Origin of the ESR spectrum in the Prussian Blue analogue RbMn[Fe(CN)6]*H2O

We present an ESR study at excitation frequencies of 9.4 GHz and 222.4 GHz of powders and single crystals of a Prussian Blue analogue (PBA), RbMn[Fe(CN)6]*H2O in which Fe and Mn undergoes a charge transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. (JMMM, 316, E680 (2007)) is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe(CN)6 vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge transfer transition and is attributed to a mixing of the Mn3+ - Fe2+ state into the prevalent Mn2+ - Fe3+ state.

Synthesis and characterization of some Mn(II) and Mn(III) complexes of N,N′-o-phenylenebis(salicylideneimine)(LH2) and N,N′-o-phenylenebis(5-bromosalicylideneimine)(L′H2). Crystal structures of [Mn(L)(H2O)(ClO4)], [Mn(L)(NCS)] and an infinite linear chain of [Mn(L)(OAc)]

A series of manganese(II) [Mn(L)] and manganese(III) [Mn(L)(X)] (X = ClO4, OAc, NCS, N3, Cl, Br and I) complexes have been synthesized from Schiff base ligands N,N′-o- phenylenebis(salicylideneimine)(LH2) and N,N′-o-phenylenebis(5- bromosalicylideneimine)(L′H2) obtained by condensation of salicylaldehyde or 5-Br salicylaldehyde with o-phenylene-diamine. The complexes have been characterized by the combination of IR, UV-Vis spectroscopy, magnetic measurements and electrochemical studies. Three manganese(III) complexes 3 [Mn(L)(ClO4)(H2O)], 5 [Mn(L)(OAc)] and 13 [Mn(L)(NCS)] have been characterized by X-ray crystallography. The X-ray structures show that the manganese(III) is hexa-coordinated in 3, it is penta-coordinated in 13, while in 5 there is an infinite chain where the MnL moieties are connected by acetate ions acting as bridging bidentate ligand. The cyclic voltammograms of all the manganese(III) complexes exhibit two reversible/quasi-reversible/ irreversible responses assignable to Mn(III)/Mn(II) and Mn(IV)/Mn(III) couples. It was observed that the ligand L′H2 containing the 5-bromosal moiety always stabilizes the lower oxidation states compared to the corresponding unsubstituted LH2. Cyclic voltammograms of the manganese(II) complexes (1 and 2) exhibit a quasi-reversible Mn(III)/Mn(II) couple at E1/2 -0.08 V for 1 and 0.054 V for 2. © 2005 Elsevier B.V. All rights reserved.

Crystal structure of [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]·3H2O

The reaction of Cs4[Re6Te8(CN)6]·2H2O with Cu(en)2Cl2 in water affords crystals of a cluster complex [{Cu(H2O)(en) 2}{Cu(en)2}Re6Te8(CN)6]·3H2O. The structure of the compound is determined by single crystal X-ray diffraction (a = 10.8082(4) Å, b = 16.5404(6) Å, c = 24.6480(7) Å, β = 92.696(1)°, V = 4401.5(3) Å3, Z = 4, space group P21/n, R 1 = 0.0331, wR 2 (all data) = 0.0652). In the complex, cluster [Re6Te8(CN)6]4- anions are linked by Cu2+ cations into zigzag chains through cyanide bridges. The coordination environment of the copper cations is complemented by ethylenediamine molecules. Each of the cluster anions is additionally coordinated by a terminal fragment {Cu(H2O)(en)2}. © 2014 Pleiades Publishing, Ltd.

The surface chemistry of nanocrystalline MgO catalysts for FAME production:an in situ XPS study of H2O, CH3OH and CH3OAc adsorption

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 − sites to OH− and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C–H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

Influence of reaction atmosphere (H2O, N2, H2, CO2, CO) on fluidized-bed fast pyrolysis of biomass using detailed tar vapor chemistry in computational fluid dynamics

Secondary pyrolysis in fluidized bed fast pyrolysis of biomass is the focus of this work. A novel computational fluid dynamics (CFD) model coupled with a comprehensive chemistry scheme (134 species and 4169 reactions, in CHEMKIN format) has been developed to investigate this complex phenomenon. Previous results from a transient three-dimensional model of primary pyrolysis were used for the source terms of primary products in this model. A parametric study of reaction atmospheres (H2O, N2, H2, CO2, CO) has been performed. For the N2 and H2O atmosphere, results of the model compared favorably to experimentally obtained yields after the temperature was adjusted to a value higher than that used in experiments. One notable deviation versus experiments is pyrolytic water yield and yield of higher hydrocarbons. The model suggests a not overly strong impact of the reaction atmosphere. However, both chemical and physical effects were observed. Most notably, effects could be seen on the yield of various compounds, temperature profile throughout the reactor system, residence time, radical concentration, and turbulent intensity. At the investigated temperature (873 K), turbulent intensity appeared to have the strongest influence on liquid yield. With the aid of acceleration techniques, most importantly dimension reduction, chemistry agglomeration, and in-situ tabulation, a converged solution could be obtained within a reasonable time (∼30 h). As such, a new potentially useful method has been suggested for numerical analysis of fast pyrolysis.

Detection of H2O and Evidence for TiO/VO in an Ultra-hot Exoplanet Atmosphere

We present a primary transit observation for the ultra-hot (T eq ~ 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12–1.64 μm wavelength range. The 1.4 μm water absorption band is detected at high confidence (5.4σ) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B, r', and z' filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone is unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12–1.3 μm wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.

