Hydrazine network on Cu(111) surface: A Density Functional Theory approach

We have used first-principles calculations, including a correction for the dispersive forces (DFT-D2), to investigate the arrangement of hydrazine (N2H4) molecules upon adsorption on the Cu(111) surface, showing that surface–molecule interactions affect the process most. Our calculations provide insight into the interplay between lateral adsorbate–adsorbate and vertical adsorbate–substrate interactions. We found that the main contributors to the assembly of the hydrazine layers are the binding interactions between the adsorbates and the substrate. The dispersion forces are predominant in both vertical and lateral interactions, whereas hydrogen-bonding is least important and organisation of the N2H4 monolayers is therefore primarily due to the long-range interactions. Optimised geometries for several hydrazine conformations were found to be coverage-dependent. The electronic properties such as charge density and density of states have been calculated for different hydrazine coverages, and indicated that no charge transfer occurs between molecules. Scanning tunnelling microscopy images were simulated, where the observed protrusions arise from the trans conformers. We also found that the effect of hydrazine adsorption on the Cu(111) surface energy is negligible and further investigation of other Cu facets is needed to determine the N2H4 effect on the nanoparticles' morphology. Finally, we have simulated the temperature programmed desorption of different coverages of hydrazine from the Cu(111) resulting in desorption peaks between 150 and 200 K

Reptile vector-borne diseases of zoonotic concern

Reptile vector-borne diseases (RVBDs) of zoonotic concern are caused by bacteria, protozoa and viruses transmitted by arthropod vectors, which belong to the subclass Acarina (mites and ticks) and the order Diptera (mosquitoes, sand flies and tsetse flies). The phyletic age of reptiles since their origin in the late Carboniferous, has favored vectors and pathogens to co-evolve through millions of years, bridging to the present host-vector-pathogen interactions. The origin of vector-borne diseases is dated to the early cretaceous with Trypanosomatidae species in extinct sand flies, ancestral of modern protozoan hemoparasites of zoonotic concern (e.g., Leishmania and Trypanosoma) associated to reptiles. Bacterial RVBDs are represented by microorganisms also affecting mammals of the genera Aeromonas, Anaplasma, Borrelia, Coxiella, Ehrlichia and Rickettsia, most of them having reptilian clades. Finally, reptiles may play an important role as reservoirs of arborivuses, given the low host specificity of anthropophilic mosquitoes and sand flies. In this review, vector-borne pathogens of zoonotic concern from reptiles are discussed, as well as the interactions between reptiles, arthropod vectors and the zoonotic pathogens they may transmit

Oxygen and nitrate enhanced in situ bioremediation of an oil -contaminated salt marsh

Salt marshes are among the most ecologically-sensitive areas to oil spills and remediation activities. Contaminated marshes may take years or decades to recover. Bioremediation is the process of enhancing naturally-occurring biodegradation by supplying limiting nutrients and terminal electron acceptors (TEAS). During this study, two TEAS (O2 and NO3 -) were evaluated for their ability to enhance natural in situ biodegradation of total petroleum hydrocarbons (TPH) in an oil-contaminated marsh. EPA (9071A) and ASTM (D5831) methods were evaluated for screening TPH in the contaminated marsh sediments. The ASTM Method was selected to evaluate TPH levels in candidate sites at the Fore River Creek salt marsh, Portland, ME impacted by the Julie N oil spill in 1996. Two plots in the marsh received air and NO3- , two served as controls. Subsurface horizontal wells were used to inject the amendments into the sediments. During 1998--1999, degradation of short chain (SC) and long chain (LC) aliphatics and aromatics, abundance of oil-degrading bacteria, nutrients and Spartina alterniora growth were monitored. Results indicated that natural attenuation (control) significantly reduced the TPH. The overall (1998--1999) degradation rates in the controls were 7.8 +/- 2.1 and 3.0 +/- 1.0 mg/kgdw/d for SC and LC aliphatics, respectively; and 6.9 +/- 4.8 mg/kgdw/d for aromatics. The NO3- amendment degradation rates for SC aliphatics and aromatics were 4.7 +/- 2.4 mg/kgdw/d and 4.5 +/- 3.3 mg/kgdw/d, respectively. These degradation rates were not significantly different than control rates. During the first season (Summer and Fall 1998), the air and NO3- amendments significantly degraded more SC aliphatics than the control, while NO 3- significantly degraded LC aliphatics. Porewater monitoring indicated more NO3- amendment was needed to promote denitrification. In addition, low degradation rates in the amendments plots may have been caused by problems with the well (distribution) system and mass transfer limitations. There was no significant change in the abundance of oil-degradees, probably because they were already established when the study began two years after the spill. Subsurface addition of air and NO3- has the potential to accelerate in situ biodegradation of Nos. 2 and 4 fuel oils in marsh sediments if problems with the supply of the amendments can be overcome

