CoO nanoparticles embedded in three-dimensional nitrogen/sulfur co-doped carbon nanofiber networks as a bifunctional catalyst for oxygen reduction/evolution reactions

High-performance and low-cost bifunctional electrocatalysts play crucial roles in oxygen reduction and evolution reactions. Herein, a novel three-dimensional (3D) bifunctional electrocatalyst was prepared by embedding CoO nanoparticles into nitrogen and sulfur co-doped carbon nanofiber networks (denoted as CoO@N/S-CNF) through a facile approach. The carbon nanofiber networks were derived from a nanostructured biological material which provided abundant functional groups to nucleate and anchor nanoparticles while retaining its interconnected 3D porous structure. The composite possesses a high specific surface area and graphitization degree, which favors both mass transport and charge transfer for electrochemical reaction. The CoO@N/S-CNF not only exhibits highly efficient catalytic activity towards oxygen reduction reaction (ORR) in alkaline media with an onset potential of about 0.84 V, but also shows better stability and stronger resistance to methanol than Pt/C. Furthermore, it only needs an overpotential of 1.55 V to achieve a current density of 10 mA cm^-2, suggesting that it is an efficient electrocatalyst for oxygen evolution reaction (OER). The ΔE value (oxygen electrode activity parameter) of CoO@N/S-CNF is calculated to be 0.828 V, which demonstrates that the composite could be a promising bifunctional electrocatalyst for both ORR and OER.

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content(similar to 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (similar to 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range similar to 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N-2 (77 K) and CO2 (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) <= 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.

Three-dimensional porous carbon nanofiber networks decorated with cobalt-based nanoparticles: A robust electrocatalyst for efficient water oxidation

Electrochemical water splitting used for generating hydrogen has attracted increasingly attention due to energy and environmental issues. It is a major challenge to design an efficient, robust and inexpensive electrocatalyst to achieve preferable catalytic performance. Herein, a novel three-dimensional (3D) electrocatalyst was prepared by decorating nanostructured biological material-derived carbon nanofibers with in situ generated cobalt-based nanospheres (denoted as CNF@Co) through a facile approach. The interconnected porous 3D networks of the resulting CNF@Co catalyst provide abundant channels and interfaces, which remarkably favor both mass transfer and oxygen evolution. The as-prepared CNF@Co shows excellent electrocatalytic activity towards the oxygen evolution reactions with an onset potential of about 0.445 V vs. Ag/AgCl. It only needs a low overpotential of 314 mV to achieve a current density of 10 mA/cm² in 1.0 M KOH. Furthermore, the CNF@Co catalyst exhibits excellent stability towards water oxidation, even outperforming commercial IrO<inf>2</inf> and RuO<inf>2</inf> catalysts.

Milling plant and soil material in plastic tubes over-estimates carbon and under-estimates nitrogen concentrations

Milling of plant and soil material in plastic tubes, such as microcentrifuge tubes, over-estimates carbon (C) and under-estimates nitrogen (N) concentrations due to the introduction of polypropylene into milled samples, as identified using Fourier-transform infra-red spectroscopy.

This study compares C and N concentrations of roots and soil milled in microcentrifuge tubes versus stainless steel containers, demonstrating that a longer milling time, greater milling intensity, smaller sample size and inclusion of abrasive sample material all increase polypropylene contamination from plastic tubes leading to overestimation of C concentrations by up to 8 % (0.08 g g(-1)).

Erroneous estimations of C and N, and other analytes, must be assumed after milling in plastic tubes and milling methods should be adapted to minimise such error.

Photodissociation and chemistry of N2 in the circumstellar envelope of carbon-rich AGB stars

The envelopes of AGB stars are irradiated externally by ultraviolet photons; hence, the chemistry is sensitive to the photodissociation of N$_2$ and CO, which are major reservoirs of nitrogen and carbon, respectively. The photodissociation of N$_2$ has recently been quantified by laboratory and theoretical studies. Improvements have also been made for CO photodissociation. For the first time, we use accurate N$_2$ and CO photodissociation rates and shielding functions in a model of the circumstellar envelope of the carbon-rich AGB star, IRC +10216. We use a state-of-the-art chemical model of an AGB envelope, the latest CO and N$_2$ photodissociation data, and a new method for implementing molecular shielding functions in full spherical geometry with isotropic incident radiation. We compare computed column densities and radial distributions of molecules with observations. The transition of N$_2$ $\to$ N (also, CO $\to$ C $\to$ C$^+$) is shifted towards the outer envelope relative to previous models. This leads to different column densities and radial distributions of N-bearing species, especially those species whose formation/destruction processes largely depend on the availability of atomic or molecular nitrogen, for example, C$_n$N ($n$=1, 3, 5), C$_n$N$^-$ ($n$=1, 3, 5), HC$_n$N ($n$=1, 3, 5, 7, 9), H$_2$CN and CH$_2$CN. The chemistry of many species is directly or indirectly affected by the photodissociation of N$_2$ and CO, especially in the outer shell of AGB stars where photodissociation is important. Thus, it is important to include N$_2$ and CO shielding in astrochemical models of AGB envelopes and other irradiated environments. In general, while differences remain between our model of IRC +10216 and the observed molecular column densities, better agreement is found between the calculated and observed radii of peak abundance.

