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Sample records for n2 oxygen o2

  1. Production of NO2/-/ and N2O by nitrifying bacteria at reduced concentrations of oxygen

    NASA Technical Reports Server (NTRS)

    Goreau, T. J.; Kaplan, W. A.; Wofsy, S. C.; Mcelroy, M. B.; Valois, F. W.; Watson, S. W.

    1980-01-01

    The influence of oxygen concentration on the production of NO2(-) and N2O by nitrifying marine bacteria of the genus Nitrosomonas is investigated. Pure cultures of the ammonium-oxiding bacteria isolated from the Western Tropical Atlantic Ocean were grown at oxygen partial pressures from 0.005 to 0.2 atm, and concentrations of N2O in the air above the growth medium and dissolved NO2(-) were determined. Decreasing oxygen concentrations are observed to induce a marked decrease in NO2(-) production rates and increase in N2O evolution, leading to an increase of the relative yield of N2O with respect to NO2(-) from 0.3% to nearly 10%. Similar yields of N2O at atmospheric oxygen levels are found for nitrifying bacteria of the genera Nitrosomonas, Nitrosolobus, Nitrosospira and Nitrosococcus, while nitrite-oxydizing bacteria and a dinoflagellate did not produce detectable quantities of N2O. Results support the view that nitrification is a major source of N2O in the environment.

  2. The natural greenhouse effect of atmospheric oxygen (O2) and nitrogen (N2)

    NASA Astrophysics Data System (ADS)

    Höpfner, M.; Milz, M.; Buehler, S.; Orphal, J.; Stiller, G.

    2012-05-01

    The effect of collision-induced absorption by molecular oxygen (O2) and nitrogen (N2) on the outgoing longwave radiation (OLR) of the Earth's atmosphere has been quantified. We have found that on global average under clear-sky conditions the OLR is reduced due to O2 by 0.11 Wm-2 and due to N2 by 0.17 Wm-2. Together this amounts to 15% of the OLR-reduction caused by CH4 at present atmospheric concentrations. Over Antarctica the combined effect of O2 and N2 increases on average to about 38% of CH4 with single values reaching up to 80%. This is explained by less interference of H2O spectral bands on the absorption features of O2 and N2 for dry atmospheric conditions.

  3. SnO2-gated AlGaN/GaN high electron mobility transistors based oxygen sensors

    SciTech Connect

    Hung, S.T.; Chung, Chi-Jung; Chen, Chin Ching

    2012-01-01

    Hydrothermally grown SnO2 was integrated with AlGaN/GaN high electron mobility transistor (HEMT) sensor as the gate electrode for oxygen detection. The crystalline of the SnO2 was improved after annealing at 400 C. The grain growth kinetics of the SnO2 nanomaterials, together with the O2 gas sensing properties and sensing mechanism of the SnO2 gated HEMT sensors were investigated. Detection of 1% oxygen in nitrogen at 100 C was possible. A low operation temperature and low power consumption oxygen sensor can be achieved by combining the SnO2 films with the AlGaN/GaN HEMT structure

  4. Oxygen vibrations in the series Bi2Sr2Ca{_{n-1}}Cu{n}O{_{4+2 n+y}}

    NASA Astrophysics Data System (ADS)

    Faulques, E.; Dupouy, P.; Lefrant, S.

    1991-06-01

    We present a discussion of the oxygen vibrations in the Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} high T_c superconductors with the aim of interpreting Raman spectra in the case of the non-symmorphic Amaa structure. Group theory shows that the oxygen atoms belonging to the central CuO{2} plane generate a Raman activity for the n=1,3 phases. Consequently, we propose a novel assignment for the lines of weak intensity at 297, 316 and 333 cm^{-1}. It is shown that the two components of the 460 cm^{-1} band may be consistent with the Amma structure. Spectra recorded in crossed polarization exhibit weak lines which could be assigned to B {1g} modes expected for the three phases. Nous présentons une discussion sur les vibrations des atomes d'oxygène dans la série des supraconducteurs Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} dans le but d'interpréter les spectres Raman. L'analyse des modes normaux de vibration de la structure Amaa pour les phases n=1 ou 3 montre que les atomes d'oxygène du plan CuO{2} contenant les centres d'inversion donnent lieu à une activité Raman. En conséquence, nous proposons une nouvelle attribution pour les raies de faible intensité à 297, 316 et 333 cm^{-1}. Nous montrons que le dédoublement de la bande à 460 cm^{-1} pourrait être dû à la structure Amaa. Les spectres enregistrés en polarization croisée montrent de faibles bandes qui peuvent être attribuées aux modes B {1g} attendus pour les trois phases.

  5. Effects of N2O narcosis on the contraction and repayment of an oxygen debt

    NASA Technical Reports Server (NTRS)

    Schatte, C. L.; Hall, P.; Fitch, J. W.; Loader, J. E.

    1974-01-01

    The oxygen deficit, oxygen debt, and the difference between them were measured in five male and three female subjects during and after exercise while breathing either air or a normoxic mixture containing 33% N2O and nitrogen. With the exception of a higher respiratory quotient at rest in N2O, there were no statistically significant differences for oxygen consumption, carbon dioxide production, expired gas volume, heart rate or blood lactate while breathing N2O during rest, exercise, or recovery. An appreciably, but not statistically, greater mean oxygen deficit was found in N2O along with a significantly greater mean oxygen debt; deficit-debt difference was unaffected by N2O. It was speculated that N2O narcosis did not affect the ability to utilize oxygen but that the response to the greater oxygen need of exercise may have been slowed with perhaps a concomitant greater depletion of stored high energy compounds.

  6. Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

    PubMed

    Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

    2004-10-04

    The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

  7. Vertical segregation among pathways mediating nitrogen loss (N2 and N2O production) across the oxygen gradient in a coastal upwelling ecosystem

    NASA Astrophysics Data System (ADS)

    Galán, Alexander; Thamdrup, Bo; Saldías, Gonzalo S.; Farías, Laura

    2017-10-01

    The upwelling system off central Chile (36.5° S) is seasonally subjected to oxygen (O2)-deficient waters, with a strong vertical gradient in O2 (from oxic to anoxic conditions) that spans a few metres (30-50 m interval) over the shelf. This condition inhibits and/or stimulates processes involved in nitrogen (N) removal (e.g. anammox, denitrification, and nitrification). During austral spring (September 2013) and summer (January 2014), the main pathways involved in N loss and its speciation, in the form of N2 and/or N2O, were studied using 15N-tracer incubations, inhibitor assays, and the natural abundance of nitrate isotopes along with hydrographic information. Incubations were developed using water retrieved from the oxycline (25 m depth) and bottom waters (85 m depth) over the continental shelf off Concepción, Chile. Results of 15N-labelled incubations revealed higher N removal activity during the austral summer, with denitrification as the dominant N2-producing pathway, which occurred together with anammox at all times. Interestingly, in both spring and summer maximum potential N removal rates were observed in the oxycline, where a greater availability of oxygen was observed (maximum O2 fluctuation between 270 and 40 µmol L-1) relative to the hypoxic bottom waters ( < 20 µmol O2 L-1). Different pathways were responsible for N2O produced in the oxycline and bottom waters, with ammonium oxidation and dissimilatory nitrite reduction, respectively, as the main source processes. Ammonium produced by dissimilatory nitrite reduction to ammonium (DNiRA) could sustain both anammox and nitrification rates, including the ammonium utilized for N2O production. The temporal and vertical variability of δ15N-NO3- confirms that multiple N-cycling processes are modulating the isotopic nitrate composition over the shelf off central Chile during spring and summer. N removal processes in this coastal system appear to be related to the availability and distribution of oxygen and

  8. Quenching of I(2P1/2) by NO2, N2O4, and N2O.

    PubMed

    Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

    2007-10-11

    Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.

  9. Nanocrystalline CeO2-δ coated β-MnO2 nanorods with enhanced oxygen transfer property

    NASA Astrophysics Data System (ADS)

    Huang, Xiubing; Zhao, Guixia; Chang, Yueqi; Wang, Ge; Irvine, John T. S.

    2018-05-01

    In this research, β-MnO2 nanorods were synthesized by a hydrothermal method, followed by a facile precipitation method to obtain nanocrystalline CeO2-δ coated β-MnO2 nanorods. The as-prepared samples were characterized by XRD, HRTEM, FESEM, XPS and in-situ high-temperature XRD. The HRTEM results show that well dispersed CeO2-δ nanocrystals sized about 5 nm were coated on the surface of β-MnO2 nanorods. The oxygen storage and transfer property of as-synthesized materials were evaluated using TGA under various atmospheres (air, pure N2, and 5%H2/95%Ar). The TGA results indicate that CeO2-δ modification could favour the reduction of Mn4+ to Mn3+ and/or Mn2+ at lower temperature as compared with pure β-MnO2 nanorods and the physically mixed CeO2-δ-β-MnO2 under low oxygen partial pressure conditions (i.e., pure N2, 5%H2/95%Ar). Specifically, CeO2-δ@β-MnO2 sample can exhibit 7.5 wt% weight loss between 100 and 400 °C under flowing N2 and 11.4 wt% weight loss between 100 and 350 °C under flowing 5%H2/95%Ar. During the reduction process under pure N2 or 5%H2/95%Ar condition, the oxygen ions in β-MnO2 nanorods are expected to be released to the surroundings in the form of O2 or H2O with the coated CeO2-δ nanocrystals acting as mediator as inferred from the synergistic effect between the well-interacted CeO2-δ nanocrystals and β-MnO2 nanorods.

  10. Interplay between O2 and SnO2: oxygen ionosorption and spectroscopic evidence for adsorbed oxygen.

    PubMed

    Gurlo, Alexander

    2006-10-13

    Tin dioxide is the most commonly used material in commercial gas sensors based on semiconducting metal oxides. Despite intensive efforts, the mechanism responsible for gas-sensing effects on SnO(2) is not fully understood. The key step is the understanding of the electronic response of SnO(2) in the presence of background oxygen. For a long time, oxygen interaction with SnO(2) has been treated within the framework of the "ionosorption theory". The adsorbed oxygen species have been regarded as free oxygen ions electrostatically stabilized on the surface (with no local chemical bond formation). A contradiction, however, arises when connecting this scenario to spectroscopic findings. Despite trying for a long time, there has not been any convincing spectroscopic evidence for "ionosorbed" oxygen species. Neither superoxide ions O(2)(-), nor charged atomic oxygen O,(-) nor peroxide ions O(2)(2-) have been observed on SnO(2) under the real working conditions of sensors. Moreover, several findings show that the superoxide ion does not undergo transformations into charged atomic oxygen at the surface, and represents a dead-end form of low-temperature oxygen adsorption on reduced metal oxide.

  11. Raman study of HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) superconductors

    NASA Astrophysics Data System (ADS)

    Zhou, Xingjiang; Cardona, M.; Chu, C. W.; Lin, Q. M.; Loureiro, S. M.; Marezio, M.

    1996-02-01

    Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) high- Tc superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm -1, with increasing number of CuO 2 layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm -1 mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm -1 mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm -1 modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.

  12. Time-dependent middle ear pressure changes under general anaesthesia in children: N2O-O2 mixture versus air-oxygen mixture.

    PubMed

    Apan, A; Muluk, N Bayar; Güler, S; Budak, B

    2013-01-01

    The aim of this study was to investigate the effects of N2O-O2 mixture (Inspired O2 30%) on middle ear pressure (MEP) in children compared with the effects of an air-oxygen mixture (Inspired O2 50%). The study included thirty child patients who underwent general anaesthesia for different reasons, with the exception of ENT problems and ear interventions. They were randomly divided into two groups. Group 1 (15 children: 10 male and 5 female) received a N2O-O2 mixture (Inspired O2 30%); and group 2 (15 children: 10 male and 5 female) were given an air-oxygen mixture (Inspired O2 50%). MEP was measured using a portable impedance analyser before the operation (PreO),10 minutes after intubation (10AEn), 30 minutes after intubation (30AEn), 10 minutes before extubation (10BEx), 15 minutes after the operation (PO15), 30 minutes after the operation (PO30), 1 hour after the operation (PO1h) and 6 hours after the operation (PO6h). The pressure and compliance values were the same in groups 1 and 2. The pressure-time graphs for the two groups were different: in Group 2, MEP rose quickly at 10AEn and positive pressure values were seen in the middle ear. MEP then fell rapidly until the end of the surgery and lower and negative pressures (Mean -50 daPa) were observed at PO6h. In Group 1, MEP was elevated at 10AEn and positive pressure was found (but not as high as in Group 2). MEP then fell more slowly. In other words, positive pressure in the middle ear persisted longer and the middle ear was subjected to positive pressure and nitrogen over a longer period. Separate analyses were made in Groups 1 and 2 of pressure differences and of compliance values at eight measurement points using the Friedman test. Differences in pressure values were found to be statistically significant in both Group 1 (p = 0.000) and Group 2 (p = 0.000). In Group 1, all the 10AEn and 30AEn values were significantly higher than the PreO, PO30, PO1h and PO6h values. The 10BEx value was significantly higher

  13. O2 and CO2 glow-discharge-assisted oxygen transport through Ag

    NASA Astrophysics Data System (ADS)

    Outlaw, R. A.

    1990-08-01

    The permeation of oxygen through Ag normally occurs by a sequence of steps which include the initial dissociative adsorption of molecular oxygen at the upstream surface, the dissolution of the atoms into the bulk, and the subsequent migration of the atoms between octahedral sites of the lattice until they arrive at the vacuum interface downstream. The dissociative adsorption step, however, proceeds slowly, as indicated by the low sticking coefficient of O2 on Ag(10-6-10-3). The application of a dc field in 0.5 Torr of O2 (E/n˜10-14 V cm2) on the upstream side of a Ag membrane generated gas phase atomic oxygen that substantially enhanced the transport. The transport flux was observed to increase from a value of 4.4×1013 cm-2 s-1 to a glow discharge value of 2.83×1014 cm-2 s-1 at a membrane temperature of 650 °C. This suggests that the dissociative adsorption step limits the supply of oxygen atoms to the upstream side of the membrane. When the upstream O2 was replaced by an equal pressure of CO2, only a small permeation signal was observed, but the application of the glow discharge substantially increased the transport flux from 3.25×1012 cm-2 s-1 to 1.74×1014 cm-2 s-1. This method of separating O2 from a CO2 environment may be a possible mechanism for providing a supply of oxygen for astronauts in a manned mission to Mars.

  14. Diffusion reaction of oxygen in HfO2/SiO2/Si stacks.

    PubMed

    Ferrari, S; Fanciulli, M

    2006-08-03

    We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.

  15. Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

    SciTech Connect

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

    2014-05-08

    We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, themore » N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.« less

  16. Impact of oxygen precursor flow on the forward bias behavior of MOCVD-Al2O3 dielectrics grown on GaN

    NASA Astrophysics Data System (ADS)

    Chan, Silvia H.; Bisi, Davide; Liu, Xiang; Yeluri, Ramya; Tahhan, Maher; Keller, Stacia; DenBaars, Steven P.; Meneghini, Matteo; Mishra, Umesh K.

    2017-11-01

    This paper investigates the effects of the oxygen precursor flow supplied during metalorganic chemical vapor deposition (MOCVD) of Al2O3 films on the forward bias behavior of Al2O3/GaN metal-oxide-semiconductor capacitors. The low oxygen flow (100 sccm) delivered during the in situ growth of Al2O3 on GaN resulted in films that exhibited a stable capacitance under forward stress, a lower density of stress-generated negative fixed charges, and a higher dielectric breakdown strength compared to Al2O3 films grown under high oxygen flow (480 sccm). The low oxygen grown Al2O3 dielectrics exhibited lower gate current transients in stress/recovery measurements, providing evidence of a reduced density of trap states near the GaN conduction band and an enhanced robustness under accumulated gate stress. This work reveals oxygen flow variance in MOCVD to be a strategy for controlling the dielectric properties and performance.

  17. Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

    NASA Astrophysics Data System (ADS)

    Yao, Guisheng; Li, Yong; Jiang, Peng; Jin, Xiuming; Long, Menglong; Qin, Haixia; Kumar, R. Vasant

    2017-04-01

    Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si3N4 and Si2N2O are formed as the nitridation products in the samples. Fibroid and short columnar Si3N4 are detected in the samples. The formation mechanisms of Si3N4 and Si2N2O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O2 in N2 atmosphere, forming a thin film of SiO2 on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO2 film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO2 film will crack, and N2 is infiltrated into the central section of the sample through cracks, generating Si2N2O and short columnar Si3N4 in situ. At the same time, metastable SiO(g) reacts with N2 and form fibroid Si3N4. In the regions where the oxygen partial pressure is high, Si3N4 is oxidized into Si2N2O.

  18. Superconductivity Induced by Oxygen Doping in Y2 O2 Bi.

    PubMed

    Cheng, Xiyue; Gordon, Elijah E; Whangbo, Myung-Hwan; Deng, Shuiquan

    2017-08-14

    When doped with oxygen, the layered Y 2 O 2 Bi phase becomes a superconductor. This finding raises questions about the sites for doped oxygen, the mechanism of superconductivity, and practical guidelines for discovering new superconductors. We probed these questions in terms of first-principles calculations for undoped and O-doped Y 2 O 2 Bi. The preferred sites for doped O atoms are the centers of Bi 4 squares in the Bi square net. Several Bi 6p x/y bands of Y 2 O 2 Bi are raised in energy by oxygen doping because the 2p x/y orbitals of the doped oxygen make antibonding possible with the 6p x/y orbitals of surrounding Bi atoms. Consequently, the condition necessary for the "flat/steep" band model for superconductivity is satisfied in O-doped Y 2 O 2 Bi. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Single-coal-particle combustion in O{sub 2}/N{sub 2} and O{sub 2}/CO{sub 2} environments

    SciTech Connect

    Bejarano, Paula A.; Levendis, Yiannis A.

    A fundamental investigation has been conducted on the combustion of single particles of a bituminous coal (45-53, 75-90, and 150-180 {mu}m), of a lignite coal (45-53 and 75-90 {mu}m), and of spherical and monodisperse synthetic chars (43 {mu}m) at increasing O{sub 2} mole fractions in either N{sub 2} or CO{sub 2} balance gases. The synthetic particles were used to facilitate the observation of combustion phenomena with minimum distractions from particle-to-particle variabilities. The laboratory setup consisted of a drop-tube furnace operated at temperatures of 1400 and 1600 K. A calibrated three-color pyrometer, interfaced with the furnace, recorded luminous particle temperature-time profiles.more » Experimental results revealed that coal particles burned at higher mean temperatures and shorter combustion times in O{sub 2}/N{sub 2} than in O{sub 2}/CO{sub 2} environments at analogous oxygen mole fractions. In the case of the bituminous coal used herein and for the experimental combustion conditions tested, measured volatile and char temperatures as in air (21% O{sub 2}) were attained with an oxygen content in the CO{sub 2} mixtures in the neighborhood of 30%. Bituminous coal volatile and char burnout times comparable to those in air (21% O{sub 2}) were attained with oxygen content in the CO{sub 2} mixtures in the range of 30-35%. In the case of the lignite coal burned, the corresponding differences in oxygen mole fractions, which result in similar particle temperatures and burnout times in the two different gas mixtures, were less pronounced. (author)« less

  20. NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

    2015-04-01

    Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

  1. Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

    2002-01-01

    Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

  2. Theoretical study of the interaction of N/sub 2/ with water molecules. (H/sub 2/O)/sub n/:N/sub 2/, n = 1--8

    SciTech Connect

    Curtiss, L.A.; Eisgruber, C.L.

    1984-03-01

    Ab initio molecular orbital calculations including correlation energy have been carried out on the interaction of a single H/sub 2/O molecule with N/sub 2/. The potential energy surface for H/sub 2/O:N/sub 2/ is found to have a minimum corresponding to a HOH xxx N/sub 2/ structure with a weak (<2 kcal mol/sup -1/) hydrogen bond. A second, less stable, configuration corresponding to a H/sub 2/O xxx N/sub 2/ structure with N/sub 2/ bonded side on to the oxygen of H/sub 2/O was found to be either a minimum or a saddle point in the potential energy surface depending on themore » level of calculation. The minimal STO-3G basis set was used to investigate the interaction of up to eight H/sub 2/O molecules with N/sub 2/. Two types of clusters, one containing only HOH xxx N/sub 2/ interactions and the other containing both HOH xxxN/sub 2/ and H/sub 2/O xxx N/sub 2/ interactions, were investigated for (N/sub 2/:(H/sub 2/O)/sub n/, n = 2--8).« less

  3. Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2

    NASA Technical Reports Server (NTRS)

    Minschwaner, K.; Salawitch, R. J.; Mcelroy, M. B.

    1993-01-01

    An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.

  4. Fe/N/C composite in Li-O2 battery: studies of catalytic structure and activity toward oxygen evolution reaction.

    PubMed

    Shui, Jiang-Lan; Karan, Naba K; Balasubramanian, Mahalingam; Li, Shu-You; Liu, Di-Jia

    2012-10-10

    Atomically dispersed Fe/N/C composite was synthesized and its role in controlling the oxygen evolution reaction during Li-O(2) battery charging was studied by use of a tetra(ethylene glycol) dimethyl ether-based electrolyte. Li-O(2) cells using Fe/N/C as the cathode catalyst showed lower overpotentials than α-MnO(2)/carbon catalyst and carbon-only material. Gases evolved during the charge step contained only oxygen for Fe/N/C cathode catalyst, whereas CO(2) was also detected in the case of α-MnO(2)/C or carbon-only material; this CO(2) was presumably generated from electrolyte decomposition. Our results reiterate the catalytic effect in reducing overpotentials, which not only enhances battery efficiency but also improves its lifespan by reducing or eliminating electrolyte decomposition. The structure of the Fe/N/C catalyst was characterized by transmission electron microscopy, scanning transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, and X-ray absorption spectroscopy. Iron was found to be uniformly distributed within the carbon matrix, and on average, Fe was coordinated by 3.3 ± 0.6 and 2.2 ± 0.3 low Z elements (C/N/O) at bond distances of ~1.92 and ~2.09 Å, respectively.

  5. Origin of Active Oxygen in a Ternary CuO x /Co 3O 4–CeO 2 Catalyst for CO Oxidation

    SciTech Connect

    Liu, Zhigang; Wu, Zili; Peng, Xihong

    2014-11-14

    In this paper, we have studied CO oxidation over a ternary CuO x/Co 3O 4-CeO 2 catalyst and employed the techniques of N 2 adsorption/desporption, XRD, TPR, TEM, in situ DRIFTS and QMS (Quadrupole mass spectrometer) to explore the origin of active oxygen. DRIFTS-QMS results with labeled 18O2 indicate that the origin of active oxygens in CuO x/Co 3O 4-CeO 2 obeys a model, called as queue mechanism. Namely gas-phase molecular oxygens are dissociated to atomic oxygens and then incorporate in oxygen vacancies located at the interface of Co 3O 4-CeO 2 to form active crystalline oxygens, and these activemore » oxygens diffuse to the CO-Cu + sites thanks to the oxygen vacancy concentration magnitude and react with the activated CO to form CO 2. This process, obeying a queue rule, provides active oxygens to form CO 2 from gas-phase O 2 via oxygen vacancies and crystalline oxygen at the interface of Co 3O 4-CeO 2.« less

  6. Mixed Matrix Membranes for O2/N2 Separation: The Influence of Temperature

    PubMed Central

    Fernández-Barquín, Ana; Casado-Coterillo, Clara; Valencia, Susana; Irabien, Angel

    2016-01-01

    In this work, mixed matrix membranes (MMMs) composed of small-pore zeolites with various topologies (CHA (Si/Al = 5), LTA (Si/Al = 1 and 5), and Rho (Si/Al = 5)) as dispersed phase, and the hugely permeable poly(1-trimethylsilyl-1-propyne) (PTMSP) as continuous phase, have been synthesized via solution casting, in order to obtain membranes that could be attractive for oxygen-enriched air production. The O2/N2 gas separation performance of the MMMs has been analyzed in terms of permeability, diffusivity, and solubility in the temperature range of 298–333 K. The higher the temperature of the oxygen-enriched stream, the lower the energy required for the combustion process. The effect of temperature on the gas permeability, diffusivity, and solubility of these MMMs is described in terms of the Arrhenius and Van’t Hoff relationships with acceptable accuracy. Moreover, the O2/N2 permselectivity of the MMMs increases with temperature, the O2/N2 selectivities being considerably higher than those of the pure PTMSP. In consequence, most of the MMMs prepared in this work exceeded the Robeson’s upper bound for the O2/N2 gas pair in the temperature range under study, with not much decrease in the O2 permeabilities, reaching O2/N2 selectivities of up to 8.43 and O2 permeabilities up to 4,800 Barrer at 333 K. PMID:27196937

  7. Influence of under pressure dissolved oxygen on trichloroethylene degradation by the H2O2/TiO2 process.

    PubMed

    Hoseini, Mohammad; Nabizadeh, Ramin; Nazmara, Shahrokh; Safari, Gholam Hossein

    2013-12-20

    The widespread use of trichloroethylene (TCE) and its frequent release into the environment has caused many environmental and health problems. In this study the degradation of TCE at different micromolar concentrations was investigated in a stainless steel reactor with various concentrations of H2O2 and TiO2 at different oxygen pressures and three different pHs. To examine the synergistic effect of under pressure oxygen on TCE degradation, the concentrations of H2O2 and TiO2 as well as pH were first optimized, and then the experiments were performed under optimal conditions. Gas chromatography with a flame ionization detector (FID) was used to measure TCE concentrations. Results showed that the percentage of TCE degradation without pressurized oxygen was low and it increased with increasing pressure of oxygen at all initial concentrations of TCE. The degradation percentages without oxygen pressure were 48.27%, 51.22%, 58.13% and 64.33% for TCE concentrations of 3000, 1500, 300 and 150 μg/L respectively. At an oxygen pressure of 2.5 atmospheres (atm) the percent degradation of TCE reached 84.85%, 89.14%, 93.13% and 94.99% respectively for the aforementioned TCE concentrations. The results of this study show that the application of dissolved oxygen under pressure increases the efficiency of the H2O2/TiO2 process on the degradation of TCE and can be used along with other oxidants as an effective method for the removal of this compound from aqueous solutions.