Pathways of the Photocatalytic Reaction of Acetate in H2O and D2O Combined: An EPR and ATR-FTIR Study

The adsorption and photocatalytic degradation of acetate on TiO2 surfaces was investigated in H2O and D2O by ATR-FTIR and EPR Spectroscopy respectively. These studies were carried out in the dark and under UV(A) illumination to gain additional insights into the adsorption behaviour with the identification of paramagnetic species formed during the oxidation of acetate. Isotopic exchange during the adsorption of D2O on TiO2 surface led to different interactions between the adsorbate and OD groups. At different pH levels, several surface complexes of acetate can be formed such as monodentate, or bidentates. Under UV(A) irradiation of TiO2 aqueous suspensions, the formation of hydroxyl and methoxy radicals evidenced as the corresponding spin-adducts, were found to dominate in alkaline and acidic suspensions respectively. Two possible pathways for the oxidation of acetate have been suggested at different pH levels in solution in terms of the source of the spin adduct formed. These proposed pathways were found to be in good agreement with ATR-FTIR and EPR results.

Critical core mass for enriched envelopes: the role of H2O condensation

Context. Within the core accretion scenario of planetary formation, most simulations performed so far always assume the accreting envelope to have a solar composition. From the study of meteorite showers on Earth and numerical simulations, we know that planetesimals must undergo thermal ablation and disruption when crossing a protoplanetary envelope. Thus, once the protoplanet has acquired an atmosphere, not all planetesimals reach the core intact, i.e. the primordial envelope (mainly H and He) gets enriched in volatiles and silicates from the planetesimals. This change of envelope composition during the formation can have a significant effect on the final atmospheric composition and on the formation timescale of giant planets. Aims. We investigate the physical implications of considering the envelope enrichment of protoplanets due to the disruption of icy planetesimals during their way to the core. Particular focus is placed on the effect on the critical core mass for envelopes where condensation of water can occur. Methods. Internal structure models are numerically solved with the implementation of updated opacities for all ranges of metallicities and the software Chemical Equilibrium with Applications to compute the equation of state. This package computes the chemical equilibrium for an arbitrary mixture of gases and allows the condensation of some species, including water. This means that the latent heat of phase transitions is consistently incorporated in the total energy budget. Results. The critical core mass is found to decrease significantly when an enriched envelope composition is considered in the internal structure equations. A particularly strong reduction of the critical core mass is obtained for planets whose envelope metallicity is larger than Z approximate to 0.45 when the outer boundary conditions are suitable for condensation of water to occur in the top layers of the atmosphere. We show that this effect is qualitatively preserved even when the atmosphere is out of chemical equilibrium. Conclusions. Our results indicate that the effect of water condensation in the envelope of protoplanets can severely affect the critical core mass, and should be considered in future studies.

The influence of promoters (Zr, La, Tb, Pr) on the catalytic performance of CuO-CeO2 systems for the preferential oxidation of CO in the presence of CO2 and H2O

CuO supported on CeO2 and Ce0.9X0.1O2, where X is Zr, La, Tb or Pr, were synthesized using nitrate precursors, giving rise ceria based materials with a small particle size which interact with CuO species generating a high amount of interfacial sites. The incorporation of cations to the ceria framework modifies the CeO2 lattice parameter, improving the redox behavior of the catalytic system. The catalysts were characterized by X-ray fluorescence spectrometry (XRFS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, thermoprogrammed reduction with H2 (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalysts were tested in the preferential oxidation of CO under a H2-rich stream (CO-PROX), reaching conversion values higher than 95% between 115 and 140 °C and being the catalyst with 6 wt.% of Cu supported on Ce0.9Zr0.1O2 (sample 6CUZRCE) the most active catalyst. The influence of the presence of CO2 and H2O was also studied simulating a PROX unit, taking place a decrease of the catalytic activity due to the inhibitor effect both CO2 and H2O.

Fluxos turbulentos de calor, H2O e CO2, sobre cana-de-açúcar em Sertãozinho, SP.

1997

Synthesis of Na-PSS geopolymers and analysis of the H2O/Na2O molar ratio influence over their mechanical properties

Geopolymers are solid aluminosilicate material made by mixing an activating solution and a solid precursor. This work studied the mechanisms of synthesis of metakaolin-based geopolymers and the influence of water content, described by the molar ratio H2O/Na2O, on the final product. The samples were tested using a Uniaxial Compressive Test (UCT) to define their compressive resistance. Two geopolymers series were synthetized and let them rest for 7- days and 28-days, each of them composed by six different sets. 7-day rest series showed that water addition had no relevant effect over its resistance while the 28-day rest series almost doubled the compressive resistance, although those with the highest H2O/Na2O molar ratio showed instead a drastic reduction. Two other series were synthesized by adding silt aggregate, a waste material obtained in the production of aggregate for concrete, corresponding to 10wt% and 20wt%of the metakaolin used. After 28 days of aging, these samples were tested via UCT to measure the variation of the compressive resistance after the silt addition. The aggregate has disruptive effects over the compressive resistance, but the 20wt% samples achieved a higher compressive resistance. Samples with highest and lowest compressive resistance have been chosen to carry out an XRD analysis. In all the samples it has been recognized the presence of Anatase (TiO2), a titanium oxide found in the metakaolin and Thermonatrite, a hydrated sodium carbonate [Na2CO3 • (H2O)]. Scanning Electron Microscopy was carried out on the samples with the highest compressive resistance and showed that the samples with lower water content developed a homogeneous geopolymeric texture, while those with higher water content showed instead a spongy-like texture and a higher air or pore solution bubbles presence. Silt/geopolymer composites showed a fracture system developing across the interstitial transition zone between the geopolymer matrix and the aggregate particle.