An exploratory non-LTE model atmosphere analysis of B-type supergiants in the Small Magellanic Cloud

A preliminary differential non-LTE model atmosphere analysis of moderate resolution (R ~ 5 000) and signal-to-noise ratio spectra of 48 Small Magellanic Cloud B-type supergiants is presented. Standard techniques are adopted, viz. plane-parallel geometry and radiative and hydrostatic equilibrium. Spectroscopic atmospheric parameters (T_eff, log g and v_turb), luminosities and chemical abundances (He, C, N, O, Mg and Si) are estimated. These are compared with those deduced for a comparable sample of Galactic supergiants. The SMC targets appear to have similar atmospheric parameters, luminosities and helium abundances to the Galactic sample. Their magnesium and silicon underabundances are compatible with those found for main sequence SMC objects and there is no evidence for any large variation in their oxygen abundances. By contrast both their carbon and nitrogen lines strengths are inconsistent with single abundances, while their nitrogen to carbon abundance ratios appear to vary by at least as much and probably more than that found in the Galactic sample.

Long-range electronic coupling in bis(cyclometalated) ruthenium complexes

Symmetrical and unsymmetrical ligands containing terpyridyl coordinating units (N, N, N) or a cyclometalating equivalent (N, C, N), connected back-to-back either directly or via a p-terphenylene or 1,3-phenylene spacer, have been used to construct new diruthenium complexes. These compounds incorporate various terdentate chelates as capping ligands, to allow a double control of the electronic properties of each subcomplex and of the ensemble: via the terminal ligand or through the bridging fragment. Electronic coupling was studied from the intervalence transitions observed in several bimetallic ruthenium complexes of the bis-(cyclometalated) type differing by the substitution of a nitrogen atom by carbon in the terminal terpyridyl unit. The largest metal-metal interaction was found in complexes for which the terminal complexing unit is of the 1,3-di-2-pyridylbenzene type, i.e., with the carbon atom located on the metal-metal C-2 axis of the molecule. Investigations of the mechanism of interaction by extended Huckel calculations showed that the replacement of nitrogen by carbon raises the filled ligand levels, increasing the mixing with ligand orbitals and thus the metal-metal coupling. Finally, the intervalence transition was still observed for a bridging ligand containing three phenylene units as spacers, corresponding to a 24-Angstrom metal-metal distance.

The human micro-vascular enclothelial cells in vitro interaction with atomic-nitrogen-doped diamond-like carbon thin films

This paper reports the initial response of atomic nitrogen doped diamond like carbon (DLC) to endothelial cells in vitro. The introduction of nitrogen atoms/molecules to the diamond like carbon structures leads to an atomic structural change favorable to the attachment of human micro-vascular enclothelial cells. Whilst the semi-conductivity induced by nitrogen in DLC is thought to play a part, the increase in the inion-bonded N atoms and N-2 molecules in the atomic doped species (with the exclusion of the charged species) seems to contribute to the improved attachment of human microvascular endothelial cells. The increased endothelial attachment is associated with a lower work function and slightly higher water contact angle in the atomic doped films, where the heavy charged particles are excluded. The films used in the study were synthesized by the RF PECVD technique followed by post deposition doping with nitrogen, and afterwards the films were characterized by XPS, Raman spectroscopy, SIMS and Kelvin probe. The water contact angles were measured, and the counts of the adherent endothelial cells on the samples were carried out. This study is relevant and contributory to improving biocompatibility of surgical implants and prostheses.

