(3) μ(B)/f.u. at 295 K. This is an extraordinary example where Mn(2+) and Fe(2+) ions are stabilized in a square-planar oxygen coordination within an infinite-layer structure. The layered SrFe(1-x)Mn(x)O(2) oxides are kinetically stable at room temperature, but in air at ~170 °C, they reoxidize and form the perovskites SrFe(1-x)Mn(x)O(3-δ). A cubic phase is obtained upon reoxidation of the layered compound, whereas the starting precursor SrFeO(2.875) (Sr(8)Fe(8)O(23)) was a tetragonal superstructure of perovskite.     

Rapid probe of the nicotine spectra by high-resolution rotational spectroscopy

Nicotine has been investigated in the gas phase and two conformational forms were characterized through their rotational spectra. Two spectroscopic techniques have been used to obtain the spectra: a new design of broadband Fourier transform microwave (FTMW) spectroscopy with an in-phase/quadrature-phase-modulation passage-acquired-coherence technique (IMPACT) and narrowband FTMW spectroscopy with coaxially oriented beam-resonator arrangement (COBRA). The rotational, centrifugal distortion and hyperfine quadrupole coupling constants of two conformers of nicotine have been determined and found to be in N-methyl trans configurations with the pyridine and pyrrolidine rings perpendicular to one another. The quadrupole hyperfine structure originated by two (14)N nuclei has been completely resolved for both conformers and used for their unambiguous identification.     

Industriall Control of the Filtration in the Beer Manufacturing Process

In the aim to improve the filtration process in the beer ma nufacture, a study on the beer turbidity have been made using two different techniques: nephelometry and V-UV spectrometry. Even though the former is the most commonly used, we propose the use of V-UV spectrometry since it is possible to follow the performace - of all the filtration line, not only in a punctual way but in a - wide range of wavelenghts. From the results of this work we deduce that V-UV spectrometry offers a better quality of results than nephelometry, being more useful in rutin periodic controls.     

Raman Spectroscopy Analysis of a Playing Card from the 18th Century

We present the characterization, by means of three complementary experimental techniques (optical microscopy [OM], scanning electron microscopy equipped with energy dispersive X-Ray spectroscopy [SEM-EDX], and micro-Raman spectroscopy [µRaman]), of a card belonging to a deck of the Spanish pattern made in Perú at the time of Virreinato de Perú (18th century). The objective is to obtain detailed information on the pictorial palette used for the decoration of the cards, where two basic colors, red and green, are seen. Small samples from both colored regions were analyzed.     

An electrochemical sensor based on TiO2/activated carbon nanocomposite modified screen printed electrode and its performance for phenolic compounds detection in water samples

Herein, we reported a titanium oxide (TiO₂) modified activated carbon nanocomposite that showed advantageous characteristics in terms of electro-conductivity, catalytic activity and surface area. The designed nanocomposite was employed to modify the screen printed carbon electrode transducer surface in the construction of an electrochemical sensor. The electrode surface modification was characterised by cyclic voltammetry and impedimetric studies. The modified transducer surface was subsequently used for the detection of four phenolic endocrine disruptors, p-nitrophenol, hydroquinone, catechol and 1-naphtol. Under optimal conditions, TiO₂ modified activated carbon sensor was evaluated by differential pulse voltammetry showing a good linearity with correlation coefficients higher than 0.99. It showed, in parallel, a high sensitivity where the detection limits were 348 ng/L, 110.1 ng/L, 3.3 ng/L and 7.2 µg/L for the respective studied compounds (S/N = 3). Finally, we validated the method with river water samples, and good recovery values were obtained showing the potential application of the reported biosensor.     

Thermoanalytical studies on lobster shell

Chromium(III) oxide reverses the sequence of dehydration of barium perchlorate trihydrate (BP). Between 223 and 310? the oxide reacts with anhydrous BP in a 1∶1 molar ratio to give the yellow barium dichromite BaCr₂O₄. Between 350 and 430? this material reacts in 1∶1 stoichiometry with BP, to give barium chromate BaCrO₄. The products have been identified by X-ray diffraction analysis. The formation of an unkown phase is also reported.     

Acid catalyzed hydrolysis of brotizolam,a thienotriazolodiazepine: Spectroscopic study

The acid catalyzed hydrolysis of the thienotriazolodiazepine, Brotizolam, 2-bromo-4-(2-chlorophenyl)-9-methyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine ( 1 ), has been studied spectrometrically (ir, pmr, cmr, and ms). The cleavage reaction of the azomethine bond is reversible and the open-ring compound is in equilibrium with the ring closed compound (protonated form of the parent drug).