  8. Influence of under pressure dissolved oxygen on trichloroethylene degradation by the H2O2/TiO2 process

    PubMed Central

    2013-01-01

    Background The widespread use of trichloroethylene (TCE) and its frequent release into the environment has caused many environmental and health problems. In this study the degradation of TCE at different micromolar concentrations was investigated in a stainless steel reactor with various concentrations of H2O2 and TiO2 at different oxygen pressures and three different pHs. Methods To examine the synergistic effect of under pressure oxygen on TCE degradation, the concentrations of H2O2 and TiO2 as well as pH were first optimized, and then the experiments were performed under optimal conditions. Gas chromatography with a flame ionization detector (FID) was used to measure TCE concentrations. Results Results showed that the percentage of TCE degradation without pressurized oxygen was low and it increased with increasing pressure of oxygen at all initial concentrations of TCE. The degradation percentages without oxygen pressure were 48.27%, 51.22%, 58.13% and 64.33% for TCE concentrations of 3000, 1500, 300 and 150 μg/L respectively. At an oxygen pressure of 2.5 atmospheres (atm) the percent degradation of TCE reached 84.85%, 89.14%, 93.13% and 94.99% respectively for the aforementioned TCE concentrations. Conclusions The results of this study show that the application of dissolved oxygen under pressure increases the efficiency of the H2O2/TiO2 process on the degradation of TCE and can be used along with other oxidants as an effective method for the removal of this compound from aqueous solutions. PMID:24359702

  9. An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 heterostructure for enhanced visible light photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Guo, Yanru; Xiao, Limin; Zhang, Min; Li, Qiuye; Yang, Jianjun

    2018-05-01

    An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 ternary nanocomposite was fabricated using nanotubular titanic acid as precursors via a simple photo-deposition of Pd nanoparticles and calcination process. The prepared nanocomposites were investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy, respectively. For g-C3N4/TiO2 binary nanocomposites, at the optimal content of g-C3N4 (2%), the apparent photocatalytic activity of 2%g-C3N4/TiO2 was 9 times higher than that of pure TiO2 under visible-light illumination. After deposition of Pd (1 wt%) at the contact interface between g-C3N4 and TiO2, the 2%g-C3N4/Pd/TiO2 ternary nanocomposites demonstrated the highest visible-light-driven photocatalytic activity for the degradation of gaseous propylene, which was 16- and 2-fold higher activities than pure TiO2 and 2%g-C3N4/TiO2, respectively. The mechanism for the enhanced photocatalytic performance of the g-C3N4/Pd/TiO2 photo-catalyst is proposed to be based on the efficient separation of photo-generated electron-hole pairs through Z-scheme system, in which uniform dispersity of Pd nanoparticles at contact interface between g-C3N4 and TiO2 and oxygen vacancies promote charge separation.

  10. Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

    NASA Astrophysics Data System (ADS)

    Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

    2016-01-01

    In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

  11. A facile photoassisted route to synthesis N, F-codoped oxygen-deficient TiO2 with enhanced photocatalytic performance under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Kang, Xiaolan; Han, Ying; Song, Xuezhi; Tan, Zhenquan

    2018-03-01

    Herein, we report a facile and economical photoassisted strategy for synthesizing the highly active N, F-codoped oxygen-deficient TiO2 with coexposed {001} and {101} facets. NH4TiOF3 mesocrystals were used to act as the resource of dopants and the intermediate to fabricate TiO2 with highly active {001} facets. Comprehensive analysis based on X-ray photoelectron spectroscopy, transmission electron microscopy and electron spin resonances manifested that F, N and oxygen vacancies were simultaneously introduced to TiO2 through the photoassisted process. The test of phenol and Rhodamine B (RhB) degradation under visible light demonstrates that the as-prepared N, F codoped oxygen-deficient TiO2 exhibits higher photocatalytic activity than its references. The increased photocatalytic performances results from the synergetic effect of the induced Vo's and N, F codoping in TiO2 with co-exposed {001} and {101} facets, favoring the visible light utilization as well as the separation of photogenerated carriers. This strategy is expected to provide a new insight into the design of high performance photocatalysts.

  12. Time-dependent one-dimensional simulation of atmospheric dielectric barrier discharge in N2/O2/H2O using COMSOL Multiphysics

    NASA Astrophysics Data System (ADS)

    Sohbatzadeh, F.; Soltani, H.

    2018-04-01

    The results of time-dependent one-dimensional modelling of a dielectric barrier discharge (DBD) in a nitrogen-oxygen-water vapor mixture at atmospheric pressure are presented. The voltage-current characteristics curves and the production of active species are studied. The discharge is driven by a sinusoidal alternating high voltage-power supply at 30 kV with frequency of 27 kHz. The electrodes and the dielectric are assumed to be copper and quartz, respectively. The current discharge consists of an electrical breakdown that occurs in each half-period. A detailed description of the electron attachment and detachment processes, surface charge accumulation, charged species recombination, conversion of negative and positive ions, ion production and losses, excitations and dissociations of molecules are taken into account. Time-dependent one-dimensional electron density, electric field, electric potential, electron temperature, densities of reactive oxygen species (ROS) and reactive nitrogen species (RNS) such as: O, O-, O+, {O}2^{ - } , {O}2^{ + } , O3, {N}, {N}2^{ + } , N2s and {N}2^{ - } are simulated versus time across the gas gap. The results of this work could be used in plasma-based pollutant degradation devices.

  13. Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

    NASA Astrophysics Data System (ADS)

    Avdeev, Vasilii I.; Bedilo, Alexander F.

    2018-03-01

    The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+<2OH>Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+<2OH>Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

  14. Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

    2017-05-01

    The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

  15. Ammonia oxidation pathways and nitrifier denitrification are significant sources of N2O and NO under low oxygen availability

    PubMed Central

    Zhu, Xia; Burger, Martin; Doane, Timothy A.; Horwath, William R.

    2013-01-01

    The continuous increase of nitrous oxide (N2O) abundance in the atmosphere is a global concern. Multiple pathways of N2O production occur in soil, but their significance and dependence on oxygen (O2) availability and nitrogen (N) fertilizer source are poorly understood. We examined N2O and nitric oxide (NO) production under 21%, 3%, 1%, 0.5%, and 0% (vol/vol) O2 concentrations following urea or ammonium sulfate [(NH4)2SO4] additions in loam, clay loam, and sandy loam soils that also contained ample nitrate. The contribution of the ammonia (NH3) oxidation pathways (nitrifier nitrification, nitrifier denitrification, and nitrification-coupled denitrification) and heterotrophic denitrification (HD) to N2O production was determined in 36-h incubations in microcosms by 15N-18O isotope and NH3 oxidation inhibition (by 0.01% acetylene) methods. Nitrous oxide and NO production via NH3 oxidation pathways increased as O2 concentrations decreased from 21% to 0.5%. At low (0.5% and 3%) O2 concentrations, nitrifier denitrification contributed between 34% and 66%, and HD between 34% and 50% of total N2O production. Heterotrophic denitrification was responsible for all N2O production at 0% O2. Nitrifier denitrification was the main source of N2O production from ammonical fertilizer under low O2 concentrations with urea producing more N2O than (NH4)2SO4 additions. These findings challenge established thought attributing N2O emissions from soils with high water content to HD due to presumably low O2 availability. Our results imply that management practices that increase soil aeration, e.g., reducing compaction and enhancing soil structure, together with careful selection of fertilizer sources and/or nitrification inhibitors, could decrease N2O production in agricultural soils. PMID:23576736

  16. Ammonia oxidation pathways and nitrifier denitrification are significant sources of N2O and NO under low oxygen availability.

    PubMed

    Zhu, Xia; Burger, Martin; Doane, Timothy A; Horwath, William R

    2013-04-16

    The continuous increase of nitrous oxide (N2O) abundance in the atmosphere is a global concern. Multiple pathways of N2O production occur in soil, but their significance and dependence on oxygen (O2) availability and nitrogen (N) fertilizer source are poorly understood. We examined N2O and nitric oxide (NO) production under 21%, 3%, 1%, 0.5%, and 0% (vol/vol) O2 concentrations following urea or ammonium sulfate [(NH4)2SO4] additions in loam, clay loam, and sandy loam soils that also contained ample nitrate. The contribution of the ammonia (NH3) oxidation pathways (nitrifier nitrification, nitrifier denitrification, and nitrification-coupled denitrification) and heterotrophic denitrification (HD) to N2O production was determined in 36-h incubations in microcosms by (15)N-(18)O isotope and NH3 oxidation inhibition (by 0.01% acetylene) methods. Nitrous oxide and NO production via NH3 oxidation pathways increased as O2 concentrations decreased from 21% to 0.5%. At low (0.5% and 3%) O2 concentrations, nitrifier denitrification contributed between 34% and 66%, and HD between 34% and 50% of total N2O production. Heterotrophic denitrification was responsible for all N2O production at 0% O2. Nitrifier denitrification was the main source of N2O production from ammonical fertilizer under low O2 concentrations with urea producing more N2O than (NH4)2SO4 additions. These findings challenge established thought attributing N2O emissions from soils with high water content to HD due to presumably low O2 availability. Our results imply that management practices that increase soil aeration, e.g., reducing compaction and enhancing soil structure, together with careful selection of fertilizer sources and/or nitrification inhibitors, could decrease N2O production in agricultural soils.

  17. Ocean N2O Emissions : Recent Global Estimates and Anthropogenically Influenced Changes

    NASA Astrophysics Data System (ADS)

    Suntharalingam, P.; Buithenuis, E.; Andrews, O.; Le Quere, C.

    2016-12-01

    Oceanic N2O is produced by microbial activity during organic matter cycling in the subsurface ocean; its production mechanisms display sensitivity to ambient oxygen level. In the oxic ocean, N2O is produced as a byproduct during the oxidation of ammonia to nitrate, mediated by ammonia oxidizing bacteria and archea. N2O is also produced and consumed in sub-oxic and anoxic waters through the action of marine denitrifiers during the multi-step reduction of nitrate to gaseous nitrogen. The oceanic N2O distribution therefore displays significant heterogeneity with background levels of 10-20 nmol/l in the well-oxygenated ocean basins, high concentrations (> 40 nmol/l) in hypoxic waters, and N2O depletion in the core of ocean oxygen minimum zones (OMZs). Oceanic N2O emissions are estimated to account for up to a third of the pre-industrial N2O fluxes to the atmosphere, however the natural cycle of ocean N2O has been perturbed in recent decades by inputs of anthropogenically derived nutrient, and by the impacts of climate change. Anthropogenic nitrogen inputs (e.g., NOx and NHy from fossil fuel combustion and agricultural fertilizer) enter the ocean via atmospheric deposition and riverine fluxes, influencing oceanic N2O production via their impact on the marine organic matter cycle. In addition, climate variations associated with surface ocean warming affect oceanic circulation and nutrient transport pathways, influencing marine productivity and the ventilation of oxygen minimum zones. Recent studies have suggested that possible expansion of oceanic OMZs in a warming climate could lead to significant changes in N2O production and fluxes from these regions. We will summarise the current state of knowledge on the ocean N2O budget and net flux to the atmosphere. Recently reported estimates have been based on (i) empirical relationships derived from ocean tracer data (e.g., involving excess N2O and Apparent Oxygen Utilization (AOU) correlations), (ii) ocean biogeochemical

  18. Production of N2O/+/ by reaction of metastable O2/+/ ions with N2

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; Rayermann, P.

    1975-01-01

    Photoionization mass spectrometry examination of the production of N2O(+) was undertaken to determine whether N2(+) or O2(+) ions are responsible for onset of N2O(+). It appears that the N2(+) ion does not contribute significantly to the production of N2O(+) in this experiment. Therefore, it is clear that excited O2(+) is responsible for the formation of N2O(+) near the appearance potential of these ions.

  19. Infrared spectroscopic and theoretical study of the HC2n+1O+ (n = 2-5) cations

    NASA Astrophysics Data System (ADS)

    Jin, Jiaye; Li, Wei; Liu, Yuhong; Wang, Guanjun; Zhou, Mingfei

    2017-06-01

    The carbon chain cations, HC2n+1O+ (n = 2-5), are produced via pulsed laser vaporization of a graphite target in supersonic expansions containing carbon monoxide and hydrogen. The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO "tagged" [HC2n+1O.CO]+ cation complexes in the 1600-3500 cm-1 region. The geometries and electronic ground states of these cation complexes are determined by their infrared spectra compared to the predications of theoretical calculations. All of the HC2n+1O+ (n = 2-5) core cations are characterized to be linear carbon chain derivatives terminated by hydrogen and oxygen, which have the closed-shell singlet ground states with polyyne-like carbon chain structures.

  20. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  1. O2(a1Δ) vibrational kinetics in oxygen-iodine laser

    NASA Astrophysics Data System (ADS)

    Torbin, A. P.; Pershin, A. A.; Heaven, M. C.; Azyazov, V. N.; Mebel, A. M.

    2018-04-01

    Kinetics of vibrationally-excited singlet oxygen O2(a1Δ,ν) in gas mixture O3/N2/CO2 was studied using a pulse laser technique. Molecules O2(a1Δ,ν) were produced by laser photolysis of ozone at 266 nm. The O3 molecules number density was followed using time-resolved absorption spectroscopy. It was found that an upper bound for the rate constant of chemical reaction O2(a1Δ,ν)+ O3 is about 10-15 cm3/s. The rate constants of O2(a1Δ,ν= 1, 2 and 3) quenching by CO2 are presented.

  2. The series Bi2Sr2Ca(n-1) Cu(n)O(2n+4) (1 less than or equal to n less than or equal to 5): Phase stability and superconducting properties

    NASA Technical Reports Server (NTRS)

    Deguire, Mark R.; Bansal, Narottam P.; Farrell, David E.; Finan, Valerie; Kim, Cheol J.; Hills, Bethanie J.; Allen, Christopher J.

    1989-01-01

    Phase relations at 850 and 870 C, melting transitions in air, oxygen, and helium were studied for Bi(2.1)Sr(1.9) CuO6 and for the Bi2Sr2Ca(n-1) Cu(n)O(2n+4) for n = 1, 2, 3, 4, 5, and infinity (CaCuO2). Up to 870 C, the n = 2 composition resides in the compatibility tetrahedron bounded by Bi(2+x)(Sr,Ca)(3-y) Cu2O8, (Sr,Ca)14 Cu24O41, Ca2CuO3, and a Bi-Sr-Ca-O phase. The n is greater than or equal to 3 compositions reside in the compatibility tetrahedron Bi(2+x)(Sr,Ca)(3-y) Cu2O8 - (Sr,Ca)14 Cu24O41 - Ca2CuO3 - CuO up to 850 C. However, Bi(2+x)Sr(4-y) Cu3O10 forms for n is greater than or equal to 3 after extended heating at 870 C. Bi(2+x)Sr(2-y) CuO6 and Bi(2+x)(Sr,Ca)(3-y) Cu2O8 melt in air at 914 C and 895 C respectively. During melting, all of the compositions studied lose 1 to 2 percent by weight of oxygen from the reduction of copper. Bi(2+x)Sr(2-y) CuO6, Bi(2+n)(Sr,Ca)(3-y) Cu2O8, and Bi(2+x)(Sr,Ca)(4-y) Cu3O10 exhibit crystallographic alignment in a magnetic field, with the c-axes orienting parallel to the field.

  3. Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

    PubMed

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-02-20

    Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

  4. First-principles study on leakage current caused by oxygen vacancies at HfO2/SiO2/Si interface

    NASA Astrophysics Data System (ADS)

    Takagi, Kensuke; Ono, Tomoya

    2018-06-01

    The relationship between the position of oxygen vacancies in HfO2/SiO2/Si gate stacks and the leakage current is studied by first-principles electronic-structure and electron-conduction calculations. We find that the increase in the leakage current due to the creation of oxygen vacancies in the HfO2 layer is much larger than that in the SiO2 interlayer. According to previous first-principles total energy calculations, the formation energy of oxygen vacancies is smaller in the SiO2 interlayer than that in the HfO2 layer under the same conditions. Therefore, oxygen vacancies will be attracted from the SiO2 interlayer to minimize the energy, thermodynamically justifying the scavenging technique. Thus, the scavenging process efficiently improves the dielectric constant of HfO2-based gate stacks without increasing the number of oxygen vacancies, which cause the dielectric breakdown.

  5. Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

    NASA Astrophysics Data System (ADS)

    Khatami Firoozabadi, Seyed Reza

    This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi

  6. Oxygen desorption from YBa2Cu3O(7-x) and Bi2CaSr2Cu2O(8 + delta) superconductors

    NASA Technical Reports Server (NTRS)

    Mesarwi, A.; Levenson, L. L.; Ignatiev, A.

    1991-01-01

    Oxygen desorption experiments from YBa2Cu3O(7-x) (YBCO) and Bi2CaSr2Cu2O(8 + delta) (BSCCO) superconductors were carried out using a quadrupole mass spectrometer for monitoring the desorbing species and X-ray photoemission spectroscopy for surface characterization. Molecular oxygen was found to desorb from both superconductors following photoirradiation with ultraviolet/optical radiation and subsequent heating at over 150 C. Both YBCO and BSCCO were found to have similar oxygen desorption rates and similar activation energies. The desorption data as well as the X-ray photoemission data indicate that the oxygen desorption is not intrinsic to the superconductors but rather due to molecular oxygen entrapped in the material.

  7. 21 CFR 868.2500 - Cutaneous oxygen (PcO2) monitor.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Cutaneous oxygen (PcO2) monitor. 868.2500 Section... (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Monitoring Devices § 868.2500 Cutaneous oxygen (PcO2) monitor. (a) Identification. A cutaneous oxygen (PcO2) monitor is a noninvasive, heated sensor (e.g., a...

  8. 21 CFR 868.2500 - Cutaneous oxygen (PcO 2) monitor.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Cutaneous oxygen (PcO 2) monitor. 868.2500 Section... (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Monitoring Devices § 868.2500 Cutaneous oxygen (PcO 2) monitor. (a) Identification. A cutaneous oxygen (PcO2) monitor is a noninvasive, heated sensor (e.g., a...

  9. 21 CFR 868.2500 - Cutaneous oxygen (PcO 2) monitor.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Cutaneous oxygen (PcO 2) monitor. 868.2500 Section... (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Monitoring Devices § 868.2500 Cutaneous oxygen (PcO 2) monitor. (a) Identification. A cutaneous oxygen (PcO2) monitor is a noninvasive, heated sensor (e.g., a...

  10. 21 CFR 868.2500 - Cutaneous oxygen (PcO2) monitor.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Cutaneous oxygen (PcO2) monitor. 868.2500 Section... (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Monitoring Devices § 868.2500 Cutaneous oxygen (PcO2) monitor. (a) Identification. A cutaneous oxygen (PcO2) monitor is a noninvasive, heated sensor (e.g., a...

  11. 21 CFR 868.2500 - Cutaneous oxygen (PcO2) monitor.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Cutaneous oxygen (PcO2) monitor. 868.2500 Section... (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Monitoring Devices § 868.2500 Cutaneous oxygen (PcO2) monitor. (a) Identification. A cutaneous oxygen (PcO2) monitor is a noninvasive, heated sensor (e.g., a...

  12. Re-induced Raman active modes in HgBa2Can-1CunO2n+2+δ compounds

    NASA Astrophysics Data System (ADS)

    Poulakis, N.; Lampakis, D.; Liarokapis, E.; Yoshikawa, Akira; Shimoyama, Jun-Ich; Kishio, Kohji; Peacock, G. B.; Hodges, J. P.; Gameson, I.; Edwards, P. P.; Panagopoulos, C.

    1999-08-01

    A comparative Raman study of Re-free and Re-doped HgBa2Can-1CunO2n+2+δ with n=1,3,4,5 is presented in an attempt to further clarify the structural and phononic modifications brought about by Re substitution. A number of extra high-frequency phonon peaks show up in the spectra of the Re-doped samples and are attributed to the oxygen modes of a strongly bound, almost decoupled ReO6 octahedron. As regards the apex oxygen in the Hg site, a clear transfer of spectral weight from the 590 to the 570 cm-1 apex phonon band is observed upon Re substitution. Such a change may well be accounted for assuming increased excess oxygen content for the Re-doped samples. Another interesting result is the enhancement upon Re doping of a narrow peak probably attributed to c-axis vibrations of Ba whose frequency shows a distinctive change with the number n of the CuO2 layers, providing an easy way to identify the various phases in a sample.

  13. SIMS study of oxygen diffusion in monoclinic HfO2

    NASA Astrophysics Data System (ADS)

    Mueller, Michael P.; De Souza, Roger A.

    2018-01-01

    The diffusion of oxygen in dense ceramics of monoclinic HfO2 was studied by means of (18O/16O) isotope exchange annealing and subsequent determination of isotope depth profiles by Secondary Ion Mass Spectrometry. Anneals were performed in the temperature range of 573 ≤T /K ≤ 973 at an oxygen partial pressure of p O2=200 mbar . All measured isotope profiles exhibited two features: the first feature, closer to the surface, was attributed mainly to slow oxygen diffusion in an impurity silicate phase; the second feature, deeper in the sample, was attributed to oxygen diffusion in bulk monoclinic HfO2 . The activation enthalpy of oxygen tracer diffusion in bulk HfO2 was found to be ΔHD∗≈0.5 eV .

  14. Isotopic Monitoring of N2O Emissions from Wastewater Treatment: Evidence for N2O Production Associated with Anammox Metabolism?

    NASA Astrophysics Data System (ADS)

    Harris, E. J.; Wunderlin, P.; Joss, A.; Emmenegger, L.; Kipf, M.; Wolf, B.; Mohn, J.

    2015-12-01

    Microbial production is the major source of N2O, the strongest greenhouse gas produced within the nitrogen cycle, and the most important stratospheric ozone destructant released in the 21st century. Wastewater treatment is an important and growing source of N2O, with best estimates predicting N2O emissions from this sector will have increased by >25% by 2020. Novel treatment employing partial nitritation-anammox, rather than traditional nitrification-denitrification, has the potential to achieve a neutral carbon footprint due to increased biogas production - if N2O production accounts for <0.5-1% of total nitrogen turnover. As a further motivation for this research, microbial pathways identified from wastewater treatment can be applied to our understanding of N cycling in the natural environment. This study presents the first online isotopic measurements of offgas N2O from a partial-nitritation anammox reactor 1. The measured N2O isotopic composition - in particular the N2O isotopic site preference (SP = δ15Nα - δ15Nβ) - was used to understand N2O production pathways in the reactor. When N2O emissions peaked due to high dissolved oxygen concentrations, low SP showed that N2O was produced primarily via nitrifier denitrification by ammonia oxidizing bacteria (AOBs). N2O production by AOBs via NH2OH oxidation, in contrast, did not appear to be important under any conditions. Over the majority of the one-month measurement period, the measured SP was much higher than expected following our current understanding of N2O production pathways 2. SP reached 41‰ during normal operating conditions and achieved a maximum of 45‰ when nitrite was added under anoxic conditions. These results could be explained by unexpectedly strong heterotrophic N2O reduction despite low dissolved organic matter concentrations, or by an incomplete understanding of isotopic fractionation during N2O production from NH2OH oxidation by AOBs - however the explanation most consistent with all

  15. Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

    NASA Technical Reports Server (NTRS)

    Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

    1988-01-01

    A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

  16. O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

    NASA Technical Reports Server (NTRS)

    Slanger, Tom G.; Copeland, Richard A.

    1997-01-01

    The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

  17. Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

    PubMed

    Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

    2017-03-21

    The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

  18. Collision cross sections and transport coefficients of O-, O2 -, O3 - and O4 - negative ions in O2, N2 and dry air for non-thermal plasmas modelling

    NASA Astrophysics Data System (ADS)

    Hennad, Ali; Yousfi, Mohammed

    2018-02-01

    The ions interaction data such as interaction potential parameters, elastic and inelastic collision cross sections and the transport coefficients (reduced mobility and diffusion coefficients) have been determined and analyzed in the case of the main negative oxygen ions (O-, O2 -, O3 - and O4 -) present in low temperature plasma at atmospheric pressure when colliding O2, N2 and dry air. The ion transport has been determined from an optimized Monte Carlo simulation using calculated elastic and experimentally fitted inelastic collision cross sections. The elastic momentum transfer collision cross sections have been calculated from a semi-classical JWKB approximation based on a ( n-4) rigid core interaction potential model. The cross sections sets involving elastic and inelastic processes were then validated using measured reduced mobility data and also diffusion coefficient whenever available in the literature. From the sets of elastic and inelastic collision cross sections thus obtained for the first time for O3-/O2, O2 -/N2, O3 -/N2, and O4 -/N2 systems, the ion transport coefficients were calculated in pure gases and dry air over a wide range of the density reduced electric field E/N.

  19. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

    PubMed

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-14

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  20. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-01

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  1. K-shell photoabsorption coefficients of O2, CO2, CO, and N2O

    NASA Technical Reports Server (NTRS)

    Barrus, D. M.; Blake, R. L.; Burek, A. J.; Chambers, K. C.; Pregenzer, A. L.

    1979-01-01

    The total photoabsorption coefficient has been measured from 500 to 600 eV around the K edge of oxygen in gases O2, CO2, CO, and N2O by means of a gold continuum source and crystal spectrometer with better than 1-eV resolution. The cross sections are dominated by discrete molecular-orbital transitions below the K-edge energy. A few Rydberg transitions were barely detectable. Broad shape resonances appear at or above the K edge. Additional broad, weak features above the K edge possibly arise from shake up. Quantitative results are given that have about 10% accuracy except on the very strong peaks. All the measured features are discussed in relation to other related measurements and theory.

