A Comparative Study of Atmospheric Chemistry with VULCAN

We present an update of the open-source photochemical kinetics code VULCAN to include C–H–N–O–S networks and photochemistry. The additional new features are advection transport, condensation, various boundary conditions, and temperature-dependent UV cross sections. First, we validate our photochemical model for hot Jupiter atmospheres by performing an intercomparison of HD 189733b models between Moses et al., Venot et al., and VULCAN, to diagnose possible sources of discrepancy. Second, we set up a model of Jupiter extending from the deep troposphere to upper stratosphere to verify the kinetics for low temperature. Our model reproduces hydrocarbons consistent with observations, and the condensation scheme successfully predicts the locations of water and ammonia ice clouds. We show that vertical advection can regulate the local ammonia distribution in the deep atmosphere. Third, we validate the model for oxidizing atmospheres by simulating Earth and find agreement with observations. Last, VULCAN is applied to four representative cases of extrasolar giant planets: WASP-33b, HD 189733b, GJ 436b, and 51 Eridani b. We look into the effects of the C/O ratio and chemistry of titanium/vanadium species for WASP-33b, we revisit HD 189733b for the effects of sulfur and carbon condensation, the effects of internal heating and vertical mixing (K zz) are explored for GJ 436b, and we test updated planetary properties for 51 Eridani b with S8 condensates. We find that sulfur can couple to carbon or nitrogen and impact other species, such as hydrogen, methane, and ammonia. The observable features of the synthetic spectra and trends in the photochemical haze precursors are discussed for each case.

Determination of the through-plane profile of vanadium species in hydrated Nafion studied with micro X-ray absorption near-edge structure spectroscopy – proof of concept

Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2 +. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2 + inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.

Pharmacologically active vanadium species: distribution in biological media and interaction with molecular targets

: Biospeciation of some of the most studied vanadium (symbol V) complexes with biological or medicinal activity is discussed in this review in order to emphasize the importance of the distribution of V species in biological media. The exact knowledge of the chemical species present in blood or cells may provide essential information about the biological effect of V potential drugs. In blood serum vanadium species can interact with low (citrate, lactate, oxalate, amino acids, etc., indicated with bL) and high molecular mass (proteins like transferrin, albumin, immunoglobulins, etc.) components, while the interaction with red blood cells can interfere with the transport of these drugs towards the target cells. The interaction with bLs and proteins is discussed through the analysis of instrumental and computational data. The fate of the active V species, when these are in the real serum samples and when reach and cross cell membranes, is also discussed. The differences in the V complexes selected in this review (donor atoms, stability, coordination geometry, electric charge, hydro- lipophilicity balance, substituents and redox properties) cover all the possible mode of interaction withbLs and proteins, allowing for the biodistribution of the studied compounds to be predicted. This approach could be applied to newly synthesized potential V drugs.

The Impact of 3-(trihydroxysilyl)-1-propanesulfonic Acid Treatment on the State of Vanadium Incorporated on SBA-15 Matrix

Bifunctional catalysts—e.g., those with acidic and redox sites—are of particular importance, especially in the cascade processes, including the one-pot transformation of glycerol to acrylic acid. In this study, we explore one aspect of the preparation of a vanadium-containing catalyst, which can be further modified with 3-(trihydroxysilyl)-1-propanesulfonic acid (TPS). The state of vanadium species loaded on mesoporous ordered silica of SBA-15 type was investigated before and after treatment with TPS, which can also be applied for the generation of acidic centers. Two vanadium sources, i.e., ammonium metavanadate and vanadium(IV) oxide sulfate, were applied to generate redox sites on SBA-15. The structure of materials obtained was analyzed using N2 adsorption/desorption and XRD measurements. For the estimation of the amount of vanadium and characterization of its state, the following techniques were applied: ICP, UV-Vis, XPS, ESR and FTIR combined with pyridine adsorption. The treatment of vanadium containing SBA-15 with TPS was found to lead to the oxidation of V4+ to V5+ and the partial removal of vanadium species, leading to a decrease in the number of penta-coordinated vanadium species. These features should be taken into account in the design of bifunctional catalysts with vanadium-active centers and SO3H acidic sites coming from TPS.

Synthesis of cyanooxovanadate and cyanosilylation of ketones

Two key catalytic vanadium species involved in cyanosilylation of ketones were observed by in situ measurement.

Temperature effects on VO2 thin films deposited by RF sputtering for the degradation by photocatalysis of methylene blue and naproxen

The temperature effect on VO2 thin films synthesized by RF sputtering on their morphological, optical, electrical properties and their activity in the photocatalytic degradation of methylene blue and naproxen was studied. Characterization results presented microcrystallinity for VO2 films treated at 50 and 100 °C. Nevertheless, the untreated films and films treated at 200 °C revealed characteristic peaks of monoclinic and tetragonal phases. SEM micrographs with elemental mapping of VO2 films showed granular morphology and a good oxygen dispersion along the film surface, possibly due to a restructuring on the film occasioned by particle coalescence and vanadium oxide island conformation. The electronic transmittance spectra showed the d–d transition characteristic for the square-pyramidal stereochemistry of vanadium (IV) ion, where the optical band interval was high for films treated at 50 °C. Raman spectroscopy results presented an increment in the V = O/V–O ratio as a function of temperature, probably related to superficial vanadium species formation. X-ray spectroscopy results showed the Onon-lattice/Olattice ratio values higher for films treated at 50 °C than the other films, related to an oxide character. The V 2p fit results presented V4+, V5+ regions and satellites for VO2 films thermal treated at 50 °C. The electrical resistivity on the VO2 films decreased as a function of temperature. Finally, the VO2 films thermal treated at 50 °C had higher photocatalytic activity in the degradation of methylene blue and naproxen compared to the other VO2 films, possibly associated with high electron mobility between the surface and the bulk, where the oxygen vacancies act as recombination sites for the e−/h+ pairs during photocatalytic degradation.