Uptake of carbon, nitrogen and phosphorus by phytoplankton along the 20 degrees W meridian in the NE Atlantic between 57.5 degrees N and 37 degrees N

Phytoplankton biomass and rate of production were measured along a transect from 57.54 degreesN to 37.01 degreesN in the northeast Atlantic during July 1996 and at a series of stations over a 7-day period at 37 degreesN 20 degreesW. Surface nutrient concentrations ranged from 4 mu mol l(-1) NO3-, and 0.35 mu mol l(-1) PO43- at 57.54 degreesN to <10 nmol l(-1) NO3- and similar to 10 nmol l(-1) PO43- at 37.01 degreesN. The greatest phytoplankton biomass and production were measured in the vicinity of a frontal system at 50 degreesN, and there was a general decline in total phytoplankton biomass and production to the south of the transect. Production was measured in three size fractions. At the station with the highest chlorophyll concentrations (50.34 degreesN), phytoplankton cells larger than 5 mum dominated the assemblage, accounting for 72% of the chlorophyll concentration (22.9 mg m(-2)) and 51% of primary production (54.1 mmol Cm-2 d(-1)), but picophytoplankton production was also high (43%). At 57 degreesN, carbon fixation by the > 5 mum fraction accounted for 75% of the daily production of 60.75 mmol Cm-2 d(-1). At 37 degreesN, picophytoplankton was the dominant group, accounting for similar to 58% (10 mg m(-2)) of chlorophyll and similar to 64% (46 mmol Cm-2 d(-1)), of primary production. Nitrate, ammonium and phosphate uptake rates also were determined. Although high nitrate uptake rates were measured in the surface water at similar to 50 degreesN, the greatest uptake rates of both depth-integrated nitrate and ammonium were at the south of the transect. At 37 degreesN, a deep euphotic zone was present and light penetrated through the nitracline; total nitrate uptake was enhanced because of assimilation at the base of the euphotic zone. As a consequence, high values of depth-integrated f-ratio were measured in the oligotrophic waters at the south of the transect. Phosphate was predominantly incorporated into the picoplankton fraction, which included heterotrophic and autotrophic components, at all stations and a significant proportion of phosphate uptake occurred in the dark. The C:N:P assimilation ratios were variable throughout the region; phosphate uptake was generally greater than would be expected if nutrient assimilation were in proportion to the Redfield ratio. (C) 2001 Elsevier Science Ltd. All rights reserved.

Solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon, and carbon monoxide in 1-butyl-3-methylimidazolium tetrafluoroborate between temperatures 283 K and 343 K and at pressures close to atmospheric

Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3- methylimidazolium tetrafluoroborate, [bmim][BF4] - a room temperature ionic liquid - are reported as a function of temperature between 283 K and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble gas with mole fraction solubilities of the order of 10-2. Ethane and methane are one order of magnitude more soluble than the other five gases that have mole fraction solubilities of the order of 10-4. Hydrogen is the less soluble of the gaseous solutes studied. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations is of 1%. © 2005 Elsevier Ltd. All rights reserved.

Iron Age Pastoral Nomadism and Agriculture in the Eastern Eurasian Steppe: Implications from Dental Palaeopathology and Stable Carbon and Nitrogen Isotopes

Iron Age societies of the eastern Eurasian steppe are traditionally viewed as nomadic pastoralists. However, recent archaeological and anthropological research in Kazakhstan has reminded us that pastoralist economies can be highly complex and involve agriculture. This paper explores the nature of the pastoralist economies in two Early Iron Age populations from the burial grounds of Ai-Dai and Aymyrlyg in Southern Siberia. These populations represent two cultural groups of the Scythian World - the Tagar Culture of the Minusinsk Basin and the Uyuk Culture of Tuva. Analysis of dental palaeopathology and carbon and nitrogen stable isotopes suggests that domesticated cereals, particularly millet, and fish formed a major component of the diet of both groups. The findings contribute to the emerging picture of the nuances of Early Iron Age subsistence strategies on the eastern steppe.

Arsenic mobilization from iron oxyhydroxides is regulated by organic matter carbon to nitrogen (C:N) ratio

Arsenic (As) is mobilized from delta and floodplain aquifer sediments throughout S.E. Asia via reductive dissolution of As bound to iron (Fe) oxyhydroxides. The reductive driving force is organic carbon, but its source and constitution is uncertain. Here batch incubation experiments were conducted to investigate the role of organic matter (OM) carbon:nitrogen (C:N) ratio on the mobilization of arsenic, Fe and N from As dosed, Fe oxyhydroxide coated sands. As mobilization into pore waters from the sand was strongly regulated by the C:N ratio of the OM, and also the concentration of OM present. The lower the C:N, the more As released. Fe and ammonium release were similarly dependent on the quality and quantity of OM, but Fe mobilization was more rapid and ammonium release slower than As suggesting that the mobilization of these 3 moieties although interdependent, were not directly linked. It was concluded that low C:N ratios for OM responsible for reducing aquifers were As in groundwater is observed were likely.