  2. Electrical and structural properties of TiO2-δ thin film with oxygen vacancies prepared by RF magnetron sputtering using oxygen radical

    NASA Astrophysics Data System (ADS)

    Kawamura, Kinya; Suzuki, Naoya; Tsuchiya, Takashi; Shimazu, Yuichi; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    Anatase TiO2-δ thin film was prepared by RF magnetron sputtering using oxygen radical and Ti-metal target. Degrees of the TiO2-δ crystal orientation in the thin film depends of the oxygen gas pressure (P\\text{O2}) in the radical gun. The (004)- and (112)-oriented TiO2-δ thin films crystallized without postannealing have the mixed valence Ti4+/Ti3+ state. The electrical conductivities, which corresponds to n-type oxide semiconductor, is higher in the case of (004)-oriented TiO2-δ thin film containing with high concentration of oxygen vacancy. The donor band of TiO2-δ thin film is observed at ˜1.0 eV from the Fermi level (E F). The density-of-state at E F is higher in (004)-oriented TiO2-δ thin film. The above results indicate that the oxygen vacancies can control by changing the P\\text{O2} of the oxygen radical.

  3. Oceanic N2O emissions in the 21st century

    NASA Astrophysics Data System (ADS)

    Martinez-Rey, J.; Bopp, L.; Gehlen, M.; Tagliabue, A.; Gruber, N.

    2014-12-01

    The ocean is a substantial source of nitrous oxide (N2O) to the atmosphere, but little is known on how this flux might change in the future. Here, we investigate the potential evolution of marine N2O emissions in the 21st century in response to anthropogenic climate change using the global ocean biogeochemical model NEMO-PISCES. We implemented two different parameterizations of N2O production, which differ primarily at low oxygen (O2) conditions. When forced with output from a climate model simulation run under the business-as-usual high CO2 concentration scenario (RCP8.5), our simulations suggest a decrease of 4 to 12% in N2O emissions from 2005 to 2100, i.e., a reduction from 4.03/3.71 to 3.54/3.56 Tg N yr-1 depending on the parameterization. The emissions decrease strongly in the western basins of the Pacific and Atlantic oceans, while they tend to increase above the Oxygen Minimum Zones (OMZs), i.e., in the Eastern Tropical Pacific and in the northern Indian Ocean. The reduction in N2O emissions is caused on the one hand by weakened nitrification as a consequence of reduced primary and export production, and on the other hand by stronger vertical stratification, which reduces the transport of N2O from the ocean interior to the ocean surface. The higher emissions over the OMZ are linked to an expansion of these zones under global warming, which leads to increased N2O production associated primarily with denitrification. From the perspective of a global climate system, the averaged feedback strength associated with the projected decrease in oceanic N2O emissions amounts to around -0.009 W m-2 K-1, which is comparable to the potential increase from terrestrial N2O sources. However, the assesment for a compensation between the terrestrial and marine feedbacks calls for an improved representation of N2O production terms in fully coupled next generation of Earth System Models.

  4. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  5. Hybrid TiO2 -Ruthenium Nano-photosensitizer Synergistically Produces Reactive Oxygen Species in both Hypoxic and Normoxic Conditions.

    PubMed

    Gilson, Rebecca C; Black, Kvar C L; Lane, Daniel D; Achilefu, Samuel

    2017-08-28

    Photodynamic therapy (PDT) is widely used to treat diverse diseases, but its dependence on oxygen to produce cytotoxic reactive oxygen species (ROS) diminishes the therapeutic effect in a hypoxic environment, such as solid tumors. Herein, we developed a ROS-producing hybrid nanoparticle-based photosensitizer capable of maintaining high levels of ROS under both normoxic and hypoxic conditions. Conjugation of a ruthenium complex (N3) to a TiO 2 nanoparticle afforded TiO 2 -N3. Upon exposure of TiO 2 -N3 to light, the N3 injected electrons into TiO 2 to produce three- and four-fold more hydroxyl radicals and hydrogen peroxide, respectively, than TiO 2 at 160 mmHg. TiO 2 -N3 maintained three-fold higher hydroxyl radicals than TiO 2 under hypoxic conditions via N3-facilitated electron-hole reduction of adsorbed water molecules. The incorporation of N3 transformed TiO 2 from a dual type I and II PDT agent to a predominantly type I photosensitizer, irrespective of the oxygen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Surveying N2O-producing pathways in bacteria.

    PubMed

    Stein, Lisa Y

    2011-01-01

    Nitrous oxide (N(2)O) is produced by bacteria as an intermediate of both dissimilatory and detoxification pathways under a range of oxygen levels, although the majority of N(2)O is released in suboxic to anoxic environments. N(2)O production under physiologically relevant conditions appears to require the reduction of nitric oxide (NO) produced from the oxidation of hydroxylamine (nitrification), reduction of nitrite (denitrification), or by host cells of pathogenic bacteria. In a single bacterial isolate, N(2)O-producing pathways can be complex, overlapping, involve multiple enzymes with the same function, and require multiple layers of regulatory machinery. This overview discusses how to identify known N(2)O-producing inventory and regulatory sequences within bacterial genome sequences and basic physiological approaches for investigating the function of that inventory. A multitude of review articles have been published on individual enzymes, pathways, regulation, and environmental significance of N(2)O-production encompassing a large diversity of bacterial isolates. The combination of next-generation deep sequencing platforms, emerging proteomics technologies, and basic microbial physiology can be used to expand what is known about N(2)O-producing pathways in individual bacterial species to discover novel inventory and unifying features of pathways. A combination of approaches is required to understand and generalize the function and control of N(2)O production across a range of temporal and spatial scales within natural and host environments. Copyright © 2011 Elsevier Inc. All rights reserved.

  7. Phase development in the Bi 2Sr 2CaCu 2O y system . Effects of oxygen pressure

    NASA Astrophysics Data System (ADS)

    List, F. A.; Hsu, H.; Cavin, O. B.; Porter, W. D.; Hubbard, C. R.; Kroeger, D. M.

    1992-11-01

    Studies have been undertaken using thermal analysis, in conjunction with high-temperature and room temperature X-ray diffraction, fraction, to elucidate phase relationships during thermal processing of thick films of initially phase pure Bi 2Sr 2CaCu 2O y (2212) on silver substrates in various oxygen-containing atmospheres (0.001 to 100% O 2). Exothermic events on cooling at 10°C/min from a partially liquid state vary with oxygen partial pressure and can be grouped into three sets (I-III). Set I is prominent for 0.001% and 0.1% O 2 in the range of 740-775°C and is believed to be associated with the crystallization of a Cu-free ∼ Bi 5Sr 3Ca 1 oxide phase. Set II results from the crystallization of 2212; it is observed for p(O 2)≥1.0% in the temperature range 800-870°C. Set III appears for 21% and 100% O 2 in the temperature range 880-910°C, and its origin is not clear from the results of this study. Subsequent room temperature X-ray diffraction from these samples suggests that in general high oxygen partial pressures (100% O 2) tend to favor the formation of Bi 2Sr 2CuO 6 (2201), whereas low oxygen partial pressures (0.001-0.1% O 2) lead to the formation of a Cu-free, Bi-Sr-Ca oxide phase. The 2212 phase forms at this cooling rate predominantly for intermediate oxygen partial pressures (7.6-21% O 2). High-temperature X-ray diffraction during cooling (2°C/h) from the partially liquid state shows a pronounced dependence of the order of evolution of crystalline 2212 and 2201 phases on p(O 2). For an oxygen partial pressure of 1.0% the formation of 2212 precedes that of 2201, whereas for 0.01% O 2 2201 crystallizes at a higher temperature than 2212. The implications of these results pertaining to thermal processing of thick 2212 films are discussed.

  8. The Impact of Iron on Soil N2O Production Depends on Oxygen Availability

    NASA Astrophysics Data System (ADS)

    Zhu, X.; Doane, T. A.; Burger, M.; Horwath, W. R.

    2014-12-01

    The continuous increase of nitrous oxide (N2O) abundance in the atmosphere is a global concern. Soils are both an important source and sink of N2O, which is produced and consumed through biological processes including ammonia oxidation, heterotrophic denitrification, codenitrification, and through abiotic processes such as chemodenitrification. Iron is the most abundant element in the earth and is also the most prevalent redox-active metal in the biosphere. Its role in both chemical and biochemical reactions in N biogeochemistry cycling is well recognized. However, iron's significance to N2O production is poorly understood, especially under varying O2 concentration. We examined N2O production under different O2 concentrations following amorphous iron (III) oxyhydroxide and ammonical N fertilizer additions in four soil slurries and two static soils (soil moisture was 50% of water holding capacity). Under 21% O2, the addition of iron (III) significantly decreased N2O production in all the soil slurries and static soils, while the opposite phenomenon was observed once the O2 concentration became limited (≤3% in the soil slurry and ≤0.5% in the static soil). Our results show that the influence of iron on soil N2O production depends on O2 availability, which is the dominant controller of N2O production pathways. We hypothesize that under ambient O2 conditions, iron can react with nitrite produced during ammonia oxidation, thus reducing the probability of NO2- being used by nitrifiers as electron acceptor in nitrifier denitrification. In contrast, under anaerobic conditions (O2<0.5%), less nitrite was detected in the presence of the iron addition. Under these conditions, iron may have inhibited N2O reductase, or reduced iron (II) reacted with nitrite, both of which would lead to greater release of N2O.These findings imply that management practices which focus on mitigating N2O emission should avoid the application of iron-rich materials such as biosolids when

  9. One-Dimensional RuO2/Mn2O3 Hollow Architectures as Efficient Bifunctional Catalysts for Lithium-Oxygen Batteries.

    PubMed

    Yoon, Ki Ro; Lee, Gil Yong; Jung, Ji-Won; Kim, Nam-Hoon; Kim, Sang Ouk; Kim, Il-Doo

    2016-03-09

    Rational design and massive production of bifunctional catalysts with fast oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics are critical to the realization of highly efficient lithium-oxygen (Li-O2) batteries. Here, we first exploit two types of double-walled RuO2 and Mn2O3 composite fibers, i.e., (i) phase separated RuO2/Mn2O3 fiber-in-tube (RM-FIT) and (ii) multicomposite RuO2/Mn2O3 tube-in-tube (RM-TIT), by controlling ramping rate during electrospinning process. Both RM-FIT and RM-TIT exhibited excellent bifunctional electrocatalytic activities in alkaline media. The air electrodes using RM-FIT and RM-TIT showed enhanced overpotential characteristics and stable cyclability over 100 cycles in the Li-O2 cells, demonstrating high potential as efficient OER and ORR catalysts.

  10. Growth and Properties of Oxygen and Ion Doped BISMUTH(2) STRONTIUM(2) Calcium COPPER(2) Oxygen (8+DELTA) Single Crystals

    NASA Astrophysics Data System (ADS)

    Mitzi, David Brian

    1990-01-01

    A directional solidification method for growing large single crystals in the Bi_2Sr _2CaCu_2O _{8+delta} system is reported. Ion substitutions, with replacement of La for Sr and Y for Ca, as well as oxygen doping in these crystals has been explored. Ion doping results in little change of the superconducting transition for substitution levels below 20-25% (as a result of simultaneous oxygen intercalation), while beyond this level, the Meissner signal broadens and the low temperature Meissner signal decreases. Microprobe analysis and x-ray diffraction performed on these more highly substituted single crystals, provides evidence for inhomogeneity and phase segregation into regions of distinct composition. Annealing unsubstituted crystals in increasing partial pressures of oxygen reversibly depresses the superconducting transition temperature from 90K (as made) to 77K (oxygen pressure annealed) while the Hall concentrations increase from n = 3.1(3) times 10 ^{21} cm^{ -3} (0.34 holes/Cu site) to 4.6(3) times 10^{21} cm^{-3} (0.50 holes/Cu site). Further suppression of T_{c} to 72K is possible by annealing in oxygen pressures up to 100atm. No degradation of the Meissner transition or other indications of inhomogeneity or phase segregation with doping are noted, suggesting that oxygen doped Bi_2Sr _2CaCu_2O _{8+delta} is a suitable system for pursuing doping studies. The decrease in T _{c} with concentration for 0.34 <=q n <=q 0.50 indicates that a high carrier concentration regime exists where T_{c} decreases with n and suggests that this decrease does not arise from material inhomogeneity or other materials problems. The physical properties of these Bi _2Sr_2CaCu _2O_{8+delta} crystals, in this high carrier concentration regime, will be discussed.

  11. Introduction of oxygen vacancies and fluorine into TiO{sub 2} nanoparticles by co-milling with PTFE

    SciTech Connect

    Senna, Mamoru, E-mail: senna@applc.keio.ac.jp; Sepelak, Vladimir; Shi, Jianmin

    2012-03-15

    Solid-state processes of introducing oxygen vacancies and transference of fluorine to n-TiO{sub 2} nanoparticles by co-milling with poly(tetrafluoroethylene) (PTFE) powder were examined by diffuse reflectance spectroscopy (DRS) of UV, visual, near- and mid-IR regions, thermal analyses (TG-DTA), energy-dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The broad absorption peak at around 8800 cm{sup -1} (1140 nm) was attributed to the change in the electronic states, viz. electrons trapped at the oxygen vacancies (Vo) and d-d transitions of titanium ions. Incorporation of fluorine into n-TiO{sub 2} was concentrated at the near surfacemore » region and amounted to ca. 40 at% of the total fluorine in PTFE, after co-milling for 3 h, as confirmed by the F1s XPS spectrum. The overall atomic ratio, F/Ti, determined by EDXS was 0.294. By combining these analytical results, a mechanism of the present solid state processes at the boundary between PTFE and n-TiO{sub 2} was proposed. The entire process is triggered by the partial oxidative decomposition of PTFE. This is accompanied by the abstraction of oxygen atoms from the n-TiO{sub 2} lattices. Loss of the oxygen atoms results in the formation of the diverse states of locally distorted coordination units of titania, i.e. TiO{sub 6-n}Vo{sub n}, located at the near surface region. This leads subsequent partial ligand exchange between F and O, to incorporate fluorine preferentially to the near surface region of n-TiO{sub 2} particles, where local non-crystalline states predominate. - Graphical abstract: Scheme of the reaction processes: (a) pristine mixture, (b) oxygen abstraction from TiO{sub 2} and (c) fluorine migration from PTFE to TiO{sub 2}. Highlights: Transfer of fluorine from PTFE to n-TiO{sub 2} in a dry solid state process was confirmed. Black-Right-Pointing-Pointer 40% of F in PTFE was incorporated to

  12. Reaction mechanism for oxygen evolution on RuO 2, IrO 2, and RuO 2@IrO 2 core-shell nanocatalysts

    SciTech Connect

    Ma, Zhong; Zhang, Yu; Liu, Shizhong

    Iridium dioxide, IrO 2, is second to the most active RuO 2 catalyst for the oxygen evolution reaction (OER) in acid, and is used in proton exchange membrane water electrolyzers due to its high durability. In order to improve the activity of IrO 2-based catalysts, we prepared RuO 2@IrO 2 core-shell nanocatalysts using carbon-supported Ru as the template. At 1.48 V, the OER specific activity of RuO 2@IrO 2 is threefold that of IrO 2. While the activity volcano plots over wide range of materials have been reported, zooming into the top region to clarify the rate limiting steps ofmore » most active catalysts is important for further activity enhancement. Here, we verified theory-proposed sequential water dissociation pathway in which the O—O bond forms on a single metal site, not via coupling of two adsorbed intermediates, by fitting measured polarization curves using a kinetic equation with the free energies of adsorption and activation as the parameters. Consistent with theoretical calculations, we show that the OER activities of IrO 2 and RuO 2@IrO 2 are limited by the formation of O adsorbed phase, while the OOH formation on the adsorbed O limits the reaction rate on RuO 2.« less

  13. Reaction mechanism for oxygen evolution on RuO 2, IrO 2, and RuO 2@IrO 2 core-shell nanocatalysts

    DOE PAGES

    Ma, Zhong; Zhang, Yu; Liu, Shizhong; ...

    2017-10-28

    Iridium dioxide, IrO 2, is second to the most active RuO 2 catalyst for the oxygen evolution reaction (OER) in acid, and is used in proton exchange membrane water electrolyzers due to its high durability. In order to improve the activity of IrO 2-based catalysts, we prepared RuO 2@IrO 2 core-shell nanocatalysts using carbon-supported Ru as the template. At 1.48 V, the OER specific activity of RuO 2@IrO 2 is threefold that of IrO 2. While the activity volcano plots over wide range of materials have been reported, zooming into the top region to clarify the rate limiting steps ofmore » most active catalysts is important for further activity enhancement. Here, we verified theory-proposed sequential water dissociation pathway in which the O—O bond forms on a single metal site, not via coupling of two adsorbed intermediates, by fitting measured polarization curves using a kinetic equation with the free energies of adsorption and activation as the parameters. Consistent with theoretical calculations, we show that the OER activities of IrO 2 and RuO 2@IrO 2 are limited by the formation of O adsorbed phase, while the OOH formation on the adsorbed O limits the reaction rate on RuO 2.« less

  14. Oxygen defect induced photoluminescence of HfO2 thin films

    NASA Astrophysics Data System (ADS)

    Ni, Jie; Zhou, Qin; Li, Zhengcao; Zhang, Zhengjun

    2008-07-01

    Amorphous HfO2 films prepared by e-beam deposition exhibited room-temperature photoluminescence (PL) in the visible range, i.e., at ˜620 and 700nm, due to oxygen vacancies involved during deposition. This PL can be enhanced by two orders in intensity by crystallizing the amorphous films in flowing argon, where a large amount of oxygen vacancies were introduced, and can be diminished by removal of the oxygen vacancies by annealing HfO2 films in oxygen. This study could help understand the defect-property relationship and provides ways to tune the PL property of HfO2 films.

  15. The source of stratospheric NO and N2O

    NASA Technical Reports Server (NTRS)

    Slanger, T. G.

    1984-01-01

    The photodissociation of O3 was investigated as a possible sources of N2O production in the stratosphere. Photolysis was conducted at 1576 A to generate the excited O2 states that react with N2 to form N2O. At this wavelength, there is a quantum yield of two for prompt production of oygen atoms, which is a consequence of the existence of two photodissociative channels giving comparable yields. One of these channels gives O(D1) and O2(b1sigma(+)subg), with a quantum yield of 0.6, whereas the other results in fragmentation of the O3, with production of three ground state oxygen atoms. The O2(b) is generated with vibrational excitation, and there are comparable populations in levels O to 3. These observations are the first to show O2(b) production from any photodissociative process, and were made under conditions in which the kinetics of vibrationally excited O2(b) can be studied. It appears that O3 photodissociation at 1576 A is not a good system for generating the higher electronic states of O2; it is likely that better results will be obtained at 1930 A.

  16. Surface Nitrification: A Major Uncertainty in Marine N2O Emissions

    NASA Technical Reports Server (NTRS)

    Zamora, Lauren M.; Oschlies, Andreas

    2014-01-01

    The ocean is responsible for up to a third of total global nitrous oxide (N2O) emissions, but uncertainties in emission rates of this potent greenhouse gas are high (approaching 100%). Here we use a marine biogeochemical model to assess six major uncertainties in estimates of N2O production, thereby providing guidance in how future studies may most effectively reduce uncertainties in current and future marine N2O emissions. Potential surface N2O production from nitrification causes the largest uncertainty in N2O emissions (estimated up to approximately 1.6 Tg N/yr (sup -1) or 48% of modeled values), followed by the unknown oxygen concentration at which N2O production switches to N2O consumption (0.8 Tg N/yr (sup -1)or 24% of modeled values). Other uncertainties are minor, cumulatively changing regional emissions by less than 15%. If production of N2O by surface nitrification could be ruled out in future studies, uncertainties in marine N2O emissions would be halved.

  17. Understanding the mechanisms of interfacial reactions during TiO{sub 2} layer growth on RuO{sub 2} by atomic layer deposition with O{sub 2} plasma or H{sub 2}O as oxygen source

    SciTech Connect

    Chaker, A.; Szkutnik, P. D.; Pointet, J.

    2016-08-28

    In this paper, TiO{sub 2} layers grown on RuO{sub 2} by atomic layer deposition (ALD) using tetrakis (dimethyla-mino) titanium (TDMAT) and either oxygen plasma or H{sub 2}O as oxygen source were analyzed using X-ray diffraction (XRD), Raman spectroscopy, and depth-resolved X-ray Photoelectron spectroscopy (XPS). The main objective is to investigate the surface chemical reactions mechanisms and their influence on the TiO{sub 2} film properties. The experimental results using XRD show that ALD deposition using H{sub 2}O leads to anatase TiO{sub 2} whereas a rutile TiO{sub 2} is obtained when oxygen-plasma is used as oxygen source. Depth-resolved XPS analysis allows tomore » determine the reaction mechanisms at the RuO{sub 2} substrate surface after growth of thin TiO{sub 2} layers. Indeed, the XPS analysis shows that when H{sub 2}O assisted ALD process is used, intermediate Ti{sub 2}O{sub 3} layer is obtained and RuO{sub 2} is reduced into Ru as evidenced by high resolution transmission electron microscopy. In this case, there is no possibility to re-oxidize the Ru surface into RuO{sub 2} due to the weak oxidation character of H{sub 2}O and an anatase TiO{sub 2} layer is therefore grown on Ti{sub 2}O{sub 3}. In contrast, when oxygen plasma is used in the ALD process, its strong oxidation character leads to the re-oxidation of the partially reduced RuO{sub 2} following the first Ti deposition step. Consequently, the RuO{sub 2} surface is regenerated, allowing the growth of rutile TiO{sub 2}. A surface chemical reaction scheme is proposed that well accounts for the observed experimental results.« less

  18. Infrared spectra of N2O-(ortho-D2)N and N2O-(HD)N clusters trapped in bulk solid parahydrogen.

    PubMed

    Lorenz, Britney D; Anderson, David T

    2007-05-14

    High-resolution infrared spectra of the clusters N2O-(ortho-D2)N and N2O-(HD)N, N=1-4, isolated in bulk solid parahydrogen at liquid helium temperatures are studied in the 2225 cm-1 region of the nu3 antisymmetric stretch of N2O. The clusters form during vapor deposition of separate gas streams of a precooled hydrogen mixture (ortho-D2para-H2 or HDpara-H2) and N2O onto a BaF2 optical substrate held at approximately 2.5 K in a sample-in-vacuum liquid helium cryostat. The cluster spectra reveal the N2O nu3 vibrational frequency shifts to higher energy as a function of N, and the shifts are larger for ortho-D2 compared to HD. These vibrational shifts result from the reduced translational zero-point energy for N2O solvated by the heavier hydrogen isotopomers. These spectra allow the N=0 peak at 2221.634 cm-1, corresponding to the nu3 vibrational frequency of N2O isolated in pure solid parahydrogen, to be assigned. The intensity of the N=0 absorption feature displays a strong temperature dependence, suggesting that significant structural changes occur in the parahydrogen solvation environment of N2O in the 1.8-4.9 K temperature range studied.

  19. Simultaneous retrieval of the solar EUV flux and neutral thermospheric O, O2, N2, and temperature from twilight airglow

    NASA Technical Reports Server (NTRS)

    Fennelly, J. A.; Torr, D. G.; Richards, P. G.; Torr, M. R.

    1994-01-01

    We present a method to retrieve neutral thermospheric composition and the solar EUV flux from ground-based twilight optical measurements of the O(+) ((exp 2)P) 7320 A and O((exp 1)D) 6300 A airglow emissions. The parameters retrieved are the neutral temperature, the O, O2, N2 density profiles, and a scaling factor for the solar EUV flux spectrum. The temperature, solar EUV flux scaling factor, and atomic oxygen density are first retrieved from the 7320-A emission, which are then used with the 6300-A emission to retrieve the O2 and N2 densities. The retrieval techniques have been verified by computer simulations. We have shown that the retrieval technique is able to statistically retrieve values, between 200 and 400 km, within an average error of 3.1 + or - 0.6% for thermospheric temperature, 3.3 + or - 2.0% for atomic oxygen, 2.3 + or - 1.3% for molecular oxygen, and 2.4 + or - 1.3% for molecular nitrogen. The solar EUV flux scaling factor was found to have a retrieval error of 5.1 + or - 2.3%. All the above errors have a confidence level of 95%. The purpose of this paper is to prove the viability and usefulness of the retrieval technique by demonstrating the ability to retrieve known quantities under a realistic simulation of the measurement process, excluding systematic effects.

  20. Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

    NASA Astrophysics Data System (ADS)

    Dors, Mirosław; Mizeraczyk, Jerzy

    1996-10-01

    This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO2 and N2O in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm3/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N2:O2:CO2 mixture the corona discharge produced NO, NO2 and N2O. In the N2:O2:CO2:NO2 mixture the reduction of NO2 was between 6-56%, depending on the concentration of O2, gas flow rate and corona discharge current. The NO2 reduction was accompanied by production of NO and N2O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N2 and O2 if reducing additives are not employed.

  1. Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

    PubMed

    Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

    2016-12-30

    Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision

  2. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

    PubMed

    De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

    2014-03-28

    New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

  3. Determination of interstitial oxygen atom position in U2N3+xOy by near edge structure study

    NASA Astrophysics Data System (ADS)

    Jiang, A. K.; Zhao, Y. W.; Long, Z.; Hu, Y.; Wang, X. F.; Yang, R. L.; Bao, H. L.; Zeng, R. G.; Liu, K. Z.

