Oxygen reduction reaction mechanism on nitrogen-doped graphene:A density functional theory study

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

BUCKLED LAYER STRUCTURE FOR ATOMIC ADSORPTION ON W(100) - THE (ROOT-2X-ROOT-2)R45-DEGREES NITROGEN STRUCTURE FROM ATLEED

Adsorption of 0.5 monolayer of N adatoms on W{100} results in a sharp (root 2 X root 2)R45 degrees LEED pattern. The only previous quantitative LEED study of this system gave a simple overlayer model with a Pendry R-factor of 0.55. An exhaustive search has been made of possible structures, including a novel vacancy reconstruction, displacive reconstructions and underlayer adsorption. From this work a new overlayer structure is derived with an R(p) value of 0.22, displaying a considerable buckling of 0.27 +/- 0.05 Angstrom within the second W layer and consequently involving large changes in the interlayer spacings of the surface. The N adatom is pseudo-five-fold coordinated to the W surface, bonding to a second-layer W atom with a nearest-neighbour bond length of 2.13 Angstrom and with the four next-nearest-neighbour W atoms in the surface plane at 2.27 Angstrom. The structure does not resolve the work function anomaly observed on this surface.

Intraspecific variation in nitrogen source utilisation by isolates of the ericoid mycorrhizal fungus Hymenoscyphus Ericae (Read) Korf and Kernan

Variation in the abilities of 35 isolates of the ericoid mycorrhizal fungal endophyte Hymenoscyphus ericae from two field sites to utilise inorganic and organic nitrogen sources in axenic culture has been investigated. While most isolates showed a preference for NH₄/^- as a sole nitrogen source, considerable variation was observed in the abilities of isolates to utilise amino acids and protein (BSA). In particular, large intraspecific variation was observed for glutamine and BSA utilisation, with some isolates thriving on these substrates while others produced little growth. The data suggest that individual isolates of H. ericae may vary considerably in their abilities to supply their host plants with nitrogen from different substrates in soil. (C) 2000 Elsevier Science Ltd.

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y^-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. their use potential as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of ¹³C:¹⁵N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of ¹³C:¹⁵N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of ¹³C and ¹⁵N labels from mineral-sorbed and dissolved amino acids.Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.

Carbon and nitrogen uptake of calcareous benthic foraminifera along a depth-related oxygen gradient in the OMZ of the Arabian Sea

Foraminifera are an important faunal element of the benthos in oxygen-depleted settings such as Oxygen Minimum Zones (OMZs) where they can play a relevant role in the processing of phytodetritus. We investigated the uptake of phytodetritus (labeled with 13C and 15N) by cal-careous foraminifera in the 0-1 cm sediment horizon under different oxygen concentrations within the OMZ in the eastern Arabian Sea. The in situ tracer experiments were carried out along a depth transect on the Indian margin over a period of 4 to 10 days. The uptake of phy-todetrital carbon within 4 days by all investigated species shows that phytodetritus is a rele-vant food source for foraminifera in OMZ sediments. The decrease of total carbon uptake from 540 to 1100 m suggests a higher demand for carbon by species in the low-oxygen core region of the OMZ or less food competition with macrofauna. Especially Uvigerinids showed high uptake of phytodetrital carbon at the lowest oxygenated site. Variation in the ratio of phytodetrital carbon to nitrogen between species and sites indicates that foraminiferal carbon and nitrogen use can be decoupled and different nutritional demands are found between spe-cies. Lower ratio of phytodetrital carbon and nitrogen at 540 m could hint for greater demand or storage of food-based nitrogen, ingestion or hosting of bacteria under almost anoxic condi-tions. Shifts in the foraminiferal assemblage structure (controlled by oxygen or food availabil-ity) and in the presence of other benthic organisms account for observed changes in the pro-cessing of phytodetritus in the different OMZ habitats. Foraminifera dominate the short-term processing of phytodetritus in the OMZ core but are less important in the lower OMZ bounda-ry region of the Indian margin as biological interactions and species distribution of foraminifera change with depth and oxygen levels.

Enhancement of Wear and Corrosion Resistance of Beta Titanium Alloy by Laser Gas Alloying with Nitrogen

The relatively high elastic modulus coupled with the presence of toxic vanadium (V) in Ti6Al4 V alloy has long been a concern in orthopaedic applications. To solve the problem, a variety of non-toxic and low modulus beta-titanium (beta-Ti) alloys have been developed. Among the beta-Ti alloy family, the quaternary Ti-Nb-Zr-Ta (TNZT) alloys have received the highest attention as a promising replacement for Ti6Al4 V due to their lower elastic modulus and outstanding long term stability against corrosion in biological environments. However, the inferior wear resistance of TNZT is still a problem that must be resolved before commercialising in the orthopaedic market. In this work, a newly-developed laser surface treatment technique was employed to improve the surface properties of Ti-35.3Nb-7.3Zr-5.7Ta alloy. The surface structure and composition of the laser-treated TNZT surface were examined by grazing incidence x-ray diffraction (GI-XRD) and x-ray photoelectron spectroscopy (XPS). The wear and corrosion resistance were evaluated by pin-on-plate sliding test and anodic polarisation test in Hanks’ solution. The experimental results were compared with the untreated (or base) TNZT material. The research findings showed that the laser surface treatment technique reported in this work can effectively improve the wear and corrosion resistance of TNZT.