Operando Insights into Nanoparticle Transformations during Catalysis

Nanostructured materials play an important role in today’s chemical industry acting as catalysts in heterogeneous thermal and electrocatalytic processes for chemical energy conversion and the production of feedstock chemicals. Although catalysis research is a long standing discipline, the fundamental properties of heterogeneous catalysts like atomic structure, morphology and surface composition under realistic reaction conditions, together with insights into the nature of the catalytically active sites, have remained largely unknown. Having access to such information is however of outmost importance in order to understand the rate-determining processes and steps of many heterogeneous reactions and identify important structure-activity/selectivity relationships enabling knowledge-driven improvement of catalysts. In the last decades, in situ and operando methods have become available to identify the structural and morphological properties of the catalysts under working conditions. Such investigations have led to important insights into the catalytically-active state of the materials at different length scales, from the atomic level to the nano-/micrometer scale. The accessible operando methods utilizing photons range from vibrational spectroscopy in the infrared and optical regime to small-angle X-ray scattering (SAXS), diffraction (XRD), absorption spectroscopy (XAFS) and photoelectron spectroscopy (XPS), whereas electron-based techniques include scanning (SEM) and transmission microscopy (TEM) methods. In this work, we summarize recent findings of structural, morphological and chemical nanoparticle transformations during selected heterogeneous and electrochemical reactions, integrate them into the current state of knowledge, and discuss important future developments

Selective hydrogenation of CO on Fe3S4{111}: a computational study

Fischer–Tropsch (FT) synthesis has been a recursive method to form valuable molecules from syngas. Metal surfaces have been extensively studied as FT catalysts; among them, iron presents several phases under reaction conditions, oxides and carbides, as active sites for the FT and reverse water gas shift reaction. We present CO reduction on an iron sulfide phase with spinel structure, Fe3S4, also considering the pathways where C–O dissociates leaving CHx species on the surface, which may feed longer aliphatic chains via the FT process. We analysed the thermodynamic and kinetic availability of each step leading to O and OH species co-adsorbed on the surface as well as the formation of H2O from the hydrogenation of the alcohol group in the molecule. This detailed analysis led to energy profiles on both active sites of the surface, and we conclude that this Fe3S4 surface is highly selective towards the formation of methanol, in full agreement with experimental results. These findings point out that the C–C bond formation on greigite takes place through a hydroxycarbene FT mechanism

A kinetic model of water adsorption, clustering and dissociation on the Fe3S4{001} surface

The interaction of water with catalyst surfaces is a common process which requires investigation. Here, we have employed density functional theory calculations to investigate the adsorption of up to ten water molecules on the {001} surface of greigite (Fe3S4), which owing to its redox properties, is of increasing interest as a catalyst, e.g. in electro-catalysis. We have systematically analyzed and characterized the modes of water adsorption on the surface, where we have considered both molecular and dissociative adsorption processes. The calculations show that molecular adsorption is the predominant state on these surfaces, from both a thermodynamic and kinetic point of view. We have explored the molecular dispersion on the surface under different coverages and found that the orientation of the molecule, and therefore the surface dipole, depends on the number of adsorbed molecules. The interactions between the water molecules become stronger with an increasing number of water molecules, following an exponential decay which tends to the interaction energy found in bulk water. We have also shown the evolution of the infra-red signals as a function of water coverage relating to the H-bond networks formed on the surface. Next we have included these results in a classical micro-kinetic model, which introduced the effects of temperature in the simulations, thus helping us to derive the water cluster size on the greigite surface as a function of the initial conditions of pressure, temperature and external potential. The kinetic model concluded that water molecules agglomerate in clusters instead of wetting the surface, which agrees with the low hydrophilicity of Fe3S4. Clusters consisting of four water molecules was shown to be the most stable cluster under a wide range of temperatures and external potential

A density functional theory study of the hydrogenation and reduction of the thio-spinel Fe3S4{111} surface

The mineral greigite, Fe3S4, shows promising electro-reduction activity, especially towards carbon dioxide conversion to small organic molecules. We have employed density functional theory calculations with correction for the long-range dispersion forces to investigate the behavior of hydrogen on the greigite{111} surface. We have studied the adsorption, diffusion, surface reduction and associative (i.e. Volmer–Tafel mechanism) and molecular desorption of hydrogen as a function of its coverage. We found that (i) the H ad-atoms adsorb on S sites far from metallic centres in the topmost surface layer; (ii) the reduction of greigite by hydrogen is energetically unfavorable at any surface coverage; and (iii) molecular hydrogen evolution has a transition state at ∼0.5 eV above the energy of the reactants on Fe3S4{111}, which is very similar to the barrier found experimentally on Pt{111}. We have also determined the electrode potential under room conditions at which the H2 evolution reaction becomes energetically barrierless