    2018-06-01

    The determination of interstitial oxygen atom site in U2N3+xOy film could facilitate the understanding of the oxidation mechanism of α-U2N3 and the effect of U2N3+xOy on anti-oxidation. By comparing the similarities and variances between N K edge and O K edge electron energy loss spectra (EELS) for oxidized α-U2N3 and UO2, the present work looks at the local structure of nitrogen and oxygen atoms in U2N3+xOy film, identifying the most possible position of interstitial O atom.

  4. O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

    NASA Astrophysics Data System (ADS)

    Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

    2018-05-01

    Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

  5. Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

    NASA Astrophysics Data System (ADS)

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-05-01

    Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

  6. Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange

    SciTech Connect

    Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel

    RuO2 catalysts exhibit record activities towards the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO2 OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online 3 electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER onmore » crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by DFT, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO2 nanoparticles by facet engineering.« less

  7. Quantification of nitrous oxide (N2O) emissions and soluble microbial product (SMP) production by a modified AOB-NOB-N2O-SMP model.

    PubMed

    Kim, MinJeong; Wu, Guangxue; Yoo, ChangKyoo

    2017-03-01

    A modified AOB-NOB-N 2 O-SMP model able to quantify nitrous oxide (N 2 O) emissions and soluble microbial product (SMP) production during wastewater treatment is proposed. The modified AOB-NOB-N 2 O-SMP model takes into account: (1) two-step nitrification by ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), (2) N 2 O production by AOB denitrification under oxygen-limited conditions and (3) SMP production by microbial growth and endogenous respiration. Validity of the modified model is demonstrated by comparing the simulation results with experimental data from lab-scale sequencing batch reactors (SBRs). To reliably implement the modified model, a model calibration that adjusts model parameters to fit the model outputs to the experimental data is conducted. The results of this study showed that the modeling accuracy of the modified AOB-NOB-N 2 O-SMP model increases by 19.7% (NH 4 ), 51.0% (NO 2 ), 57.8% (N 2 O) and 16.7% (SMP) compared to the conventional model which does not consider the two-step nitrification and SMP production by microbial endogenous respiration. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

    SciTech Connect

    Xu, Yue-Feng; Chen, Yuan; Xu, Gui-Liang

    RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presentedmore » much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge

  9. Dynamics of oxygen species on reduced TiO2 (110) rutile

    NASA Astrophysics Data System (ADS)

    Wang, Yun; Pillay, Devina; Hwang, Gyeong S.

    2004-11-01

    Using density functional theory calculations, we have investigated the adsorption and diffusion of oxygen species on the reduced TiO2(110) surface. We have found that molecular O2 strongly binds not only to O vacancies, but also to Ti(5c) neighbors, due to delocalization of unpaired electrons arising from removal of neutral bridging oxygen. Our results show that molecular O2 can jump across an oxygen vacancy and diffuse along a Ti(5c) row with moderate barriers. On the other hand, atomic O diffusion along a Ti(5c) row is rather unlikely at low temperatures (<300K) , because of the relatively higher probability of O-O formation from interaction with an adjacent bridging O(2c) atom. Based on our calculation results, we discuss the diffusion and healing of O vacancies associated with O2 adsorption.

  10. The combined effect of dissolved oxygen and nitrite on N2O production by ammonia oxidizing bacteria in an enriched nitrifying sludge.

    PubMed

    Peng, Lai; Ni, Bing-Jie; Ye, Liu; Yuan, Zhiguo

    2015-04-15

    Both nitrite [Formula: see text] and dissolved oxygen (DO) play important roles in nitrous oxide (N2O) production by ammonia oxidizing bacteria (AOB). However, few studies focused on the combined effect of them on N2O production by AOB as well as the corresponding mechanisms. In this study, N2O production by an enriched nitrifying sludge, consisting of both AOB and nitrite-oxidizing bacteria (NOB), was investigated under various [Formula: see text] and DO concentrations. At each investigated DO level, both the biomass specific N2O production rate and the N2O emission factor (the ratio between N2O nitrogen emitted and the ammonium nitrogen converted) increased as [Formula: see text] concentration increased from 3 mg N/L to 50 mg N/L. However, at each investigated [Formula: see text] level, the maximum biomass specific N2O production rate occurred at DO of 0.85 mg O2/L, while the N2O emission factor decreased as DO increased from 0.35 to 3.5 mg O2/L. The analysis of the process data using a mathematical N2O model incorporating both the AOB denitrification and hydroxylamine (NH2OH) oxidation pathways indicated that the contribution of AOB denitrification pathway increased as [Formula: see text] concentration increased, but decreased as DO concentration increased, accompanied by a corresponding change in the contribution of NH2OH oxidation pathway to N2O production. The AOB denitrification pathway was predominant in most cases, with the NH2OH oxidation pathway making a comparable contribution only at high DO level (e.g. 3.5 mg O2/L). Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Toxic effect of Cr(VI) in presence of n-TiO2 and n-Al2O3 particles towards freshwater microalgae.

    PubMed

    Dalai, Swayamprava; Pakrashi, Sunandan; Bhuvaneshwari, M; Iswarya, V; Chandrasekaran, N; Mukherjee, Amitava

    2014-01-01

    The reactivity and toxicity of the soluble toxicants in the presence of the engineered nanomaterials is not well explored. In this study, the probable effects of TiO2 and Al2O3 nanoparticles (n-TiO2, n-Al2O3) on the toxicity of Cr(VI) were assessed with the dominant freshwater algae, Scenedesmus obliquus, in a low range of exposure concentrations (0.05, 0.5 and 1μg/mL). In the presence of 0.05μg/mL n-TiO2, the toxicity of Cr(VI) decreased considerably, which was presumably due to the Cr(VI) adsorption on the nanoparticle surface leading to its aggregation and precipitation. The elevated n-TiO2 concentrations (0.5 and 1μg/mL) did not significantly influence Cr(VI) bio-availability, and a dose dependent toxicity of Cr(VI) was observed. On the other hand, n-Al2O3 did not have any significant effect on the Cr(VI) toxicity. The microscopic observations presented additional information on the morphological changes of the algal cells in the presence of the binary toxicants. The generation of reactive oxygen species (ROS) suggested contribution of oxidative stress on toxicity and LDH release confirmed membrane permeability of algal cells upon stress. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

    NASA Astrophysics Data System (ADS)

    Dou, Ming-Yu; Lu, Jing

    2017-12-01

    A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

  13. Reaction of Rb and oxygen overlayers with single-crystalline Bi2Sr2CaCu2O8+δ superconductors

    NASA Astrophysics Data System (ADS)

    Lindberg, P. A. P.; Shen, Z.-X.; Wells, B. O.; Dessau, D. S.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

    1989-02-01

    Single crystals of Bi2Sr2CaCu2O8+δ superconductors, in situ cleaved and modified by Rb and oxygen overlayers, have been studied using ultraviolet and x-ray photoemission spectroscopy. The core-level results show that Rb strongly reacts with the Bi and O states, while the Cu and Sr states are left unchanged. This observation strongly indicates that the Bi-O plane forms the surface layer. Subsequent exposure to oxygen results in new oxygen states at the surface as monitored by the O 1s core-level data. For both Rb and oxygen overlayers the valence-band spectra are severely altered. In particular, new valence-band states, presumably of oxygen character, are formed.

  14. The structure, stability, and infrared spectrum of B 2N, B 2N +, B 2N -, BO, B 2O and B 2N 2.

    NASA Astrophysics Data System (ADS)

    Martin, J. M. L.; François, J. P.; Gijbels, R.

    1992-05-01

    The structure, infrared spectrum, and heat of formation of B 2N, B 2N -, BO, and B 2O have been studied ab initio. B 2N is very stable; B 2O even more so. B 2N, B 2N -, B 2O, and probably B 2N + have symmetric linear ground-state structures; for B 2O, an asymmetric linear structure lies about 12 kcal/mol above the ground state. B 2N +, B 2N - and B 2O have intense asymmetric stretching frequencies, predicted near 870, 1590 and 1400 cm -1, respectively. Our predicted harmonic frequencies and isotopic shifts for B 2O confirm the recent experimental identification by Andrews and Burkholder. Absorptions at 1889.5 and 1998.5 cm -1 in noble-gas trapped boron nitride vapor belong the BNB and BNBN ( 3Π), respectively; a tentative assignment of 882.5 cm -1 to BNB + is proposed. Total atomization energies Σ De (Σ D0) are computed (accuracy ±2 kcal/mol) as: BO 193.1 (190.4), B 2O 292.5 (288.7), B 2N 225.0 (250.3) kcal/mol. The ionization potential and electron affinity of B 2N are predicted to be 8.62±0.1 and 3.34±0.1 eV. The MP4-level additivity approximations involved in G1 theory results in errors on the order of 1 kcal/mol in the Σ De values.

  15. Quantifying N2O reduction to N2 based on N2O isotopocules - validation with independent methods (helium incubation and 15N gas flux method)

    NASA Astrophysics Data System (ADS)

    Lewicka-Szczebak, Dominika; Augustin, Jürgen; Giesemann, Anette; Well, Reinhard

    2017-02-01

    Stable isotopic analyses of soil-emitted N2O (δ15Nbulk, δ18O and δ15Nsp = 15N site preference within the linear N2O molecule) may help to quantify N2O reduction to N2, an important but rarely quantified process in the soil nitrogen cycle. The N2O residual fraction (remaining unreduced N2O, rN2O) can be theoretically calculated from the measured isotopic enrichment of the residual N2O. However, various N2O-producing pathways may also influence the N2O isotopic signatures, and hence complicate the application of this isotopic fractionation approach. Here this approach was tested based on laboratory soil incubations with two different soil types, applying two reference methods for quantification of rN2O: helium incubation with direct measurement of N2 flux and the 15N gas flux method. This allowed a comparison of the measured rN2O values with the ones calculated based on isotopic enrichment of residual N2O. The results indicate that the performance of the N2O isotopic fractionation approach is related to the accompanying N2O and N2 source processes and the most critical is the determination of the initial isotopic signature of N2O before reduction (δ0). We show that δ0 can be well determined experimentally if stable in time and then successfully applied for determination of rN2O based on δ15Nsp values. Much more problematic to deal with are temporal changes of δ0 values leading to failure of the approach based on δ15Nsp values only. For this case, we propose here a dual N2O isotopocule mapping approach, where calculations are based on the relation between δ18O and δ15Nsp values. This allows for the simultaneous estimation of the N2O-producing pathways' contribution and the rN2O value.

  16. Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

    PubMed

    Rusanova, Julia A; Semenaka, Valentina V; Dyakonenko, Viktoriya V; Shishkin, Oleg V

    2015-09-01

    The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands. The Cu(II) ion adopts a distorted square-pyramidal coordination while the Cr(III) ion has a distorted octa-hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O-H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two -CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1).

  17. Comparison of O2 and H2O as oxygen source for homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Konishi, Keita; Goto, Ken; Togashi, Rie; Murakami, Hisashi; Higashiwaki, Masataka; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Kumagai, Yoshinao

    2018-06-01

    Homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy (HVPE) using O2 or H2O as an oxygen source was investigated by thermodynamic analysis, and compared with measured properties after growth. The thermodynamic analysis revealed that Ga2O3 growth is expected even at 1000 °C using both oxygen sources due to positive driving forces for Ga2O3 deposition. The experimental results for homoepitaxial growth on (0 0 1) β-Ga2O3 substrates showed that the surfaces of the layers grown with H2O were smoother than those grown with O2, although the growth rate with H2O was approximately half that with O2. However, in the homoepitaxial layer grown using H2O, incorporation of Si impurities with a concentration almost equal to the effective donor concentration (2 × 1016 cm-3) was confirmed, which was caused by decomposition of the quartz glass reactor due to the presence of hydrogen in the system.

  18. Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

    PubMed

    Tang, Jian; McKellar, A R W

    2005-09-15

    High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

  19. Spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide: a highly active and stable hybrid electrocatalyst for the oxygen reduction reaction.

    PubMed

    Ning, Rui; Tian, Jingqi; Asiri, Abdullah M; Qusti, Abdullah H; Al-Youbi, Abdulrahman O; Sun, Xuping

    2013-10-29

    In this Letter, for the first time, we demonstrated the preparation of a highly efficient electrocatalyst, spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide (CuCo2O4/N-rGO), for an oxygen reduction reaction (ORR) under alkaline media. The hybrid exhibits higher ORR catalytic activity than CuCo2O4 or N-rGO alone, the physical mixture of CuCo2O4 nanoparticles and N-rGO, and Co3O4/N-rGO. Moreover, such a hybrid affords superior durability to the commercial Pt/C catalyst.

  20. The reaction of N/2D/ with O2 as a source of O/1D/ atoms in aurorae

    NASA Technical Reports Server (NTRS)

    Rusch, D. W.; Sharp, W. E.; Gerard, J.-C.

    1978-01-01

    The source of O(1D) atoms in the auroral ionosphere is investigated using sounding rocket data. Previously, it has been shown that the conventional sources of O(1D) atoms in the aurora, dissociative recombination of O2(plus) and electron impact excitation of atomic oxygen, fail to explain the measured 6300 A volume emission rate profile. It is suggested that the atom-atom interchange reaction of N(2D) with O2 can be the major source of auroral 6300 A emission if O(1D) is created with high efficiency.

  1. {μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II).

    PubMed

    Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

    2012-08-01

    Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

  2. Thermophysical properties and oxygen transport in (Th x,Pu 1-x)O 2

    SciTech Connect

    Galvin, C. O. T.; Cooper, M. W. D.; Rushton, M. J. D.

    Using Molecular Dynamics, this paper investigates the thermophysical properties and oxygen transport of (Th x,Pu 1–x)O 2 (0 ≤ x ≤ 1) between 300–3500 K. Specifically, the superionic transition is investigated and viewed via the thermal dependence of lattice parameter, linear thermal expansion coefficient, enthalpy and specific heat at constant pressure. Oxygen diffusivity and activation enthalpy are also investigated. Below the superionic temperature an increase of oxygen diffusivity for certain compositions of (Th x,Pu 1–x)O 2 compared to the pure end members is predicted. Oxygen defect formation enthalpies are also examined, as they underpin the superionic transition temperature and themore » increase in oxygen diffusivity. The increase in oxygen diffusivity for (Th x,Pu 1–x)O 2 is explained in terms of lower oxygen defect formation enthalpies for (Th x,Pu 1–x)O 2 than PuO 2 and ThO 2, while links are drawn between the superionic transition temperature and oxygen Frenkel disorder.« less

  3. Thermophysical properties and oxygen transport in (Th x,Pu 1-x)O 2

    DOE PAGES

    Galvin, C. O. T.; Cooper, M. W. D.; Rushton, M. J. D.; ...

    2016-10-31

    Using Molecular Dynamics, this paper investigates the thermophysical properties and oxygen transport of (Th x,Pu 1–x)O 2 (0 ≤ x ≤ 1) between 300–3500 K. Specifically, the superionic transition is investigated and viewed via the thermal dependence of lattice parameter, linear thermal expansion coefficient, enthalpy and specific heat at constant pressure. Oxygen diffusivity and activation enthalpy are also investigated. Below the superionic temperature an increase of oxygen diffusivity for certain compositions of (Th x,Pu 1–x)O 2 compared to the pure end members is predicted. Oxygen defect formation enthalpies are also examined, as they underpin the superionic transition temperature and themore » increase in oxygen diffusivity. The increase in oxygen diffusivity for (Th x,Pu 1–x)O 2 is explained in terms of lower oxygen defect formation enthalpies for (Th x,Pu 1–x)O 2 than PuO 2 and ThO 2, while links are drawn between the superionic transition temperature and oxygen Frenkel disorder.« less

  4. Growth and properties of oxygen- and ion-doped Bi2Sr2CaCu2O8+δ single crystals

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Lombardo, L. W.; Kapitulnik, A.; Laderman, S. S.; Jacowitz, R. D.

    1990-04-01

    A directional solidification method for growing large single crystals in the Bi2Sr2CaCu2O8+δ system is reported. Ion doping, with replacement of La for Sr and Y for Ca, as well as oxygen doping in these crystals has been explored. Doped and undoped crystals have been characterized using microprobe analysis, x-ray diffraction, thermogravimetric analysis, and magnetic and Hall measurements. Ion doping results in little change of the superconducting transition for substitution levels below 20-25%, while beyond this level the Meissner signal broadens and the low-temperature Meissner signal decreases. Microprobe analysis and x-ray diffraction performed on these more highly substituted single crystals provide evidence for inhomogeneity and phase segregation into regions of distinct composition. Annealing unsubstituted crystals in increasing partial pressures of oxygen reversibly depresses the superconducting transition temperature from 90 (as made) to 77 K (oxygen pressure annealed), while the carrier concentrations, as determined from Hall effect measurements, increase from n=3.1(3)×1021 cm-3 (0.34 holes per Cu site) to 4.6(3)×1021 cm-3 (0.50 holes per Cu site). No degradation of the Meissner transition or other indications of inhomogeneity or phase segregation with doping are noted, suggesting that oxygen-doped Bi2Sr2CaCu2O8+δ is a suitable system for pursuing doping studies. The decrease in Tc with concentration for 0.34<=n<=0.50 indicates that a high-carrier-concentration regime exists in which Tc decreases with n and suggests that this decrease does not arise from material inhomogeneity or other materials problems. An examination of the variation of Tc with the density of states and lattice constants for all of the doped and undoped superconducting samples considered here indicates that changes in Tc with doping are primarily affected by changes in the density of states (or carrier concentration) rather than by structural variation induced by the doping.

  5. Spectrophotometric determination of H2O2-generating oxidases using oxyhemoglobin as oxygen donor and indicator.

    PubMed

    Bârzu, O; Dânşoreanu, M

    1980-01-01

    1. Spectrophotometric determination of oxygen uptake using oxyhemoglobin as oxygen donor and indicator was used for assay of H2O2-generating oxidases like monoamine oxidase and glucose oxidase. 2. In order to decompose H2O2 formed during the oxygen uptake, catalase and methanol (or ethanol) was added to the respiratory system. At pH values higher than 7.5 the oxydation of deoxygenated hemoglobin to methemoglobin was less than 3%. 2. Oxidases with low Km for oxygen can be assayed using the spectrophotometric method if suitable correction factors are introduced into the calculation of oxygen uptake. The correction factor represents the ratio of the rate of formation (or disappearance) of one of the reactants and the rate of oxyhemoglobin deoxygenation, measured under identical experimental conditions.

  6. Effect of ambient oxygen on the photoluminescence of sol-gel-derived nanocrystalline ZrO2:Eu,Nb

    NASA Astrophysics Data System (ADS)

    Puust, Laurits; Kiisk, Valter; Eltermann, Marko; Mändar, Hugo; Saar, Rando; Lange, Sven; Sildos, Ilmo; Dolgov, Leonid; Matisen, Leonard; Jaaniso, Raivo

    2017-06-01

    The development of inorganic nanophosphors is an active research field due to many applications, including optical gas sensing materials. We found a systematic dependence of the photoluminescence (PL) of europium (Eu3+) impurity ions in zirconia (ZrO2) nanocrystals on the ambient oxygen concentration in a O2/N2 mixture at normal pressure. Europium-doped ZrO2 powders were synthesized via a sol-gel route. Heat-treatment at 1200 °C resulted in a well-developed monoclinic phase (XRD crystallite size of ~50 nm) and an intense PL of Eu3+ ions residing in the dominant phase (Eu3+ was excited directly at 395 or 464 nm). Co-doping with niobium resulted in a narrowing of the PL emission lines. Only Nb5+ was detected by XPS and is believed to charge-compensate Eu3+ activators throughout the material leading to a more regular crystal lattice. At room temperature, the exposure to oxygen suppressed the Eu3+ fluorescence, whereas, at elevated temperatures (300 °C), the effect was reversed. At 300 °C and under a focused continuous laser beam, a substantial PL response (>50%) was achieved when switching 100% of N2 for 100% of O2. PL decay kinetics clearly showed that at 300 °C fluorescence quenching centers were induced within the material by oxygen desorption. The relatively fast (<5 min) and sub-linear PL response to the changes of oxygen concentration shows that ZrO2:Eu,Nb is a promising PL-based oxygen sensing material over a wide-range of oxygen pressures.

  7. Theoretical investigation of thermodynamic stability and mobility of the oxygen vacancy in ThO 2 –UO 2 solid solutions

    DOE PAGES

    Liu, B.; Aidhy, D. S.; Zhang, Y.; ...

    2014-10-16

    The thermodynamic stability and the migration energy barriers of oxygen vacancies in ThO 2 –UO 2 solid solutions are investigated by density functional theory calculations. In pure ThO 2, the formation energy of oxygen vacancy is 7.58 eV and 1.46 eV under O rich and O poor conditions, respectively, while its migration energy barrier is 1.97 eV. The addition of UO 2 into ThO 2 significantly decreases the energetics of formation and migration of the oxygen vacancy. Among the range of UO 2-ThO 2 solid solutions studied in this work, UO 2 exhibits the lowest formation energy (5.99 eV andmore » -0.13 eV under O rich and O poor conditions, respectively) and Th 0.25U0 .75O 2 exhibits the lowest migration energy barrier (~ 1 eV). Moreover, by considering chemical potential, the phase diagram of oxygen vacancy as a function of both temperature and oxygen partial pressure is shown, which could help to gain experimental control over oxygen vacancy concentration.« less

  8. Oxygen potentials, oxygen diffusion coefficients and defect equilibria of nonstoichiometric (U,Pu)O2±x

    NASA Astrophysics Data System (ADS)

    Kato, Masato; Watanabe, Masashi; Matsumoto, Taku; Hirooka, Shun; Akashi, Masatoshi

    2017-04-01

    Oxygen potential of (U,Pu)O2±x was evaluated based on defect chemistry using an updated experimental data set. The relationship between oxygen partial pressure and deviation x in (U,Pu)O2±x was analyzed, and equilibrium constants of defect formation were determined as functions of Pu content and temperature. Brouwer's diagrams were constructed using the determined equilibrium constants, and a relational equation to determine O/M ratio was derived as functions of O/M ratio, Pu content and temperature. In addition, relationship between oxygen potential and oxygen diffusion coefficients were described.

  9. Synthesis, structure, and properties of nickel complexes with nitrilotris(methylenephosphonic acid) [Ni(H{sub 2}O)3N(CH2PO{sub 3}H){sub 3}] and Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O

    SciTech Connect

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@yandex.ru; Zakirova, R. M.

    2016-03-15

    Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato) aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H{sub 2}O){sub 3}N(CH{sub 2}PO{sub 3}H){sub 3}] is composed of linear coordination polymers and belongs to sp. gr. P2{sub 1}/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O has an island dimeric chelate structuremore » and belongs to sp. gr. C2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond.« less

  10. Year-round N2O production by benthic NOx reduction in a monomictic south-alpine lake

    NASA Astrophysics Data System (ADS)

    Freymond, C. V.; Wenk, C. B.; Frame, C. H.; Lehmann, M. F.

    2013-12-01

    Nitrous oxide (N2O) is a potent greenhouse gas, generated through microbial nitrogen (N) turnover processes, such as nitrification, nitrifier denitrification, and denitrification. Previous studies quantifying natural sources have mainly focused on soils and the ocean, but the potential role of terrestrial water bodies in the global N2O budget has been widely neglected. Furthermore, the biogeochemical controls on the production rates and the microbial pathways that produce benthic N2O in lakes are essentially unknown. In this study, benthic N2O fluxes and the contributions of the microbial pathways that produce N2O were assessed using 15N label flow-through sediment incubations in the eutrophic, monomictic south basin of Lake Lugano in Switzerland. The sediments were a significant source of N2O throughout the year, with production rates ranging between 140 and 2605 nmol N2O h-1 m-2, and the highest observed rates coinciding with periods of water column stratification and stably anoxic conditions in the overlying bottom water. Nitrate (NO3-) reduction via denitrification was found to be the major N2O production pathway in the sediments under both oxygen-depleted and oxygen-replete conditions in the overlying water, while ammonium oxidation did not contribute significantly to the benthic N2O flux. A marked portion (up to 15%) of the total NO3- consumed by denitrification was reduced only to N2O, without complete denitrification to N2. These fluxes were highest when the bottom water had stabilized to a low-oxygen state, in contrast with the notion that stable anoxia is particularly conducive to complete denitrification without accumulation of N2O. This study provides evidence that lake sediments are a significant source of N2O to the overlying water and may produce large N2O fluxes to the atmosphere during seasonal mixing events.

  11. Temperature Dependence of the Collisional Removal of O2(A(sup 3)Sigma(sup +)(sub u), upsilon=9 ) with O2 and N2

    NASA Technical Reports Server (NTRS)

    Hwang, Eunsook S.; Copeland, Richard A.

    1997-01-01

    The temperature dependence of the collisional removal of O2 molecules in the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) electronic state has been studied for the colliders O2 and N2, over the temperature range 150 to 300 K. In a cooled flow cell, the output of a pulsed dye laser excites the O2 to the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) state, and the output of a time-delayed second laser monitors the temporal evolution of this level via a resonance-enhanced ionization. We find the u thermally averaged removal cross section for O2 collisions is constant (approx. 10 A(sup 2)) between room temperature and 200 K, then increases rapidly with decreasing temperature, doubling by 150 K. In contrast, the N2 cross section at 225 K is approx. 8% smaller and gradually increases to a value at 150 K that is approx. 60% larger than the room temperature value. The difference between the temperature dependence of the O2 and N2 collision cross section implies that the removal by oxygen becomes more important at the lower temperatures found in the mesosphere, but removal by N2 still dominates.

  12. The denitrification paradox: The role of O2 in sediment N2O production

    NASA Astrophysics Data System (ADS)

    Barnes, Jonathan; Upstill-Goddard, Robert C.

    2018-01-01

    We designed a novel laboratory sediment flux chamber in which we maintained the headspace O2 partial pressure at preselected values, allowing us to experimentally regulate "in-situ" O2 to evaluate its role in net N2O production by an intertidal estuarine sediment (Tyne, UK). In short-term (30 h) incubations with 10 L of overlying estuarine water (∼3 cm depth) and headspace O2 regulation (headspace: sediment/water ratio ∼9:1), net N2O production was highest at 1.2% O2 (sub-oxic; 32.3 nmol N2O m-2 d-1), an order of magnitude higher than at either 0.0% (anoxic; 2.5 N2O nmol m-2 d-1) or 20.85% (ambient; 2.3 nmol N2O m-2 d-1) O2. In a longer-term sealed incubation (∼490 h) without O2 control, time-dependent behaviour of N2O in the tank headspace was highly non-linear with time, showing distinct phases: (i) an initial period of no or little change in O2 or N2O up to ∼ 100 h; (ii) a quasi-linear, inverse correlation between O2 and N2O to ∼360 h, in which O2 declined to ∼2.1% and N2O rose to ∼7800 natm; (iii) over the following 50 h a slower O2 decline, to ∼1.1%, and a more rapid N2O increase, to ∼12000 natm; (iv) over the next 24 h a slowed O2 decline towards undetectable levels and a sharp fall in N2O to ∼4600 natm; (iv) a continued N2O decrease at zero O2, to ∼3000 natm by ∼ 490 h. These results show clearly that rapid N2O consumption (∼115 nmol m-2 d-1), presumably via heterotrophic denitrification (HD), occurs under fully anoxic conditions and therefore that N2O production, which was optimal for sub-oxic O2, results from other nitrogen transformation processes. In experiments in which we amended sediment overlying water to either 1 mM NH4+ or 1 mM NO3-, N2O production rates were 2-134 nmol N2O m-2 d-1 (NH4+ addition) and 0.4-2.2 nmol N2O m-2 d-1 (NO3- addition). We conclude that processes involving NH4+ oxidation (nitrifier nitrification; nitrifier denitrification; nitrification-coupled denitrification) are principally responsible for N2O

  13. Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

    PubMed

    Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

    2010-04-20

    The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

  14. Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

    PubMed

    Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

    2017-05-01

    An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

    PubMed

    Li, Xiang; Wang, Haopeng; Bowen, Kit H

    2010-10-14

    The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  16. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.

    2010-10-01

    The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  17. Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks

    NASA Technical Reports Server (NTRS)

    Nguyen, Quang-Viet

    2008-01-01

    A fiber-optic sensor system has been developed that can remotely measure the concentration of molecular oxygen (O2), nitrogen (N2), hydrocarbon vapor, and other gases (CO2, CO, H2O, chlorofluorocarbons, etc.) in the ullage of a liquid-fuel tank. The system provides an accurate and quantitative identification of the above gases with an accuracy of better than 1 percent by volume (for O2 or N2) in real-time (5 seconds). In an effort to prevent aircraft fuel tank fires or explosions similar to the tragic TWA Flight 800 explosion in 1996, OBIGGS are currently being developed for large commercial aircraft to prevent dangerous conditions from forming inside fuel tanks by providing an inerting gas blanket that is low in oxygen, thus preventing the ignition of the fuel/air mixture in the ullage. OBIGGS have been used in military aircraft for many years and are now standard equipment on some newer large commercial aircraft (such as the Boeing 787). Currently, OBIGGS are being developed for retrofitting to existing commercial aircraft fleets in response to pending mandates from the FAA. Most OBIGGS use an air separation module (ASM) that separates O2 from N2 to make nitrogen-enriched air from compressed air flow diverted from the engine (bleed air). Current OBIGGS systems do not have a closed-loop feedback control, in part, due to the lack of suitable process sensors that can reliably measure N2 or O2 and at the same time, do not constitute an inherent source of ignition. Thus, current OBIGGS operate with a high factor-of-safety dictated by process protocol to ensure adequate fuel-tank inerting. This approach is inherently inefficient as it consumes more engine bleed air than is necessary compared to a closed-loop controlled approach. The reduction of bleed air usage is important as it reduces fuel consumption, which translates to both increased flight range and lower operational costs. Numerous approaches to developing OBIGGS feedback-control sensors have been under

  18. REMPI detection of singlet oxygen 1O2 arising from UV-photodissociation of van der Waals complex isoprene-oxygen C5H8-O2

    NASA Astrophysics Data System (ADS)

    Bogomolov, Alexandr S.; Dozmorov, Nikolay V.; Kochubei, Sergei A.; Baklanov, Alexey V.

    2018-01-01

    The one-laser two-color resonance enhanced multiphoton ionization REMPI [(1 + 1‧) + 1] and velocity map imaging have been applied to investigate formation of molecular oxygen in excited singlet O2(a1Δg) and ground O2(X3Σg-) states in the photodissociation of van der Waals complex isoprene-oxygen C5H8-O2. These molecules were found to appear in the different rotational states with translational energy varied from a value as low as ∼1 meV to a distribution with temperature of about 940 K. The observed traces of electron recoil in the images of photoions reveal participation of several ionization pathways of the resonantly excited intermediate states of O2.

  19. Crystal structure, chemical composition, and extended defects of the high-Tc (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta compounds.

    PubMed

    Eibl, O

    1995-02-15

    This paper summarizes results obtained by high-resolution transmission electron microscopy on the crystal structure and microstructure of the (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta high-Tc superconducting oxides. The experimental basis for the work presented here are high-resolution structure images obtained at ultra-thin (3 nm) areas of carefully prepared transmission electron microscope (TEM) samples. The analysis was carried out on a 400 kV TEM equipped with a pole piece yielding 0.17 nm point-to-point resolution. From the images obtained the projected crystal potential of the cations can be extracted directly, as confirmed by detailed image simulation. Structural analysis of the oxygen sublattice remains an unsolved problem by high-resolution TEM (HRTEM), mainly because of the small scattering factors, and thus the contribution of the oxygen sublattice to the image contrast is small. The (BiPb)2Sr2Ca(n)-1CunO4 + 2n + delta phases are modulated structures that can be understood as an average structure plus a superimposed displacement field. The crystal structure consists of BiO double layers and perovskite-type cuboids (containing Sr, Ca, Cu, and O), which are sandwiched between the BiO double layers. The displacement field can be directly analyzed by HRTEM, and the largest displacement amplitudes of 70 pm were determined for the Bi atoms in the n = 1 compound. The chemical composition of the n = 2 and n = 3 compounds was determined by EDX in the TEM for the cation sublattice. A significant (Ca + Sr) deficiency (approximately 10%) with respect to Cu was found. The (Sr + Ca)/Cu mole fraction ratio was 1.31 for the Bi-2212 phase and 1.14 for the Bi(Pb)-2223 phase. The oxygen content cannot be determined by EDX in the TEM with the accuracy necessary for a correlation with electrical and superconducting properties. The defect structure present in these materials, that is, intergrown lamellae with different crystal structures and equal or different chemical

  20. Soil Nitrification and N2O Production: the connection with N concentration and Soil Water Content

    NASA Astrophysics Data System (ADS)

    Zhu-Barker, X.; Horwath, W. R.

    2016-12-01

    The development of mitigation strategies to reduce nitrous oxide (N2O) emission from soils is dependent on explicating the biophysical factors affecting different N2O production pathways. Ammonia oxidation and heterotrophic denitrification are the main pathways of N2O production, depending on soil conditions such as soil moisture content, oxygen (O2) content and N substrate. Many researchers have reported that N2O production increased as substrate concentration and soil moisture content increased. However, less understood is how N fertilizer concentration and moisture content interact to affect N2O production pathways. To investigate interaction and its effect on O2 consumption, we incubated three agricultural soils (clay, sandy loam, and peat) with different concentrations of (NH4)2SO4 (0-1000 µg N g-1) under 50 %, 75%, and 100% of water holding capacity. All treatments received 15N -KNO3 to bring the concentrations of NO3-_N in soils to 50 mg kg-1 soil and the NO3- pool to an enrichment of 10 atom% 15N. In all soils, the total amount of O2 consumption and N2O production increased as soil ammonical N concentration increased. The increased soil moisture significantly promoted N2O production in sandy loam and clay loam soils, compared to the peat soil. These results indicate that N2O production increased as substrate concentration increased likely due to the onset of O2 limitation caused by ammonia oxidation.

  1. A toy model for estimating N2O emissions from natural soils

    NASA Technical Reports Server (NTRS)

    Fung, Inez

    1992-01-01

    A model of N2O emissions from natural soils, whose ultimate objective is to evaluate what contribution natural ecosystems make to the global N2O budget and how the contribution would change with global change, is presented. Topics covered include carbon and nitrogen available in the soil, delivery of nitrifiable N, soil water and oxygen status, soil water budget model, effects of drainage, nitrification and denitrification potentials, soil fertility, N2O production, and a model evaluation. A major implication of the toy model is that the tropics account for more than 80 percent of global emission.

  2. Oxygen-deficient photostable Cu2O for enhanced visible light photocatalytic activity.

    PubMed

    Singh, Mandeep; Jampaiah, Deshetti; Kandjani, Ahmad E; Sabri, Ylias M; Della Gaspera, Enrico; Reineck, Philipp; Judd, Martyna; Langley, Julien; Cox, Nicholas; van Embden, Joel; Mayes, Edwin L H; Gibson, Brant C; Bhargava, Suresh K; Ramanathan, Rajesh; Bansal, Vipul

    2018-03-29

    Oxygen vacancies in inorganic semiconductors play an important role in reducing electron-hole recombination, which may have important implications in photocatalysis. Cuprous oxide (Cu2O), a visible light active p-type semiconductor, is a promising photocatalyst. However, the synthesis of photostable Cu2O enriched with oxygen defects remains a challenge. We report a simple method for the gram-scale synthesis of highly photostable Cu2O nanoparticles by the hydrolysis of a Cu(i)-triethylamine [Cu(i)-TEA] complex at low temperature. The oxygen vacancies in these Cu2O nanoparticles led to a significant increase in the lifetimes of photogenerated charge carriers upon excitation with visible light. This, in combination with a suitable energy band structure, allowed Cu2O nanoparticles to exhibit outstanding photoactivity in visible light through the generation of electron-mediated hydroxyl (OH˙) radicals. This study highlights the significance of oxygen defects in enhancing the photocatalytic performance of promising semiconductor photocatalysts.

  3. Kinetics of NH3 -oxidation, NO-turnover, N2 O-production and electron flow during oxygen depletion in model bacterial and archaeal ammonia oxidisers.

    PubMed

    Hink, Linda; Lycus, Pawel; Gubry-Rangin, Cécile; Frostegård, Åsa; Nicol, Graeme W; Prosser, James I; Bakken, Lars R

    2017-12-01

    Ammonia oxidising bacteria (AOB) are thought to emit more nitrous oxide (N 2 O) than ammonia oxidising archaea (AOA), due to their higher N 2 O yield under oxic conditions and denitrification in response to oxygen (O 2 ) limitation. We determined the kinetics of growth and turnover of nitric oxide (NO) and N 2 O at low cell densities of Nitrosomonas europaea (AOB) and Nitrosopumilus maritimus (AOA) during gradual depletion of TAN (NH 3  + NH4+) and O 2 . Half-saturation constants for O 2 and TAN were similar to those determined by others, except for the half-saturation constant for ammonium in N. maritimus (0.2 mM), which is orders of magnitudes higher than previously reported. For both strains, cell-specific rates of NO turnover and N 2 O production reached maxima near O 2 half-saturation constant concentration (2-10 μM O 2 ) and decreased to zero in response to complete O 2 -depletion. Modelling of the electron flow in N. europaea demonstrated low electron flow to denitrification (≤1.2% of the total electron flow), even at sub-micromolar O 2 concentrations. The results corroborate current understanding of the role of NO in the metabolism of AOA and suggest that denitrification is inconsequential for the energy metabolism of AOB, but possibly important as a route for dissipation of electrons at high ammonium concentration. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  4. Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

    PubMed Central

    Yang, Jingbin; Li, Dongxu; Fang, Yuan

    2017-01-01

    C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

  5. Turbulent piloted partially-premixed flames with varying levels of O2/N2: stability limits and PDF calculations

    NASA Astrophysics Data System (ADS)

    Juddoo, Mrinal; Masri, Assaad R.; Pope, Stephen B.

    2011-12-01

    This paper reports measured stability limits and PDF calculations of piloted, turbulent flames of compressed natural gas (CNG) partially-premixed with either pure oxygen, or with varying levels of O2/N2. Stability limits are presented for flames of CNG fuel premixed with up to 20% oxygen as well as CNG-O2-N2 fuel where the O2 content is varied from 8 to 22% by volume. Calculations are presented for (i) Sydney flame B [Masri et al. 1988] which uses pure CNG as well as flames B15 to B25 where the CNG is partially-premixed with 15-25% oxygen by volume, respectively and (ii) Sandia methane-air (1:3 by volume) flame E [Barlow et al. 2005] as well as new flames E15 and E25 that are partially-premixed with 'reconstituted air' where the O2 content in nitrogen is 15 and 25% by volume, respectively. The calculations solve a transported PDF of composition using a particle-based Monte Carlo method and employ the EMST mixing model as well as detailed chemical kinetics. The addition of oxygen to the fuel increases stability, shortens the flames, broadens the reaction zone, and shifts the stoichiometric mixture fraction towards the inner side of the jet. It is found that for pure CNG flames where the reaction zone is narrow (∼0.1 in mixture fraction space), the PDF calculations fail to reproduce the correct level of local extinction on approach to blow-off. A broadening in the reaction zone up to about 0.25 in mixture fraction space is needed for the PDF/EMST approach to be able to capture these finite-rate chemistry effects. It is also found that for the same level of partial premixing, increasing the O2/N2 ratio increases the maximum levels of CO and NO but shifts the peak to richer mixture fractions. Over the range of oxygenation investigated here, stability limits have shown to improve almost linearly with increasing oxygen levels in the fuel and with increasing the contribution of release rate from the pilot.

  6. On the production of N2O from the reaction of O/1D/with N2.

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Lissi, E.; Heicklen, J.

    1972-01-01

    Ozone was photolyzed at 2537 A and at 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions O(1D) + N2 + M leading to N2O + M and O(1D) + N2 leading to O(3P) + N2. In this study N2O was not found as a product. Thus from our detectability limit for N2O an upper limit to the efficiency of the first reaction relative to the second of 2.5 times 10 to the -6 power at 1000-torr total pressure was computed.

  7. Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes.

    PubMed

    Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian; Yang, Weimin; Li, Jian-Feng; Li, Ang; Yang, Zhilin; Ozin, Geoffrey A; Gong, Jinlong

    2018-05-04

    A hundred years on, the energy-intensive Haber-Bosch process continues to turn the N 2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N 2 that is based on clean energy. Surface oxygen vacancies (surface O vac ) hold great potential for N 2 adsorption and activation, but introducing O vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O vac by atomic layer deposition is described, forming a thin amorphous TiO 2 layer on plasmon-enhanced rutile TiO 2 /Au nanorods. Surface O vac in the outer amorphous TiO 2 thin layer promote the adsorption and activation of N 2 , which facilitates N 2 reduction to ammonia by excited electrons from ultraviolet-light-driven TiO 2 and visible-light-driven Au surface plasmons. The findings offer a new approach to N 2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Oxygen vacancies dependent phase transition of Y2O3 films

    NASA Astrophysics Data System (ADS)

    Yu, Pengfei; Zhang, Kan; Huang, Hao; Wen, Mao; Li, Quan; Zhang, Wei; Hu, Chaoquan; Zheng, Weitao

    2017-07-01

    Y2O3 films have great application potential in high-temperature metal matrix composite and nuclear engineering, used as interface diffusion and reaction barrier coating owing to their excellent thermal and chemical stability, high melting point and extremely negative Gibbs formation energy, and thus their structural and mechanical properties at elevated temperature are especially important. Oxygen vacancies exist commonly in yttrium oxide (Y2O3) thin films and act strongly on the phase structure and properties, but oxygen vacancies dependent phase transition at elevated temperature has not been well explored yet. Y2O3 thin films with different oxygen vacancy concentrations have been achieved by reactive sputtering through varying substrate temperature (Ts), in which oxygen vacancies increase monotonously with increasing Ts. For as-deposited Y2O3 films, oxygen vacancies present at high Ts can promote the nucleation of monoclinic phase, meanwhile, high Ts can induce the instability of monoclinic phase. Thus their competition results in forming mixed phases of cubic and monoclinic at high Ts. During vacuum annealing at 1000 °C, a critical oxygen vacancy concentration is observed, below which phase transition from monoclinic to cubic takes place, and above which phase transfer from monoclinic to the oxygen defective phase (ICDD file no. 39-1063), accompanying by stress reversal from compressive to tensile and maintenance of high hardness.

  9. O2(a1Δ) quenching in O/O2/O3/CO2/He/Ar mixtures

    NASA Astrophysics Data System (ADS)

    Azyazov, V. N.; Mikheyev, P. A.; Postell, D.; Heaven, M. C.

    2010-02-01

    The development of discharge singlet oxygen generators (DSOG's) that can operate at high pressures is required for the power scaling of the discharge oxygen iodine laser. In order to achieve efficient high-pressure DSOG operation it is important to understand the mechanisms by which singlet oxygen (O2(a1Δ)) is quenched in these devices. It has been proposed that three-body deactivation processes of the type O2(a1Δ))+O+M-->2O2+M provide significant energy loss channels. To further explore these reactions the physical and reactive quenching of O2(a1Δ)) in O(3P)/O2/O3/CO2/He/Ar mixtures has been investigated. Oxygen atoms and singlet oxygen molecules were produced by the 248 nm laser photolysis of ozone. The kinetics of O2(a1Δ)) quenching were followed by observing the 1268 nm fluorescence of the O2 a1Δ-X3Ε transition. Fast quenching of O2(a1Δ)) in the presence of oxygen atoms and molecules was observed. The mechanism of the process has been examined using kinetic models, which indicate that quenching by vibrationally excited ozone is the dominant reaction.

  10. On the production of N2O from the reaction of O(1 D) with N2

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Lissi, E.; Heicklen, J.

    1972-01-01

    Ozone was photolyzed at 2537 A and 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions: (1) O(1D) + N2 + M yields N2O + M, and (2) O(1D) + N2 yields O(3P) + N2. N2O was not found as a product. Thus from our detectability limit for N2O (0.3 micron), an upper limit to the efficiency of the first reaction relative to the second of 0.0000025 at 1000 torr total pressure was computed. This corresponds to k1/k2 smaller than 0.8 x 10 to the minus 25 power cu cm/particle.

  11. Oxygen Vacancies in Shape Controlled Cu2O/Reduced Graphene Oxide/In2O3 Hybrid for Promoted Photocatalytic Water Oxidation and Degradation of Environmental Pollutants.

    PubMed

    Liu, Jie; Ke, Jun; Li, Degang; Sun, Hongqi; Liang, Ping; Duan, Xiaoguang; Tian, Wenjie; Tadé, Moses O; Liu, Shaomin; Wang, Shaobin

    2017-04-05

    A novel shape controlled Cu 2 O/reduced graphene oxide/In 2 O 3 (Cu 2 O/RGO/In 2 O 3 ) hybrid with abundant oxygen vacancies was prepared by a facile, surfactant-free method. The hybrid photocatalyst exhibits an increased photocatalytic activity in water oxidation and degradation of environmental pollutants (methylene blue and Cr 6+ solutions) compared with pure In 2 O 3 and Cu 2 O materials. The presence of oxygen vacancies in Cu 2 O/RGO/In 2 O 3 and the formation of heterojunction between In 2 O 3 and Cu 2 O induce extra diffusive electronic states above the valence band (VB) edge and reduce the band gap of the hybrid consequently. Besides, the increased activity of Cu 2 O/RGO/In 2 O 3 hybrid is also attributed to the alignment of band edge, a process that is assisted by different Fermi levels between In 2 O 3 and Cu 2 O, as well as the charge transfer and distribution onto the graphene sheets, which causes the downshift of VB of In 2 O 3 and the significant increase in its oxidation potential. Additionally, a built-in electric field is generated on the interface of n-type In 2 O 3 and p-type Cu 2 O, suppressing the recombination of photoinduced electron-hole pairs and allowing the photogenerated electrons and holes to participate in the reduction and oxidation reactions for oxidizing water molecules and pollutants more efficiently.

  12. Seasonal effect on N2O formation in nitrification in constructed wetlands.

    PubMed

    Inamori, Ryuhei; Wang, Yanhua; Yamamoto, Tomoko; Zhang, Jixiang; Kong, Hainan; Xu, Kaiqin; Inamori, Yuhei

    2008-10-01

    Constructed wetlands are considered to be important sources of nitrous oxide (N(2)O). In order to investigate the contribution of nitrification in N(2)O formation, some environmental factors, plant species and ammonia-oxidizing bacteria (AOB) in active layers have been compared. Vegetation cells indicated remarkable effect of seasons and different plant species on N(2)O emission and AOB amount. Nitrous oxide data showed large temporal and spatial fluctuations ranging 0-52.8 mg N(2)O m(-2)d(-1). Higher AOB amount and N(2)O flux rate were observed in the Zizania latifolia cell, reflecting high potential of global warming. Roles of plants as ecosystem engineers are summarized with rhizosphere oxygen release and organic matter transportation to affect nitrogen transformation. The Phragmites australis cell contributed to keeping high T-N removal performance and lower N(2)O emission. The distribution of AOB also supported this result. Statistical analysis showed several environmental parameters affecting the strength of observed greenhouse gases emission, such as water temperature, water level, TOC, plant species and plant cover.

  13. Experimental Studies on the Formation of D2O and D2O2 by Implantation of Energetic D+ Ions into Oxygen Ices

    NASA Astrophysics Data System (ADS)

    Bennett, Chris J.; Ennis, Courtney P.; Kaiser, Ralf I.

    2014-02-01

    The formation of water (H2O) in the interstellar medium is intrinsically linked to grain-surface chemistry; thought to involve reactions between atomic (or molecular) hydrogen with atomic oxygen (O), molecular oxygen (O2), and ozone (O3). Laboratory precedent suggests that H2O is produced efficiently when O2 ices are exposed to H atoms (~100 K). This leads to the sequential generation of the hydroxyperoxyl radical (HO2), then hydrogen peroxide (H2O2), and finally H2O and a hydroxyl radical (OH); despite a barrier of ~2300 K for the last step. Recent detection of the four involved species toward ρ Oph A supports this general scenario; however, the precise formation mechanism remains undetermined. Here, solid O2 ice held at 12 K is exposed to a monoenergetic beam of 5 keV D+ ions. Products formed during the irradiation period are monitored through FTIR spectroscopy. O3 is observed through seven archetypal absorptions. Three additional bands found at 2583, 2707, and 1195 cm -1 correspond to matrix isolated DO2 (ν1) and D2O2 (ν1, ν5), and D2O2), respectively. During subsequent warming, the O2 ice sublimates, revealing a broad band at 2472 cm-1 characteristic of amorphous D2O (ν1, ν3). Sublimating D2, D2O, D2O2, and O3 products were confirmed through their subsequent detection via quadrupole mass spectrometry. Reaction schemes based on both thermally accessible and suprathermally induced chemistries were developed to fit the observed temporal profiles are used to elucidate possible reaction pathways for the formation of D2-water. Several alternative schemes to the hydrogenation pathway (O2→HO2→H2O2→H2O) were identified; their astrophysical implications are briefly discussed.

  14. Reduction of the Powerful Greenhouse Gas N2O in the South-Eastern Indian Ocean.

    PubMed

    Raes, Eric J; Bodrossy, Levente; Van de Kamp, Jodie; Holmes, Bronwyn; Hardman-Mountford, Nick; Thompson, Peter A; McInnes, Allison S; Waite, Anya M

    2016-01-01

    Nitrous oxide (N2O) is a powerful greenhouse gas and a key catalyst of stratospheric ozone depletion. Yet, little data exist about the sink and source terms of the production and reduction of N2O outside the well-known oxygen minimum zones (OMZ). Here we show the presence of functional marker genes for the reduction of N2O in the last step of the denitrification process (nitrous oxide reductase genes; nosZ) in oxygenated surface waters (180-250 O2 μmol.kg(-1)) in the south-eastern Indian Ocean. Overall copy numbers indicated that nosZ genes represented a significant proportion of the microbial community, which is unexpected in these oxygenated waters. Our data show strong temperature sensitivity for nosZ genes and reaction rates along a vast latitudinal gradient (32°S-12°S). These data suggest a large N2O sink in the warmer Tropical waters of the south-eastern Indian Ocean. Clone sequencing from PCR products revealed that most denitrification genes belonged to Rhodobacteraceae. Our work highlights the need to investigate the feedback and tight linkages between nitrification and denitrification (both sources of N2O, but the latter also a source of bioavailable N losses) in the understudied yet strategic Indian Ocean and other oligotrophic systems.

  15. Effect of interfacial SiO2- y layer and defect in HfO2- x film on flat-band voltage of HfO2- x /SiO2- y stacks for backside-illuminated CMOS image sensors

    NASA Astrophysics Data System (ADS)

    Na, Heedo; Lee, Jimin; Jeong, Juyoung; Kim, Taeho; Sohn, Hyunchul

    2018-03-01

    In this study, the effect of oxygen gas fraction during deposition of a hafnium oxide (HfO2- x ) film and the influence of the quality of the SiO2- y interlayer on the nature of flat-band voltage ( V fb) in TiN/HfO/SiO2- y /p-Si structures were investigated. X-ray photoemission spectroscopy analysis showed that the non-lattice oxygen peak, indicating an existing oxygen vacancy, increased as the oxygen gas fraction decreased during sputtering. From C- V and J- E analyses, the V fb behavior was significantly affected by the characteristics of the SiO2- y interlayer and the non-lattice oxygen fraction in the HfO2- x films. The HfO2- x /native SiO2- y stack presented a V fb of - 1.01 V for HfO2- x films with an oxygen gas fraction of 5% during sputtering. Additionally, the V fb of the HfO2- x /native SiO2- y stack could be controlled from - 1.01 to - 0.56 V by changing the deposition conditions of the HfO2- x film with the native SiO2- y interlayer. The findings of this study can be useful to fabricate charge-accumulating layers for backside-illuminated image sensor devices.

  16. Theoretical prediction of a self-forming gallium oxide layer at an n-type GaN/SiO2 interface

    NASA Astrophysics Data System (ADS)

    Chokawa, Kenta; Narita, Tetsuo; Kikuta, Daigo; Kachi, Tetsu; Shiozaki, Koji; Shiraishi, Kenji

    2018-03-01

    We examine the energy band diagram at the n-type GaN (n-GaN)/SiO2 interface and show that electron transfer from n-GaN to SiO2 leads to the formation of negatively charged oxygen vacancies in the SiO2, resulting in the self-formation of an n-GaN/Ga2O3/SiO2 structure. On the other hand, it is difficult to automatically form Ga2O3 at a p-type GaN (p-GaN)/SiO2 interface. This electron-transfer-induced self-formation of Ga2O3 causes an interface dipole, which leads to band bending, resulting in an increase in the conduction band offset between GaN and SiO2. Accordingly, by using this self-forming phenomenon, GaN MOSFETs with lower leakage current can be realized.

  17. N(2)O in small para-hydrogen clusters: Structures and energetics.

    PubMed

    Zhu, Hua; Xie, Daiqian

    2009-04-30

    We present the minimum-energy structures and energetics of clusters of the linear N(2)O molecule with small numbers of para-hydrogen molecules with pairwise additive potentials. Interaction energies of (p-H(2))-N(2)O and (p-H(2))-(p-H(2)) complexes were calculated by averaging the corresponding full-dimensional potentials over the H(2) angular coordinates. The averaged (p-H(2))-N(2)O potential has three minima corresponding to the T-shaped and the linear (p-H(2))-ONN and (p-H(2))-NNO structures. Optimization of the minimum-energy structures was performed using a Genetic Algorithm. It was found that p-H(2) molecules fill three solvation rings around the N(2)O axis, each of them containing up to five p-H(2) molecules, followed by accumulation of two p-H(2) molecules at the oxygen and nitrogen ends. The first solvation shell is completed at N = 17. The calculated chemical potential oscillates with cluster size up to the completed first solvation shell. These results are consistent with the available experimental measurements. (c) 2009 Wiley Periodicals, Inc.

  18. Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites

    NASA Astrophysics Data System (ADS)

    Chen, Daixi; Habu, Daiki; Masubuchi, Yuji; Torii, Shuki; Kamiyama, Takashi; Kikkawa, Shinichi

    2016-04-01

    SrTaO2N heated in a helium atmosphere began to release nitrogen of approximately 30 at% at 950 °C while maintaining the perovskite structure and its color changed from orange to dark green. Then it decomposed above 1200 °C to a black mixture of Sr1.4Ta0.6O2.73, Ta2N, and Sr5Ta4O15. The second decomposition was not clearly observed when SrTaO2N was heated in a nitrogen atmosphere below 1550 °C. After heating at 1500 °C for 3 h under a 0.2 MPa nitrogen atmosphere, the perovskite product became dark green and conductive. Structure refinement results suggested that the product was a mixture of tetragonal and cubic perovskites with a decreased ordering of N3-/O2-. The sintered body was changed to an n-type semiconductor after a partial loss of nitrogen to be reduced from the originally insulating SrTaO2N perovskite lattice. LaTiO2N was confirmed to have a similar cis-configuration of the TiO4N2 octahedron as that of TaO4N2 in SrTaO2N. It also released some of its nitrogen at 800 °C changing its color from brown to black and then decomposed to a mixture of LaTiO3, La2O3, and TiN at 1100 °C. These temperatures are lower than those in SrTaO2N.

  19. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2.

    PubMed

    Maitra, Urmimala; House, Robert A; Somerville, James W; Tapia-Ruiz, Nuria; Lozano, Juan G; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A; Massel, Felix; Pickup, David M; Ramos, Silvia; Lu, Xingye; McNally, Daniel E; Chadwick, Alan V; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C; Roberts, Matthew R; Bruce, Peter G

    2018-03-01

    The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li + -O(2p)-Li + interactions). Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg 2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg 2+ remains in Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 , which stabilizes oxygen.

  20. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2

    NASA Astrophysics Data System (ADS)

    Maitra, Urmimala; House, Robert A.; Somerville, James W.; Tapia-Ruiz, Nuria; Lozano, Juan G.; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A.; Massel, Felix; Pickup, David M.; Ramos, Silvia; Lu, Xingye; McNally, Daniel E.; Chadwick, Alan V.; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C.; Roberts, Matthew R.; Bruce, Peter G.

    2018-03-01

    The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li+-O(2p)-Li+ interactions). Na2/3[Mg0.28Mn0.72]O2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na2/3[Mg0.28Mn0.72]O2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2, which stabilizes oxygen.

  1. Oxygen deficiency and Sn doping of amorphous Ga{sub 2}O{sub 3}

    SciTech Connect

    Heinemann, M. D.; Unold, T.; Berry, J.

    2016-01-11

    The potential of effectively n-type doping Ga{sub 2}O{sub 3} considering its large band gap has made it an attractive target for integration into transistors and solar cells. As a result amorphous GaO{sub x} is now attracting interest as an electron transport layer in solar cells despite little information on its opto-electrical properties. Here we present the opto-electronic properties, including optical band gap, electron affinity, and charge carrier density, for amorphous GaO{sub x} thin films deposited by pulsed laser deposition. These properties are strongly dependent on the deposition temperature during the deposition process. The deposition temperature has no significant influence onmore » the general structural properties but produces significant changes in the oxygen stoichiometry of the films. The density of the oxygen vacancies is found to be related to the optical band gap of the GaO{sub x} layer. It is proposed that the oxygen deficiency leads to defect band below the conduction band minimum that increases the electron affinity. These properties facilitate the use of amorphous GaO{sub x} as an electron transport layer in Cu(In,Ga)Se{sub 2} and in Cu{sub 2}O solar cells. Further it is shown that at low deposition temperatures, extrinsic doping with Sn is effective at low Sn concentrations.« less

  2. Microwave dielectric properties of BaO-2CeO{sub 2}-nTiO{sub 2} ceramics

    SciTech Connect

    Sreemoolanadhan, H.; Sebastian, M.T.; Ratheesh, R.

    2004-11-01

    The BaO-2CeO{sub 2}-nTiO{sub 2} ceramics with n=3, 4 and 5 have been prepared with CeO{sub 2} as starting material. The ceramics have been characterized using scanning electron microscopy, X-ray diffraction, Raman and X-ray photoelectron spectroscopy techniques. The microwave dielectric properties have been measured using standard dielectric resonator techniques. BaO-2CeO{sub 2}-3TiO{sub 2} (123), BaO-2CeO{sub 2}-4TiO{sub 2} (124) and BaO-2CeO{sub 2}-5TiO{sub 2} (125) ceramics showed dielectric constants of 38, 27 and 32, respectively. All the ceramics showed fairly good unloaded Q-factors. 124 and 125 compounds exhibited low {tau}f values, while 123 showed a high {tau}f value.

  3. Theoretical evidence of the observed kinetic order dependence on temperature during the N(2)O decomposition over Fe-ZSM-5.

    PubMed

    Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov

    2010-03-28

    The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.

  4. Tidal and spatial variability of nitrous oxide (N2O) in Sado estuary (Portugal)

    NASA Astrophysics Data System (ADS)

    Gonçalves, Célia; Brogueira, Maria José; Nogueira, Marta

    2015-12-01

    The estimate of the nitrous oxide (N2O) fluxes is fundamental to assess its impact on global warming. The tidal and spatial variability of N2O and the air-sea fluxes in the Sado estuary in July/August 2007 are examined. Measurements of N2O and other relevant environmental parameters (temperature, salinity, dissolved oxygen and dissolved inorganic nitrogen - nitrate plus nitrite and ammonium) were recorded during two diurnal tidal cycles performed in the Bay and Marateca region and along the estuary during ebb, at spring tide. N2O presented tidal and spatial variability and varied spatially from 5.0 nmol L-1 in Marateca region to 12.5 nmol L-1 in Sado river input. Although the Sado river may constitute a considerable N2O source to the estuary, the respective chemical signal discharge was rapidly lost in the main body of the estuary due to the low river flow during the sampling period. N2O varied with tide similarly between 5.2 nmol L-1 (Marateca) and 10.0 nmol L-1 (Sado Bay), with the maximum value reached two hours after flooding period. The influence of N2O enriched upwelled seawater (˜10.0 nmol L-1) was well visible in the estuary mouth and apparently represented an important contribution of N2O in the main body of Sado estuary. Despite the high water column oxygen saturation in most of Sado estuary, nitrification did not seem a relevant process for N2O production, probably as the concentration of the substrate, NH4+, was not adequate for this process to occur. Most of the estuary functioned as a N2O source, and only Marateca zone has acted as N2O sink. The N2O emission from Sado estuary was estimated to be 3.7 Mg N-N2O yr-1 (FC96) (4.4 Mg N-N2O yr-1, FRC01). These results have implications for future sampling and scaling strategies for estimating greenhouse gases (GHGs) fluxes in tidal ecosystems.

  5. Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy­ethyl)methylamino]ethanolato-2:1κ4 O 1,N,O 2:O 1}[μ-2,2′-(methylimino)diethanolato-1:2κ4 O,N,O′:O]dithiocyanato-1κN,2κN-chromium(III)copper(II)

    PubMed Central

    Rusanova, Julia A.; Semenaka, Valentina V.; Dyakonenko, Viktoriya V.; Shishkin, Oleg V.

    2015-01-01

    The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal CuII/CrIII complex. The mol­ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio­cyanato ligands. The CuII ion adopts a distorted square-pyramidal coordination while the CrIII ion has a distorted octa­hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O—H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two –CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1). PMID:26396853

  6. Potassium (2,2'-bipyridine-κN,N')bis-(carbonato-κO,O')cobaltate(III) dihydrate.

    PubMed

    Wang, Jian-Fei; Lin, Jian-Li

    2010-09-30

    In the title compound, K[Co(CO(3))(2)(C(10)H(8)N(2))]·2H(2)O, the Co(III) atom is coordinated by two bipyridine N atoms and four O atoms from two bidentate chelating carbonate anions, and thus adopts a distorted octa-hedral N(2)O(4) environment. The [Co(bipy)(CO(3))(2)](-) (bipy is 2,2'-bipyridine) -units are stacked along [100] via π-π stacking inter-actions, with inter-planar distances between the bipyridine rings of 3.36 (4) and 3.44 (6) Å, forming chains. Classical O-H⋯O hydrogen-bonding inter-actions link the chains, forming channels along (100) in which the K(+) ions reside and leading to a three-dimensional supra-molecular architecture.

  7. 2D polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n

    NASA Astrophysics Data System (ADS)

    Mahmood, Rashid; Ahmad, Saeed; Fettouhi, Mohammed; Roisnel, Thierry; Gilani, Mazhar Amjad; Mehmood, Kashif; Murtaza, Ghulam; Isab, Anvarhusein A.

    2018-03-01

    The present study aims at preparing and carrying out the structural investigation of two polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions, [Cd(Imt)(H2O)2(SO4)]n (1) and [Cd(Imt)2(N3)2]n (2). The structures of the complexes were determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of 2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium coordination sphere is completed by two Imt molecules binding through the sulfur atoms and four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.

  8. Net Community and Gross Photosynthetic Production Rates in the Eastern Tropical South Pacific, as Determined from O2/AR Ratios and Triple Oxygen Isotopic Composition of Dissolved O2

    NASA Astrophysics Data System (ADS)

    Prokopenko, M. G.; Yeung, L. Y.; Berelson, W.; Fleming, J.; Rollins, N.; Young, E. D.; Haskell, W. Z.; Hammond, D. E.; Capone, D. G.

    2010-12-01

    This study assesses the rates of ocean carbon production and its fate with respect to recycling or export in the Eastern Tropical South Pacific (ETSP). ETSP has been previously identified as a region where N2 fixation and denitrification may be spatially coupled; this is also a region of localized CO2 outgassing. Using an Equilibrated Inlet Mass Spectrometer (EIMS) system, we obtained continuous measurements of the biological O2 supersaturation in the mixed layer along the ship track encompassing a region bounded by 10-20° S and 80-100° W in January - March, 2010. Vertical profiles were also taken at selected stations and analyzed for dissolved O2/Ar ratios on EIMS and triple oxygen isotope composition (17O excess) on a multi-collector IRMS (Isotope Ratio Mass Spectrometer) at UCLA. Gas exchange rates were estimated using two approaches: the Rn-222 deficit method and the wind parameterization method, which utilized wind speeds extracted from ASCAT satellite database. Oxygen Net Community Production (O-NCP) rates calculated based on biological O2 supersaturation ranged from slightly negative to ~ 0.3 - 15 mmol/m2d, with higher rates along the northern part of the transect. Oxygen Gross Community Production (O-GPP) rates calculated from 17O excess were between 50 ± 20 and 200 ± 40 mmol/m2d, with higher rates observed along the northern cruise transect as well. Notably, the NCP/GPP ratios along the northern transect were higher by the factor of 2 to 3 than their southern counterparts. The O2/Ar-based NCP rates were comparable to POC flux measured with floating traps deployed at the southern stations, but exceeded by a factor of 5-10 the trap POC fluxes obtained at the northern stations. A one-dimensional box model has been constructed to quantify the magnitude of oxygen primary production below the mixed layer. The results of this work will be integrated with measurements of 15-N2 uptake that are in progress, to constrain the potential contribution of N2 fixation

  9. Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

    PubMed

    Almond, Philip M; Albrecht-Schmitt, Thomas E

    2002-10-21

    The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta

  10. Synergetic effect of Ti 3+ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO 2/g-C 3N 4 heterojunctions

    SciTech Connect

    Li, Kai; Huang, Zhenyu; Zeng, Xiaoqiao

    To improve the utilization of visible light and reduce photogenerated electron/hole recombination, Ti 3+ self-doped TiO 2/oxygen-doped graphitic carbon nitride (Ti 3+-TiO 2/O-g-C 3N 4) heterojunctions were prepared via hydrothermal treatment of a mixture of g-C 3N 4 and titanium oxohydride sol obtained from the reaction of TiH 2 with H 2O 2. In this way, exfoliated O-g-C 3N 4 and Ti 3+-TiO 2 nanoparticles were obtained. Simultaneously, strong bonding was formed between Ti 3+-TiO 2 nanoparticles and exfoliated O-g-C 3N 4 during the hydrothermal process. Charge transfer and recombination processes were characterized by transient photocurrent responses, electrochemical impedance test,more » and photoluminescence spectroscopy. The photocatalytic performances were investigated through rhodamine B degradation test under an irradiation source based on 30 W cold visible-light-emitting diode. The highest visible-light photoelectrochemical and photocatalytic activities were observed from the heterojunction with 1:2 mass ratio of Ti 3+-TiO 2 to O-g-C 3N 4. The photodegradation reaction rate constant based on this heterojuction is 0.0356 min -1, which is 3.87 and 4.56 times higher than those of pristine Ti 3+-TiO 2 and pure g-C 3N 4, respectively. Here, the remarkably high photoelectrochemical and photocatalytic performances of the heterojunctions are mainly attributed to the synergetic effect of efficient photogenerated electron-hole separation, decreased electron transfer resistance from interfacial chemical hydroxy residue bonds, and oxidizing groups originating from Ti 3+-TiO 2 and O-g-C 3N 4.« less

  11. Synergetic Effect of Ti3+ and Oxygen Doping on Enhancing Photoelectrochemical and Photocatalytic Properties of TiO2/g-C3N4 Heterojunctions.

    PubMed

    Li, Kai; Huang, Zhenyu; Zeng, Xiaoqiao; Huang, Baibiao; Gao, Shanmin; Lu, Jun

    2017-04-05

    To improve the utilization of visible light and reduce photogenerated electron/hole recombination, Ti 3+ self-doped TiO 2 /oxygen-doped graphitic carbon nitride (Ti 3+ -TiO 2 /O-g-C 3 N 4 ) heterojunctions were prepared via hydrothermal treatment of a mixture of g-C 3 N 4 and titanium oxohydride sol obtained from the reaction of TiH 2 with H 2 O 2 . In this way, exfoliated O-g-C 3 N 4 and Ti 3+ -TiO 2 nanoparticles were obtained. Simultaneously, strong bonding was formed between Ti 3+ -TiO 2 nanoparticles and exfoliated O-g-C 3 N 4 during the hydrothermal process. Charge transfer and recombination processes were characterized by transient photocurrent responses, electrochemical impedance test, and photoluminescence spectroscopy. The photocatalytic performances were investigated through rhodamine B degradation test under an irradiation source based on 30 W cold visible-light-emitting diode. The highest visible-light photoelectrochemical and photocatalytic activities were observed from the heterojunction with 1:2 mass ratio of Ti 3+ -TiO 2 to O-g-C 3 N 4 . The photodegradation reaction rate constant based on this heterojuction is 0.0356 min -1 , which is 3.87 and 4.56 times higher than those of pristine Ti 3+ -TiO 2 and pure g-C 3 N 4 , respectively. The remarkably high photoelectrochemical and photocatalytic performances of the heterojunctions are mainly attributed to the synergetic effect of efficient photogenerated electron-hole separation, decreased electron transfer resistance from interfacial chemical hydroxy residue bonds, and oxidizing groups originating from Ti 3+ -TiO 2 and O-g-C 3 N 4 .

  12. Synergetic effect of Ti 3+ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO 2/g-C 3N 4 heterojunctions

    DOE PAGES

    Li, Kai; Huang, Zhenyu; Zeng, Xiaoqiao; ...

    2017-03-07

    To improve the utilization of visible light and reduce photogenerated electron/hole recombination, Ti 3+ self-doped TiO 2/oxygen-doped graphitic carbon nitride (Ti 3+-TiO 2/O-g-C 3N 4) heterojunctions were prepared via hydrothermal treatment of a mixture of g-C 3N 4 and titanium oxohydride sol obtained from the reaction of TiH 2 with H 2O 2. In this way, exfoliated O-g-C 3N 4 and Ti 3+-TiO 2 nanoparticles were obtained. Simultaneously, strong bonding was formed between Ti 3+-TiO 2 nanoparticles and exfoliated O-g-C 3N 4 during the hydrothermal process. Charge transfer and recombination processes were characterized by transient photocurrent responses, electrochemical impedance test,more » and photoluminescence spectroscopy. The photocatalytic performances were investigated through rhodamine B degradation test under an irradiation source based on 30 W cold visible-light-emitting diode. The highest visible-light photoelectrochemical and photocatalytic activities were observed from the heterojunction with 1:2 mass ratio of Ti 3+-TiO 2 to O-g-C 3N 4. The photodegradation reaction rate constant based on this heterojuction is 0.0356 min -1, which is 3.87 and 4.56 times higher than those of pristine Ti 3+-TiO 2 and pure g-C 3N 4, respectively. Here, the remarkably high photoelectrochemical and photocatalytic performances of the heterojunctions are mainly attributed to the synergetic effect of efficient photogenerated electron-hole separation, decreased electron transfer resistance from interfacial chemical hydroxy residue bonds, and oxidizing groups originating from Ti 3+-TiO 2 and O-g-C 3N 4.« less

  13. Thermoelectric Properties in the TiO2/SnO2 System

    NASA Technical Reports Server (NTRS)

    Dynys, F.; Sayir, A.; Sehirlioglu, A.; Berger, M.

    2009-01-01

    Nanotechnology has provided a new interest in thermoelectric technology. A thermodynamically driven process is one approach in achieving nanostructures in bulk materials. TiO2/SnO2 system exhibits a large spinodal region with exceptional stable phase separated microstructures up to 1400 C. Fabricated TiO2/SnO2 nanocomposites exhibit n-type behavior with Seebeck coefficients greater than -300 .V/K. Composites exhibit good thermal conductance in the range of 7 to 1 W/mK. Dopant additions have not achieved high electrical conductivity (<1000 S/m). Formation of oxygen deficient composites, TixSn1-xO2-y, can change the electrical conductivity by four orders of magnitude. Achieving higher thermoelectric ZT by oxygen deficiency is being explored. Seebeck coeffcient, thermal conductivity, electrical conductance and microstructure will be discussed in relation to composition and doping.

  14. Quenched Magnon excitations by oxygen sublattice reconstruction in (SrCuO2)n/(SrTiO3)2 superlattices.

    PubMed

    Dantz, M; Pelliciari, J; Samal, D; Bisogni, V; Huang, Y; Olalde-Velasco, P; Strocov, V N; Koster, G; Schmitt, T

    2016-09-12

    The recently discovered structural reconstruction in the cuprate superlattice (SrCuO2)n/(SrTiO3)2 has been investigated across the critical value of n = 5 using resonant inelastic x-ray scattering (RIXS). We find that at the critical value of n, the cuprate layer remains largely in the bulk-like two-dimensional structure with a minority of Cu plaquettes being reconstructed. The partial reconstruction leads to quenching of the magnons starting at the Γ-point due to the minority plaquettes acting as scattering points. Although comparable in relative abundance, the doped charge impurities in electron-doped cuprate superconductors do not show this quenching of magnetic excitations.

  15. Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

    PubMed

    McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

    2015-07-06

    Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

  16. Effects of Hydration and Oxygen Vacancy on CO2 Adsorption and Activation on β-Ga2O3(100)

    SciTech Connect

    Pan, Yunxiang; Liu, Chang-jun; Mei, Donghai

    The effects of hydration and oxygen vacancy on CO2 adsorption on the β-Ga2O3(100) surface have been studied using density functional theory slab calculations. Adsorbed CO2 is activated on the dry perfect β-Ga2O3(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect β-Ga2O3(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect β-Ga2O3(100) surface. Adsorption of CO2 on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slight repulsive interactionmore » when H2O and CO2 are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the co-adsorbed H2O to a bicarbonate species, making the overall process exothermic with an adsorption energy of -0.13 eV. The effect of defects on CO2 adsorption and activation has been examined by creating an oxygen vacancy on the dry β-Ga2O3(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O2 molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO2. In the most stable CO2 adsorption configuration on the dry defective β-Ga2O3(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO2 occupies the oxygen vacancy site and the CO2 adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is instantaneous with an adsorption energy of -0.62 eV. These results indicate that, when water and CO2 are both present in the adsorption system simultaneously, the water molecule will compete with CO2 for the oxygen vacancy sites and impact CO2 adsorption and conversion negatively. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the computing time

  17. Theoretical characterization of stable eta1-N2O-, eta2-N2O-, eta1-N2-, and eta2-N2-bound species: intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion.

    PubMed

    Olabe, José A; Estiú, Guillermina L

    2003-08-11

    The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the eta(1)- and eta(2)-linkage isomers of N(2)O and N(2), depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The eta(2)-N(2)O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the eta(1)-N(2)O isomer is followed by Fe-N(2)O dissociation. Only the eta(1)-N(2)O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N(2)O formation. eta(1)-N(2) and eta(2)-N(2) isomers are also predicted as stable species.

  18. Potential short-term losses of N2O and N2 from high concentrations of biogas digestate in arable soils

    NASA Astrophysics Data System (ADS)

    Fiedler, Sebastian Rainer; Augustin, Jürgen; Wrage-Mönnig, Nicole; Jurasinski, Gerald; Gusovius, Bertram; Glatzel, Stephan

    2017-09-01

    Biogas digestate (BD) is increasingly used as organic fertilizer, but has a high potential for NH3 losses. Its proposed injection into soils as a countermeasure has been suggested to promote the generation of N2O, leading to a potential trade-off. Furthermore, the effect of high nutrient concentrations on N2 losses as they may appear after injection of BD into soil has not yet been evaluated. Hence, we performed an incubation experiment with soil cores in a helium-oxygen atmosphere to examine the influence of soil substrate (loamy sand, clayey silt), water-filled pore space (WFPS; 35, 55, 75 %) and application rate (0, 17.6 and 35.2 mL BD per soil core, 250 cm3) on the emission of N2O, N2 and CO2 after the usage of high loads of BD. To determine the potential capacity for gaseous losses, we applied anaerobic conditions by purging with helium for the last 24 h of incubation. Immediate N2O and N2 emissions as well as the N2 / (N2O+N2) product ratio depended on soil type and increased with WFPS, indicating a crucial role of soil gas diffusivity for the formation and emission of nitrogenous gases in agricultural soils. However, emissions did not increase with the application rate of BD. This is probably due to an inhibitory effect of the high NH4+ content of BD on nitrification. Our results suggest a larger potential for N2O formation immediately following BD injection in the fine-textured clayey silt compared to the coarse loamy sand. By contrast, the loamy sand showed a higher potential for N2 production under anaerobic conditions. Our results suggest that short-term N losses of N2O and N2 after injection may be higher than probable losses of NH3 following surface application of BD.

  19. Oxygen vacancies: The origin of n -type conductivity in ZnO

    NASA Astrophysics Data System (ADS)

    Liu, Lishu; Mei, Zengxia; Tang, Aihua; Azarov, Alexander; Kuznetsov, Andrej; Xue, Qi-Kun; Du, Xiaolong

    2016-06-01

    Oxygen vacancy (VO) is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n -type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n -type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

  20. Hollow SnO2 nanospheres with oxygen vacancies entrapped by a N-doped graphene network as robust anode materials for lithium-ion batteries.

    PubMed

    Wu, Naiteng; Du, Wuzhou; Gao, Xu; Zhao, Liang; Liu, Guilong; Liu, Xianming; Wu, Hao; He, Yan-Bing

    2018-06-21

    The practical application of tin dioxide (SnO2) in lithium-ion batteries has been greatly hindered by its large volumetric expansion and low conductivity. Thus, a rational design of the size, geometry and the pore structure of SnO2-based nanomaterials is still a dire demand. To this end, herein we report an effective approach for engineering hollow-structured SnO2 nanospheres with adequate surface oxygen vacancies simultaneously wrapped by a nitrogen-doped graphene network (SnO2-x/N-rGO) through an electrostatic adsorption-induced self-assembly together with a thermal reduction process. The close electrostatic attraction achieved a tight and uniform combination of positively charged SnO2 nanospheres with negatively charged graphene oxide (GO), which can alleviate the aggregation and volume expansion of the entrapped SnO2 nanospheres. Subsequent thermal treatment not only ensures a significant reduction of the GO sheets accompanying nitrogen-doping, but also induces the generation of oxygen vacancies on the surface of the SnO2 hollow nanospheres, together building up a long-range and bicontinuous transfer channel for rapid electron and ion transport. Because of these structural merits, the as-built SnO2-x/N-rGO composite used as the anode material exhibits excellent robust cycling stability (∼912 mA h g-1 after 500 cycles at 0.5 A g-1 and 652 mA h g-1 after 200 cycles at 1 A g-1) and superior rate capability (309 mA h g-1 at 10 A g-1). This facile fabrication strategy may pave the way for the construction of high performance SnO2-based anode materials for potential application in advanced lithium-ion batteries.

  1. Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

    PubMed

    Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

    2014-02-03

    High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

  2. Theoretical study of negatively charged Fe(-)-(H2O)(n ≤ 6) clusters.

    PubMed

    Castro, Miguel

    2012-06-14

    Interactions of a singly negatively charged iron atom with water molecules, Fe(-)-(H(2)O)(n≤6), in the gas phase were studied by means of density functional theory. All-electron calculations were performed using the B3LYP functional and the 6-311++G(2d,2p) basis set for the Fe, O, and H atoms. In the lowest total energy states of Fe(-)-(H(2)O)(n), the metal-hydrogen bonding is stronger than the metal-oxygen one, producing low-symmetry structures because the water molecules are directly attached to the metal by basically one of their hydrogen atoms, whereas the other ones are involved in a network of hydrogen bonds, which together with the Fe(δ-)-H(δ+) bonding accounts for the nascent hydration of the Fe(-) anion. For Fe(-)-(H(2)O)(3≤n), three-, four-, five-, and six-membered rings of water molecules are bonded to the metal, which is located at the surface of the cluster in such a way as to reduce the repulsion with the oxygen atoms. Nevertheless, internal isomers appear also, lying less than 3 or 5 kcal/mol for n = 2-3 or n = 4-6. These results are in contrast with those of classical TM(+)-(H(2)O)(n) complexes, where the direct TM(+)-O bonding usually produces high symmetry structures with the metal defining the center of the complex. They show also that the Fe(-) anions, as the TM(+) ions, have great capability for the adsorption of water molecules, forming Fe(-)-(H(2)O)(n) structures stabilized by Fe(δ-)-H(δ+) and H-bond interactions.

  3. Influence of oxygen annealing on the dielectric properties of SrBi2(V0.1Nb0.9)2O9 ceramics

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Forbess, M.; Seraji, S.; Limmer, S.; Chou, T.; Cao, G. Z.

    2001-09-01

    The influences of O2 and N2 annealing on the dielectric properties of SrBi2(V0.1Nb0.9)2O9 (SBVN) ferroelectrics were studied. Ceramic samples were prepared by reaction sintering a powder mixture of constituent oxides at 950 °C for 2 h in air. Some samples were also subsequently annealed at 800 °C for 3 h in O2 or N2. With O2 annealing, the Curie point of the SBVN ferroelectrics changed from ~433 to ~438 °C and the peak dielectric constant increased from ~760 to ~1010 (at 100 kHz). However, no change in the Curie point was found with N2 annealing. Furthermore, O2 annealing was found to reduce significantly both the dielectric constant and loss tangent of the SBVN ferroelectrics at frequencies below 1000 Hz. XRD results revealed a small reduction in the lattice constants with O2 annealing, but no appreciable change with N2 annealing. In addition, no detectable change in the microstructure of the SBVN samples was found with annealing. These results imply that some V4+ ions, which are compensated by the formation of oxygen vacancies, existed in the SBVN ferroelectrics prior to O2 annealing. V4+ ions were oxidized to V5+ with O2 annealing, which resulted in improved dielectric properties.

  4. Impact of oxygen plasma postoxidation process on Al2O3/n-In0.53Ga0.47As metal-oxide-semiconductor capacitors

    NASA Astrophysics Data System (ADS)

    Lechaux, Y.; Fadjie-Djomkam, A. B.; Bollaert, S.; Wichmann, N.

    2016-09-01

    Capacitance-voltage (C-V) measurements and x-ray photoelectron spectroscopy (XPS) analysis were performed in order to investigate the effect of a oxygen (O2) plasma after oxide deposition on the Al2O3/n-In0.53Ga0.47As metal-oxide-semiconductor structure passivated with ammonia NH4OH solution. From C-V measurements, an improvement of charge control is observed using the O2 plasma postoxidation process on In0.53Ga0.47As, while the minimum of interface trap density remains at a good value lower than 1 × 1012 cm-2 eV-1. From XPS measurements, we found that NH4OH passivation removes drastically the Ga and As native oxides on the In0.53Ga0.47As surface and the O2 plasma postoxidation process enables the reduction of interface re-oxidation after post deposition annealing (PDA) of the oxide. The advanced hypothesis is the formation of interfacial barrier between Al2O3 and In0.53Ga0.47As which prevents the diffusion of oxygen species into the semiconductor surface during PDA.

  5. Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

    PubMed

    Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

    2012-04-19

    The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

  6. (Carbonato-κ(2)O,O')bis-(5,5'-dimethyl-2,2'-bipyridyl-κ(2)N,N')cobalt(III) bromide trihydrate.

    PubMed

    Arun Kumar, Kannan; Meera, Parthsarathi; Amutha Selvi, Madhavan; Dayalan, Arunachalam

    2012-04-01

    In the title complex, [Co(CO(3))(C(12)H(12)N(2))(2)]Br·3H(2)O, the Co(III) cation has a distorted octa-hedral coordination environment. It is chelated by four N atoms of two different 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water mol-ecules are disordered and their H atoms were not located, there are typical O⋯O distances between 2.8 and 3.0 Å, indicating O-H⋯O hydrogen bonding. The crystal packing is consolidated by C-H⋯O and C-H⋯Br hydrogen bonds, as well as π-π stacking inter-actions between adjacent pyridine rings of the dmbpy ligands, with centroid-centroid distances of 3.694 (3) and 3.7053 (3) Å.

  7. N2O molecular tagging velocimetry

    NASA Astrophysics Data System (ADS)

    ElBaz, A. M.; Pitz, R. W.

    2012-03-01

    A new seeded velocity measurement technique, N2O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide "laughing gas" is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N2O to O(1D) that subsequently reacts with N2O to form NO. O2 fluorescence induced by the ArF laser "writes" the original position of the NO line. After a time delay, the shifted NO line is "read" by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N2O in air, ˜1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800-1200 ppm of NO for 190-750 K at 1 atm and 850-1000 ppm of NO for 0.25-1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N2O MTV method amenable to low- and high-speed air flow measurements. The N2O MTV technique is demonstrated in air jet to measure its velocity profile. The N2O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N2O with O(1D) from N2O photodissociation and thus does not depend on the bulk gas composition.

  8. Platinum catalytic effect on oxygen fugacity of CO 2H 2 gas mixtures measured with ZrO 2 oxygen sensor at 105 Pa from 1300 to 700°C

    NASA Astrophysics Data System (ADS)

    Miyamoto, M.; Mikouchi, T.

    1996-08-01

    The oxygen fugacity of CO 2H 2 gas mixtures were measured with a ZrO 2 oxygen sensor at high temperatures in a furnace. We confirmed that the oxygen fugacity values measured by the ZrO 2 cell are more reducing than those of the CO 2H 2 gas mixtures calculated by using JANAF data at temperatures below 1150°C as was previously reported by Huebner (1975). We successfully decreased the deviation of the measured oxygen-fugacity value from the calculated one down to temperature of 800°C by using a Pt catalyst. Our results suggest that the deviation is probably due to incomplete equilibration of the gases.

  9. A novel fuzzy-logic control strategy minimizing N2O emissions.

    PubMed

    Boiocchi, Riccardo; Gernaey, Krist V; Sin, Gürkan

    2017-10-15

    A novel control strategy for achieving low N 2 O emissions and low effluent NH 4 + concentration is here proposed. The control strategy uses the measurements of ammonium and nitrate concentrations in inlet and outlet of the aerobic zone of a wastewater treatment plant to calculate a ratio indicating the balance among the microbial groups. More specifically, the ratio will indicate if there is a complete nitrification. In case nitrification is not complete, the controller will adjust the aeration level of the plant in order to inhibit the production of N 2 O from AOB and HB denitrification. The controller was implemented using the fuzzy logic approach. It was comprehensively tested for different model structures and different sets of model parameters with regards to its ability of mitigating N 2 O emissions for future applications in real wastewater treatment plants. It is concluded that the control strategy is useful for those plants having AOB denitrification as the main N 2 O producing process. However, in treatment plants having incomplete NH 2 OH oxidation as the main N 2 O producing pathway, a cascade controller configuration adapting the oxygen supply to respect only the effluent ammonium concentration limits was found to be more effective to ensure low N 2 O emissions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Estimating N2O processes during grassland renewal and grassland conversion to maize cropping using N2O isotopocules

    NASA Astrophysics Data System (ADS)

    Buchen, Caroline; Well, Reinhard; Flessa, Heinz; Fuß, Roland; Helfrich, Mirjam; Lewicka-Szczebak, Dominika

    2017-04-01

    Grassland break-up due to grassland renewal and grassland conversion to cropland can lead to a flush of mineral nitrogen from decomposition of the old grass sward and the decomposition of soil organic matter. Moreover, increased carbon and nitrogen mineralisation can result in enhanced nitrous oxide (N2O) emissions. As N2O is known to be an important greenhouse gas and a major precursor for ozone depletion, its emissions need to be mitigated by adjusting agricultural management practices. Therefore, it is necessary to understand the N2O processes involved, as well as the contribution of N2O reduction to N2. Apart from the widely used 15N gas flux method, natural abundance isotopic analysis of the four most abundant isotopocules of N2O species is a promising alternative to assess N2O production pathways. We used stable isotope analyses of soil-emitted N2O (δ18ON2O, δ15NN2Obulk and δ15NN2OSP= intramolecular distribution of 15N within the linear N2O molecule) with an isotopocule mapping approach to simultaneously estimate the magnitude of N2O reduction to N2 and the fraction of N2O originating from the bacterial denitrification pathway or fungal denitrification and/or nitrification. This approach is based on endmember areas of isotopic values for the N2O produced from different sources reported in the literature. For this purpose, we calculated two main scenarios with different assumptions for N2O produced: N2O is reduced to N2 before residual N2O is mixed with N2O of various sources (Scenario a) and vice versa (Scenario b). Based on this, we applied seven different scenario variations, where we evaluated the range of possible values for the potential N2O production pathways (heterotrophic bacterial denitrification and/or nitrifier denitrification and fungal denitrification and/or nitrification). This was done by using a range of isotopic endmember values and assuming different fractionation factors of N2O reduction in order to find the most reliable scenario

  11. Oxygen miscibility gap and spin glass formation in the pyrochlore Lu{sub 2}Mo{sub 2}O{sub 7}

    SciTech Connect

    Clark, L.; Ritter, C.; Harrison, A.

    2013-07-15

    Rare earth (R) molybdate pyrochlores, R{sub 2}Mo{sub 2}O{sub 7}, are of interest as frustrated magnets. Polycrystalline samples of Lu{sub 2}Mo{sub 2}O{sub 7−x} prepared at 1600 °C display a coexistence of cubic pyrochlore phases. Rietveld fits to powder neutron diffraction data and chemical analyses show that the miscibility gap is between a stoichiometric x=0 and an oxygen-deficient x≈0.4 phase. Lu{sub 2}Mo{sub 2}O{sub 7} behaves as a spin glass material, with a divergence of field cooled and zero field cooled DC magnetic susceptibilities at a spin freezing temperature T{sub f}=16 K, that varies with frequency in AC measurements following a Vogel–Fulcher law.more » Lu{sub 2}Mo{sub 2}O{sub 6.6} is more highly frustrated spin glass and has T{sub f}=20 K. - Graphical abstract: The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system exhibits a miscibility gap between coexisting pyrochlore phases at 1600 °C. Neutron powder diffraction refinement and chemical analysis shows that the gap separates stoichiometric x=0 and oxygen-deficient x≈0.4 phases. Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content. - Highlights: • The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system has a miscibility gap between coexisting pyrochlore phases at 1600 °C. • Neutron powder diffraction shows that the gap separates x=0 and oxygen-deficient x≈0.4 phases. • Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content.« less

  12. Microhabitat Effects on N2O Emissions from Floodplain Soils under Controlled Conditions

    NASA Astrophysics Data System (ADS)

    Ley, Martin; Lehmann, Moritz; Niklaus, Pascal; Frey, Beat; Kuhn, Thomas; Luster, Jörg

    2015-04-01

    Semi-terrestrial soils such as floodplain soils are considered to be potential hotspots of nitrous oxide (N2O) emissions. The quantitative assessment of N2O release from these hot spots under field conditions, and of the microbial pathways that underlie net N2O production (ammonium oxidation, nitrifier-denitrification, and denitrification) is challenging in the environment because of the high spatial and temporal variability. The production and consumption of N2O appears to be linked to the presence or absence of micro-niches, providing specific conditions that may be favorable to either of the microbial pathways that produce or consume N2O. The availability of oxygen, reactive organic carbon, and dissolved nitrogen substrates likely play key roles with regards to the net production of N2O. Previous field studies demonstrated, for example, that flooding can trigger "hot moments" of enhanced N2O emission through a close coupling of niches with high and low oxygen availabilities. Such microhabitat effects likely depend on soil aggregate formation, plant soil interactions in the rhizosphere and the degradation of organic matter accumulations. In order to assess how these factors can modulate N2O production and consumption under simulated flooding/drying conditions, we have set up a mesocosm experiment with model soils comprising various mixtures of N-rich floodplain soil aggregates (4000 - 250 µm representing large aggregates, or <250 µm representing small aggregates) and inert matrix material (glass beads of 150 - 250 µm size, or quartz sand of 2000 - 3200 µm size, respectively). Soils containing the different aggregate size groups were either planted with willow (Salix viminalis L.), mixed with leaf litter or left untreated. At several time points before, during and after a simulated flood event, we measure the net efflux rate of N2O. In addition, soil water content, redox potential as well as carbon and nitrogen substrate availability are monitored. In order to

  13. Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

    PubMed

    Padilha, A C M; Raebiger, H; Rocha, A R; Dalpian, G M

    2016-07-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

  14. Photocatalytic decomposition of N2O over TiO2/g-C3N4 photocatalysts heterojunction

    NASA Astrophysics Data System (ADS)

    Kočí, K.; Reli, M.; Troppová, I.; Šihor, M.; Kupková, J.; Kustrowski, P.; Praus, P.

    2017-02-01

    TiO2/g-C3N4 photocatalysts with the various TiO2/g-C3N4 weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO2 was prepared by thermal hydrolysis and pure g-C3N4 was prepared from commercial melamine by thermal annealing at 620 °C. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, Raman spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, photoelectrochemical measurements and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic decomposition of nitrous oxide under UVC (λ = 254 nm), UVA (λ = 365 nm) and Vis (λ > 400 nm) irradiation. The TiO2/g-C3N4 nanocomposites showed moderate improvement compared to pure g-C3N4 but pure TiO2 proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO2/g-C3N4 (1:2) nanocomposite exhibited an increase compared to pure TiO2. Nevertheless, further increase of g-C3N4 amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO2 and g-C3N4 have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C3N4. This is probably due to the generation of heterojunction on the TiO2/g-C3N4 interface.

  15. Nano-sized TiO2 (nTiO2) induces metabolic perturbations in Physarum polycephalum macroplasmodium to counter oxidative stress under dark conditions.

    PubMed

    Zhang, Zhi; Liang, Zhi Cheng; Zhang, Jian Hua; Tian, Sheng Li; Le Qu, Jun; Tang, Jiao Ning; De Liu, Shi

    2018-06-15

    Nano-sized TiO 2 (nTiO 2 ) exerts an oxidative effect on cells upon exposure to solar or UV irradiation and ecotoxicity of the nTiO 2 is an urgent concern. Little information is available regarding the effect of TiO 2 on cells under dark conditions. Metabolomics is a unique approach to the discovery of biomarkers of nTiO 2 cytotoxicity, and leads to the identification of perturbed metabolic pathways and the mechanism underlying nTiO 2 toxicity. In the present study, gas chromatography mass spectrometry (GC/MS)-based metabolomics was performed to investigate the effect of nTiO 2 on sensitive cells (P. polycephalum macroplasmodium) under dark conditions. According to the multivariate pattern recognition analysis, at least 60 potential metabolic biomarkers related to sugar metabolism, amino acid metabolism, nucleotide metabolism, polyamine biosynthesis, and secondary metabolites pathways were significantly perturbed by nTiO 2 . Notably, many metabolic biomarkers and pathways were related to anti-oxidant mechanisms in the living organism, suggesting that nTiO 2 may induce oxidative stress, even under dark conditions. This speculation was further validated by the biochemical levels of reactive oxygen species (ROS), 8-hydroxy-2-deoxyguanosine (8-OHdG), and total soluble phenols (TSP). We inferred that the oxidative stress might be related to nTiO 2 -induced imbalance of cellular ROS. To the best of our knowledge, the present study is the first to investigate the nTiO 2 -induced metabolic perturbations in slime mold, provide a new perspective of the mechanism underlying nTiO 2 toxicity under dark conditions, and show that metabolomics can be employed as a rapid, reliable and powerful tool to investigate the interaction among organisms, the environment, and nanomaterials. Copyright © 2018 Elsevier Inc. All rights reserved.

  16. Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

    NASA Astrophysics Data System (ADS)

    Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

    2012-02-01

    We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

  17. Enhanced Intrinsic Catalytic Activity of λ-MnO2 by Electrochemical Tuning and Oxygen Vacancy Generation.

    PubMed

    Lee, Sanghan; Nam, Gyutae; Sun, Jie; Lee, Jang-Soo; Lee, Hyun-Wook; Chen, Wei; Cho, Jaephil; Cui, Yi

    2016-07-18

    Chemically prepared λ-MnO2 has not been intensively studied as a material for metal-air batteries, fuel cells, or supercapacitors because of their relatively poor electrochemical properties compared to α- and δ-MnO2 . Herein, through the electrochemical removal of lithium from LiMn2 O4 , highly crystalline λ-MnO2 was prepared as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The ORR activity of the material was further improved by introducing oxygen vacancies (OVs) that could be achieved by increasing the calcination temperature during LiMn2 O4 synthesis; a concentration of oxygen vacancies in LiMn2 O4 could be characterized by its voltage profile as the cathode in a lithiun-metal half-cell. λ-MnO2-z prepared with the highest OV exhibited the highest diffusion-limited ORR current (5.5 mA cm(-2) ) among a series of λ-MnO2-z electrocatalysts. Furthermore, the number of transferred electrons (n) involved in the ORR was >3.8, indicating a dominant quasi-4-electron pathway. Interestingly, the catalytic performances of the samples were not a function of their surface areas, and instead depended on the concentration of OVs, indicating enhancement in the intrinsic catalytic activity of λ-MnO2 by the generation of OVs. This study demonstrates that differences in the electrochemical behavior of λ-MnO2 depend on the preparation method and provides a mechanism for a unique catalytic behavior of cubic λ-MnO2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Generating Breathable Air Through Dissociation of N2O

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Frankie, Brian

    2006-01-01

    A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS

  19. Life on N2O: deciphering the ecophysiology of N2O respiring bacterial communities in a continuous culture.

    PubMed

    Conthe, Monica; Wittorf, Lea; Kuenen, J Gijs; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Hallin, Sara

    2018-04-01

    Reduction of the greenhouse gas N 2 O to N 2 is a trait among denitrifying and non-denitrifying microorganisms having an N 2 O reductase, encoded by nosZ. The nosZ phylogeny has two major clades, I and II, and physiological differences among organisms within the clades may affect N 2 O emissions from ecosystems. To increase our understanding of the ecophysiology of N 2 O reducers, we determined the thermodynamic growth efficiency of N 2 O reduction and the selection of N 2 O reducers under N 2 O- or acetate-limiting conditions in a continuous culture enriched from a natural community with N 2 O as electron acceptor and acetate as electron donor. The biomass yields were higher during N 2 O limitation, irrespective of dilution rate and community composition. The former was corroborated in a continuous culture of Pseudomonas stutzeri and was potentially due to cytotoxic effects of surplus N 2 O. Denitrifiers were favored over non-denitrifying N 2 O reducers under all conditions and Proteobacteria harboring clade I nosZ dominated. The abundance of nosZ clade II increased when allowing for lower growth rates, but bacteria with nosZ clade I had a higher affinity for N 2 O, as defined by μ max /K s . Thus, the specific growth rate is likely a key factor determining the composition of communities living on N 2 O respiration under growth-limited conditions.

  20. O2(a1Δ) Quenching In The O/O2/O3 System

    NASA Astrophysics Data System (ADS)

    Azyazov, V. N.; Mikheyev, P. A.; Postell, D.; Heaven, M. C.

    2010-10-01

    The development of discharge singlet oxygen generators (DSOG's) that can operate at high pressures is required for the power scaling of the discharge oxygen iodine laser. In order to achieve efficient high-pressure DSOG operation it is important to understand the mechanisms by which singlet oxygen (O2(a1Δ)) is quenched in these devices. It has been proposed that three-body deactivation processes of the type O2(a1Δ)+O+M→2O2+M provide significant energy loss channels. To further explore these reactions the physical and reactive quenching of O2(a1Δ) in O(3P)/O2/O3/CO2/He/Ar mixtures has been investigated. Oxygen atoms and singlet oxygen molecules were produced by the 248 nm laser photolysis of ozone. The kinetics of O2(a1Δ) quenching were followed by observing the 1268 nm fluorescence of the O2a1Δ-X3∑ transition. Fast quenching of O2(a1Δ) in the presence of oxygen atoms and molecules was observed. The mechanism of the process has been examined using kinetic models, which indicate that quenching by vibrationally excited ozone is the dominant reaction.

  1. Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

    PubMed

    Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

    2005-08-31

    A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

  2. A composite material with CeO2-ZrO2 nanocrystallines embedded in SiO2 matrices and its enhanced thermal stability and oxygen storage capacity

    NASA Astrophysics Data System (ADS)

    Yang, Runnong; Liu, Yumei; Yu, Lin; Zhao, Xiangyun; Yang, Xiaobo; Sun, Ming; Luo, Junyin; Fan, Qun; Xiao, Jianming; Zhao, Yuzhong

    2018-06-01

    A simple hydrothermal procedure is introduced, which leads to the successful synthesis of a new composite material with fine CeO2-ZrO2 nanocrystallites embedded in amorphous and porous SiO2 matrices. The composite material possesses an extraordinary high thermal stability. After being calcined at 1000 °C, it retains CeO2-ZrO2 nanocrystallites of the size around 5 nm, a BET-specific surface area of 165 m2/g, and an oxygen storage capacity of 468 μmol/g. No phase segregation for CeO2-ZrO2 nanocrystallites is detected and the SiO2 matrices remain not crystallized. The composite material shows a great potential as a support of three-way catalyst, as evidenced in catalytic tests with supported Pt.

  3. Why O2 is required by complex life on habitable planets and the concept of planetary "oxygenation time".

    PubMed

    Catling, David C; Glein, Christopher R; Zahnle, Kevin J; McKay, Christopher P

    2005-06-01

    Life is constructed from a limited toolkit: the Periodic Table. The reduction of oxygen provides the largest free energy release per electron transfer, except for the reduction of fluorine and chlorine. However, the bonding of O2 ensures that it is sufficiently stable to accumulate in a planetary atmosphere, whereas the more weakly bonded halogen gases are far too reactive ever to achieve significant abundance. Consequently, an atmosphere rich in O2 provides the largest feasible energy source. This universal uniqueness suggests that abundant O2 is necessary for the high-energy demands of complex life anywhere, i.e., for actively mobile organisms of approximately 10(-1)-10(0) m size scale with specialized, differentiated anatomy comparable to advanced metazoans. On Earth, aerobic metabolism provides about an order of magnitude more energy for a given intake of food than anaerobic metabolism. As a result, anaerobes do not grow beyond the complexity of uniseriate filaments of cells because of prohibitively low growth efficiencies in a food chain. The biomass cumulative number density, n, at a particular mass, m, scales as n (> m) proportional to m(-1) for aquatic aerobes, and we show that for anaerobes the predicted scaling is n proportional to m (-1.5), close to a growth-limited threshold. Even with aerobic metabolism, the partial pressure of atmospheric O2 (P(O2)) must exceed approximately 10(3) Pa to allow organisms that rely on O2 diffusion to evolve to a size approximately 10(3) m x P(O2) in the range approximately 10(3)-10(4) Pa is needed to exceed the threshold of approximately 10(2) m size for complex life with circulatory physiology. In terrestrial life, O(2) also facilitates hundreds of metabolic pathways, including those that make specialized structural molecules found only in animals. The time scale to reach P(O(2)) approximately 10(4) Pa, or "oxygenation time," was long on the Earth (approximately 3.9 billion years), within almost a factor of 2 of the Sun

  4. Mechanisms of nitrous oxide (N2 O) formation and reduction in denitrifying biofilms.

    PubMed

    Sabba, Fabrizio; Picioreanu, Cristian; Nerenberg, Robert

    2017-12-01

    Nitrous oxide (N 2 O) is a potent greenhouse gas that can be formed in wastewater treatment processes by ammonium oxidizing and denitrifying microorganisms. While N 2 O emissions from suspended growth systems have been extensively studied, and some recent studies have addressed emissions from nitrifying biofilms, much less is known about N 2 O emissions from denitrifying biofilm processes. This research used modeling to evaluate the mechanisms of N 2 O formation and reduction in denitrifying biofilms. The kinetic model included formation and consumption of key denitrification species, including nitrate (NO3-), nitrite (NO2-), nitric oxide (NO), and N 2 O. The model showed that, in presence of excess of electron donor, denitrifying biofilms have two distinct layers of activity: an outer layer where there is net production of N 2 O and an inner layer where there is net consumption. The presence of oxygen (O 2 ) had an important effect on N 2 O emission from suspended growth systems, but a smaller effect on biofilm systems. The effects of NO3- and O 2 differed significantly based on the biofilm thickness. Overall, the effects of biofilm thickness and bulk substrate concentrations on N 2 O emissions are complex and not always intuitive. A key mechanism for denitrifying biofilms is the diffusion of N 2 O and other intermediates from one zone of the biofilm to another. This leads to zones of N 2 O formation or consumption transformations that would not exist in suspended growth systems. © 2017 Wiley Periodicals, Inc.

  5. Microbial CH4 and N2O Consumption in Acidic Wetlands

    PubMed Central

    Kolb, Steffen; Horn, Marcus A.

    2012-01-01

    Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

  6. P-type ZnO:N Films Prepared by Thermal Oxidation of Zn3N2

    NASA Astrophysics Data System (ADS)

    Zhang, Bin; Li, Min; Wang, Jian-Zhong; Shi, Li-Qun

    2013-02-01

    We prepare p-type ZnO:N films by annealing Zn3N2 films in oxygen over a range of temperatures. The prepared films are characterized by various techniques, such as Rutherford backscattering spectroscopy, x-ray diffraction, x-ray photoemission spectroscopy, the Hall effect and photoluminescence spectra. The results show that the Zn3N2 films start to transform to ZnO at 300°C and the N content decreases with an increase in annealing temperature. N has two local chemical states: zinc oxynitride (ZnO1-xNx) and substitutional NO in O-rich local environments (α -NO). The conduction type changes from n-type to p-type upon oxidation at 400-600°C, indicating that N is an effective acceptor in the ZnO film. The photoluminescence spectra show the UV emission and defect-related emissions of ZnO:N films. The mechanism and efficiency of p-type doping are briefly discussed.

  7. Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions.

    PubMed

    Wunderlin, Pascal; Mohn, Joachim; Joss, Adriano; Emmenegger, Lukas; Siegrist, Hansruedi

    2012-03-15

    Nitrous oxide (N2O) is an important greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment, microbial processes such as autotrophic nitrification and heterotrophic denitrification have been identified as major sources; however, the underlying pathways remain unclear. In this study, the mechanisms of N2O production were investigated in a laboratory batch-scale system with activated sludge for treating municipal wastewater. This relatively complex mixed population system is well representative for full-scale activated sludge treatment under nitrifying and denitrifying conditions. Under aerobic conditions, the addition of nitrite resulted in strongly nitrite-dependent N2O production, mainly by nitrifier denitrification of ammonia-oxidizing bacteria (AOB). Furthermore, N2O is produced via hydroxylamine oxidation, as has been shown by the addition of hydroxylamine. In both sets of experiments, N2O production was highest at the beginning of the experiment, then decreased continuously and ceased when the substrate (nitrite, hydroxylamine) had been completely consumed. In ammonia oxidation experiments, N2O peaked at the beginning of the experiment when the nitrite concentration was lowest. This indicates that N2O production via hydroxylamine oxidation is favored at high ammonia and low nitrite concentrations, and in combination with a high metabolic activity of ammonia-oxidizing bacteria (at 2 to 3 mgO2/l); the contribution of nitrifier denitrification by AOB increased at higher nitrite and lower ammonia concentrations towards the end of the experiment. Under anoxic conditions, nitrate reducing experiments confirmed that N2O emission is low under optimal growth conditions for heterotrophic denitrifiers (e.g. no oxygen input and no limitation of readily biodegradable organic carbon). However, N2O and nitric oxide (NO) production rates increased significantly in the presence of nitrite or low dissolved oxygen concentrations. Copyright

  8. Promoting formation of noncrystalline Li2O2 in the Li-O2 battery with RuO2 nanoparticles.

    PubMed

    Yilmaz, Eda; Yogi, Chihiro; Yamanaka, Keisuke; Ohta, Toshiaki; Byon, Hye Ryung

    2013-10-09

    Low electrical efficiency for the lithium-oxygen (Li-O2) electrochemical reaction is one of the most significant challenges in current nonaqueous Li-O2 batteries. Here we present ruthenium oxide nanoparticles (RuO2 NPs) dispersed on multiwalled carbon nanotubes (CNTs) as a cathode, which dramatically increase the electrical efficiency up to 73%. We demonstrate that the RuO2 NPs contribute to the formation of poorly crystalline lithium peroxide (Li2O2) that is coated over the CNT with large contact area during oxygen reduction reaction (ORR). This unique Li2O2 structure can be smoothly decomposed at low potential upon oxygen evolution reaction (OER) by avoiding the energy loss associated with the decomposition of the more typical Li2O2 structure with a large size, small CNT contact area, and insulating crystals.

  9. Syntheses and multi-NMR study of fac- and mer-OsO(3)F(2)(NCCH(3)) and the X-ray crystal structure (n = 2) and Raman spectrum (n = 0) of fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN.

    PubMed

    Hughes, Michael J; Gerken, Michael; Mercier, Hélène P A; Schrobilgen, Gary J

    2010-06-07

    Dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in CH(3)CN solvent at -40 degrees C followed by solvent removal under vacuum at -40 degrees C yielded fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN (n >/= 2). Continued pumping at -40 degrees C with removal of uncoordinated CH(3)CN yielded fac-OsO(3)F(2)(NCCH(3)). Both fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN and fac-OsO(3)F(2)(NCCH(3)) are yellow-brown solids and were characterized by low-temperature (-150 degrees C) Raman spectroscopy. The crystal structure (-173 degrees C) of fac-OsO(3)F(2)(NCCH(3)).2CH(3)CN consists of two co-crystallized CH(3)CN molecules and a pseudo-octahedral OsO(3)F(2).NCCH(3) molecule in which three oxygen atoms are in a facial arrangement and CH(3)CN is coordinated trans to an oxygen atom in an end-on fashion. The Os---N bond length (2.205(3) A) is among the shortest M---N adduct bonds observed for a d(0) transition metal oxide fluoride. The (19)F NMR spectrum of (OsO(3)F(2))(infinity) in CH(3)CN solvent (-40 degrees C) is a singlet (-99.6 ppm) corresponding to fac-OsO(3)F(2)(NCCH(3)). The (1)H, (15)N, (13)C, and (19)F NMR spectra of (15)N-enriched OsO(3)F(2)(NCCH(3)) were recorded in SO(2)ClF solvent (-84 degrees C). Nitrogen-15 enrichment resulted in splitting of the (19)F resonance of fac-OsO(3)F(2)((15)NCCH(3)) into a doublet ((2)J((15)N-(19)F), 21 Hz). In addition, a doublet of doublets ((2)J((19)F(ax)-(19)F(eq)), 134 Hz; (2)J((15)N-(19)F(eq)), 18 Hz) and a doublet ((2)J((19)F(ax)-(19)F(eq)), 134 Hz) were observed in the (19)F NMR spectrum that have been assigned to mer-OsO(3)F(2)((15)NCCH(3)); however, coupling of (15)N to the axial fluorine-on-osmium environment could not be resolved. The nitrogen atom of CH(3)CN is coordinated trans to a fluorine ligand in the mer-isomer. Quantum-chemical calculations at the SVWN and B3LYP levels of theory were used to calculate the energy-minimized gas-phase geometries, vibrational frequencies of fac- and mer-OsO(3)F(2)(NCCH(3)) and of CH(3)CN. The

  10. Octa-akis(4-amino-pyridine)-1κN,2κN-aqua-2κO-μ-carbonato-1:2κO,O':O''-dinickel(II) dichloride penta-hydrate.

    PubMed

    Fun, Hoong-Kun; Sinthiya, A; Jebas, Samuel Robinson; Ravindran Durai Nayagam, B; Alfred Cecil Raj, S

    2008-10-18

    In the title compound, [Ni(2)(CO(3))(C(5)H(6)N(2))(8)(H(2)O)]Cl(2)·5H(2)O, one of the the Ni(II) ions is six-coordinated in a distorted octa-hedral geometry, with the equatorial plane defined by four pyridine N atoms from four amino-pyridine ligands, the axial positions being occupied by one water O and a carbonate O atom. The other Ni(II) ion is also six-coordinated, by four other pyridine N atoms from four other amino-pyridine ligands and two carbonate O atoms to complete a distorted octa-hedral geometry. In the crystal structure, mol-ecules are linked into an infinite three-dimensional network by O-H⋯O, N-H⋯Cl, N-H⋯O, O-H⋯N, C-H⋯O, C-H⋯N and C/N-H⋯π inter-actions involving the pyridine rings.

  11. Spatially-controlled NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

    2018-07-01

    Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

  12. Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

    PubMed

    Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

    2018-07-13

    Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo 2 O 4 @MnO 2 core-shell nanoarray with hollow NiCo 2 O 4 Cores and MnO 2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo 2 O 4 and MnO 2 compositions.

  13. Characterization of the N2O isotopic composition (15N, 18O and N2O isotopomers) emitted from incubated Amazon forest soils. Implications for the global N2O isotope budget

    NASA Astrophysics Data System (ADS)

    Pérez, T.; García, D.; Trumbore, S.; Tyler, S.; de Camargo, P.; Moreira, M.; Piccolo, M.; Park, S.; Boering, K.; Cerri, C.

    2003-04-01

    Tropical rain forest soils are the largest natural source of N2O to the atmosphere. Uncertainty in the signature of this source limits the utility of isotopes in constraining the global N2O budget. Differentiating the relative contribution of nitrification and denitrification to the emitted N2O using stable isotopes has been difficult due to the lack of enrichment factors values for each process measured in situ. We have devised a method for measuring enrichment factors using soil incubation experiments. We selected three Amazon rain forest soils: (1) Clay and (2) Sandy from Santarem, Pará State, and (3) Sandy from Nova Vida Farm, Rondonia State, Brazil. The enrichment factor values for nitrification and denitrification are: -97.8±4.2 and -9.9±3.8 per mil for clay Santarem soil, -86.8±4.3 and -45.2±4.5 per mil for sandy Santarem soil and-112.6±3.8 and -10.4±3.5 per mil for Nova Vida Farm soils, respectively. Our results show that enrichment factors for both processes differ with soil texture and location. The enrichment factors for nitrification are significantly smaller than the range reported in the literature (-66 to -42 per mil). Also, the enrichment factors for the Santarem soils (clay and sandy) differ significantly implying that soil texture (which will affect the soil air filled pore space at a given water content) is influencing the bacteria isotopic discrimination. However, the enrichment factors for the Santarem clay sand Nova Vida sandy soils do not differ by much. This suggests that the enrichment factors not only can be affected by texture but also by the microbial fauna present in these soils. We also determined the measurement of the N2O positional dependence. N2O is a linear molecule with two nitrogen atoms. The 15N isotope can be located in either the central nitrogen (alpha position) or in the terminal nitrogen (beta position). The isotopomer site preference (15N alpha - 15N beta) can be used to differentiate processes of production and

  14. N and O isotope (δ15 Nα , δ15 Nβ , δ18 O, δ17 O) analyses of dissolved NO3- and NO2- by the Cd-azide reduction method and N2 O laser spectrometry.

    PubMed

    Wassenaar, Leonard I; Douence, Cedric; Altabet, Mark A; Aggarwal, Pradeep K

    2018-02-15

    The nitrogen and oxygen (δ 15 N, δ 18 O, δ 17 O) isotopic compositions of NO 3 - and NO 2 - are important tracers of nutrient dynamics in soil, rain, groundwater and oceans. The Cd-azide method was used to convert NO 3 - or NO 2 - to N 2 O for N and triple-O isotopic analyses by N 2 O laser spectrometry. A protocol for laser-based headspace isotope analyses was compared with isotope ratio mass spectrometry. Lasers provide the ability to directly measure 17 O anomalies which can help discern atmospheric N sources. δ 15 N, δ 18 O and δ 17 O values were measured on N/O stable isotopic reference materials (IAEA, USGS) by conversion to N 2 O using the Cd-azide method and headspace N 2 O laser spectrometry. A 15 N tracer test assessed the position-specific routing of N to the α or β positions in the N 2 O molecule. A data processing algorithm was used to correct for isotopic dependencies on N 2 O concentration, cavity pressure and water content. NO 3 - /NO 2 - nitrogen is routed to the 15 N α position of N 2 O in the azide reaction; hence the δ 15 N α value should be used for N 2 O laser spectrometry results. With corrections for cavity pressure, N 2 O concentration and water content, the δ 15 N α AIR , δ 18 O VSMOW and δ 17 O VSMOW values (‰) of international reference materials were +4.8 ± 0.1, +25.9 ± 0.3, +12.7 ± 0.2 (IAEA NO 3 ), -1.7 ± 0.1, -26.8 ± 0.8, -14.4 ± 1.1 (USGS34) and +2.6 ± 0.1, +57.6 ± 1.2, +51.2 ± 2.0 (USGS35), in agreement with their values and with the isotope ratio mass spectrometry results. The 17 O excess for USGS35 was +21.2 ± 9‰, in good agreement with previous results. The Cd-azide method yielded excellent results for routine determination of δ 15 N, δ 18 O and δ 17 O values (and the 17 O excess) of nitrate or nitrite by laser spectrometry. Disadvantages are the toxicity of Cd-azide chemicals and the lack of automated sampling devices for N 2 O laser spectrometers. The 15 N-enriched tracer test revealed potential

  15. Bis(2,2'-bipyridyl-κN,N')(carbonato-κO,O')cobalt(III) bromide trihydrate.

    PubMed

    Ma, Peng-Tao; Wang, Yu-Xia; Zhang, Guo-Qian; Li, Ming-Xue

    2007-12-06

    The title complex, [Co(CO(3))(C(10)H(8)N(2))(2)]Br·3H(2)O, is isostructural with the chloride analogue. The six-coordinated octahedral [Co(2,2'-bipy)(2)CO(3)](+) cation (2,2'-bipy is 2,2'-bipyrid-yl), bromide ion and water mol-ecules are linked together via O-H⋯Br and O-H⋯O hydrogen bonds, generating a one-dimensional chain.

  16. Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

    PubMed

    Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

    2011-05-01

    Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

  17. Oxygen vacancy and hole conduction in amorphous TiO2.

    PubMed

    Pham, Hieu H; Wang, Lin-Wang

    2015-01-07

    The amorphous titanium dioxide (a-TiO2) has drawn attention recently due to the finding that it holds promise for coating conventional photoelectrodes for corrosion protection while still allowing the holes to transport to the surface. The mechanism of hole conductivity at a level much higher than the edge of the valence band is still a mystery. In this work, an amorphous TiO2 model is obtained from molecular dynamics employing the "melt-and-quench" technique. The electronic properties, polaronic states and the hole conduction mechanism in amorphous structure were investigated by means of density functional theory with Hubbard's energy correction (DFT + U) and compared to those in crystalline (rutile) TiO2. The formation energy of the oxygen vacancy was found to reduce significantly (by a few eV) upon amorphization. Our theoretical study suggested that the oxygen vacancies and their defect states provide hopping channels, which are comparable to experimental observations and could be responsible for hole conduction in the "leaky" TiO2 recently discovered for the photochemical water-splitting applications.

  18. Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

    NASA Technical Reports Server (NTRS)

    Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

    1996-01-01

    Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

  19. Isotopomeric characterization of N2O produced, consumed, and emitted by automobiles.

    PubMed

    Toyoda, Sakae; Yamamoto, Sei-ichiro; Arai, Shinji; Nara, Hideki; Yoshida, Naohiro; Kashiwakura, Kiriko; Akiyama, Ken-ichi

    2008-01-01

    Fossil fuel combustion is the second largest anthropogenic source of nitrous oxide (N2O) after agriculture. The estimated global N2O flux from combustion sources, as well as from other sources, still has a large uncertainty. Herein, we characterize automobile sources using N2O isotopomer ratios (nitrogen and oxygen isotope ratios and intramolecular site preference of 15N, SP) to assess their contributions to total global sources and to deconvolute complex production/consumption processes during combustion and subsequent catalytic treatments of exhaust. Car exhaust gases were sampled under running and idling state, and N2O isotopomer ratios were measured by mass spectrometry. The N2O directly emitted from an engine of a vehicle running at constant velocity had almost constant isotopomer ratios (delta15Nbulk = -28.7 +/- 1.2 per thousand, delta18O = 28.6 +/- 3.3 per thousand, and SP = 4.2 +/- 0.8 per thousand) irrespective of the velocity. After passing through catalytic converters, the isotopomer ratios showed an increase which varied with the temperature and the aging of the catalysts. The increase suggests that both production and consumption of N2O occur on the catalyst and that their rates can be comparable. It was noticed that in the idling state, the N2O emitted from a brand new car has higher isotopomer ratios than that from used cars, which indicate that technical improvements in catalytic converters can reduce the N2O from mobile combustion sources. On average, the isotopomeric signatures of N2O finally emitted from automobiles are not sensitive to running/idling states or to aging of the catalysts. Characteristic average isotopomer ratios of N2O from automobile sources are estimated at -4.9 +/- 8.2 per thousand, 43.5 +/- 13.9 per thousand, and 12.2 +/- 9.1 per thousand for delta15Nbulk, delta18O, and SP, respectively.

  20. Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications

    NASA Astrophysics Data System (ADS)

    Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi; Zhang, Nan; Xu, Yi-Jun

    2013-04-01

    Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the

  1. Spatial variability in groundwater N2 and N2O in the San Joaquin River

    NASA Astrophysics Data System (ADS)

    Hinshaw, S.; Dahlgren, R. A.

    2010-12-01

    The San Joaquin River is surrounded by nearly 2 million acres of irrigated agricultural land. Groundwater inputs from agricultural areas can have severe negative effects on water quality with high nitrate concentrations being a major concern. Riparian zones are important ecological habitats that mitigate nitrogen loading from groundwater discharging into rivers primarily by denitrification. Denitrification is a permanent removal of nitrate by anaerobic microbial communities via the reduction to NO, N2O and N2. However, previous studies have shown that these areas can be source of N2O emissions. Although removal of nitrate through denitrification is advantageous from a water quality perspective, N2O is a harmful greenhouse gas. This study aimed to investigate nitrogen dynamics and dissolved N gases in surface and groundwater of the riparian zones of the San Joaquin River. Excess N2 and N2O concentrations were measured in surface and groundwater at 4 locations along a 33 km reach of the river. Samples were collected within bank sediments and 5 transect points across the river at depth intervals between 2-3 cm and 150 cm. Dissolved N2 and Ar were measured by membrane inlet mass spectrometry and used to estimate excess dissolved N2 concentrations. Dissolved N2O concentrations were measured using the headspace equilibrium technique and analyzed with a gas chromatograph. Both N2 uptake and excess N2 were present, ranging from -3.40 to 8.65 N2 mg/L with a median concentration of 1.20 N2 mg/L. Significantly lower concentrations of N2O were present ranging from 0.0 to 0.12 N2O mg/L. Deeper groundwater sites had significantly higher N2 and N2O concentrations coinciding with decreased O2. The presence of excess N2 and low N2O concentrations documents the importance of denitrification in removing nitrate from groundwater. Further investigation will examine N2O emissions from riparian soils and benthic sediments using static chambers and focus on nitrogen pathways that

  2. Giant thermally-enhanced electrostriction and polar surface phase in L a2M o2O9 oxygen ion conductors

    NASA Astrophysics Data System (ADS)

    Li, Qian; Lu, Teng; Schiemer, Jason; Laanait, Nouamane; Balke, Nina; Zhang, Zhan; Ren, Yang; Carpenter, Michael A.; Wen, Haidan; Li, Jiangyu; Kalinin, Sergei V.; Liu, Yun

    2018-04-01

    Ferroelectrics possess spontaneous electric polarization at macroscopic scales which nonetheless imposes strict limitations on the material classes. Recent discoveries of untraditional symmetry-breaking phenomena in reduced material dimensions have indicated feasibilities to extend polar properties to broader types of materials, potentially opening up the freedom for designing materials with hybrid functionalities. Here, we report the unusual electromechanical properties of L a2M o2O9 (LAMOX) oxygen ion conductors, systematically investigated at both bulk and surface length levels. We first observed giant electrostriction effects in L a2M o2O9 bulk ceramics that are thermally enhanced in concert with their low-energy oxygen-vacancy hopping dynamics. Moreover, while no clear bulk polarization was detected, the surface phases of LAMOX were found to be manifestly polar, likely originating from the coupling between the intrinsic structural flexibilities with strain gradients (i.e., flexoelectricity) and/or chemical heterogeneities present in the materials. These findings identify L a2M o2O9 as a promising electromechanical material system and suggest that the flexible structural and chemical configurations in ionically active materials could enable fundamentally different venues to accommodate electric polarization.

  3. Interplay of tumor vascular oxygenation and pO2 in tumors using NIRS and needle electrode

    NASA Astrophysics Data System (ADS)

    Kim, Jae Gwan; Song, Yulin; Zhao, Dawen; Constantinescu, Anca; Mason, Ralph P.; Liu, Hanli

    2001-06-01

    The effective measurement of dynamic changes of blood and tissue oxygenation of tumors could be valuable for optimizing tumor treatment plans. For this study, a near- infrared spectroscopy system and pO2 needle electrode were used to measure simultaneously changes in total hemoglobin concentration ([Hb]total), oxygenated hemoglobin concentration ([HbO2[) and local oxygen tension (pO2) in the vascular bed of prostate tumors implanted in rats in response to respiratory challenge. The inhaled gas was alternated between air and carbogen (95% oxygen, 5% CO2). Significant changes in tumor vascular oxygenation were observed with an apparent threshold for variation in [HbO2]/[HbO2]max. For comparison, a phantom study was undertaken with 1% intralipid solution and blood. The slope of [HbO2]/[HbO2[max vs. pO2 in the phantom was ten times larger than in the tumor indicating that tumor cells are relatively resistant to oxygenation. This study demonstrates that the NIR technology can provide an efficient, real-time, non-invasive approach to monitoring tumor physiology and is compatible with additional techniques.

  4. KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

    PubMed

    Schlueter, John A; Geiser, Urs; Funk, Kylee A

    2008-02-01

    The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

  5. Characteristics of surface-wave plasma with air-simulated N2 O2 gas mixture for low-temperature sterilization

    NASA Astrophysics Data System (ADS)

    Xu, L.; Nonaka, H.; Zhou, H. Y.; Ogino, A.; Nagata, T.; Koide, Y.; Nanko, S.; Kurawaki, I.; Nagatsu, M.

    2007-02-01

    Sterilization experiments using low-pressure air discharge plasma sustained by the 2.45 GHz surface-wave have been carried out. Geobacillus stearothermoplilus spores having a population of 3.0 × 106 were sterilized for only 3 min using air-simulated N2-O2 mixture gas discharge plasma, faster than the cases of pure O2 or pure N2 discharge plasmas. From the SEM analysis of plasma-irradiated spores and optical emission spectroscopy measurements of the plasmas, it has been found that the possible sterilization mechanisms of air-simulated plasma are the chemical etching effect due to the oxygen radicals and UV emission from the N2 molecules and NO radicals in the wavelength range 200-400 nm. Experiment suggested that UV emission in the wavelength range less than 200 nm might not be significant in the sterilization. The UV intensity at 237.0 nm originated from the NO γ system (A 2Σ+ → X 2Π) in N2-O2 plasma as a function of the O2 percentage added to N2-O2 mixture gas has been investigated. It achieved its maximum value when the O2 percentage was roughly 10-20%. This result suggests that air can be used as a discharge gas for sterilization, and indeed we have confirmed a rapid sterilization with the actual air discharge at a sample temperature of less than 65 °C.

  6. Kinetic modeling of the formation and growth of inorganic nano-particles during pulverized coal char combustion in O 2/N 2 and O 2/CO 2 atmospheres

    DOE PAGES

    Shaddix, Christopher R.; Niu, Yanqing; Hui, Shi'en; ...

    2016-08-01

    In this formation of nano-particles during coal char combustion, the vaporization of inorganic components in char and the subsequent homogeneous particle nucleation, heterogeneous condensation, coagulation, and coalescence play decisive roles. Furthermore, conventional measurements cannot provide detailed information on the dynamics of nano-particle formation and evolution, In this study, a sophisticated intrinsic char kinetics model that considers ash effects (including ash film formation, ash dilution, and ash vaporization acting in tandem), both oxidation and gasification by CO 2 and H 2O, homogeneous particle nucleation, heterogeneous vapor condensation, coagulation, and and coalescence mechanisms is developed and used to compare the temporal evolutionmore » of the number and size of nano-particles during coal char particle combustion as a function of char particle size, ash content, and oxygen content in O 2/N 2 and O 2/CO 2 atmospheres .« less

  7. Kinetic modeling of the formation and growth of inorganic nano-particles during pulverized coal char combustion in O 2/N 2 and O 2/CO 2 atmospheres

    SciTech Connect

    Shaddix, Christopher R.; Niu, Yanqing; Hui, Shi'en

    In this formation of nano-particles during coal char combustion, the vaporization of inorganic components in char and the subsequent homogeneous particle nucleation, heterogeneous condensation, coagulation, and coalescence play decisive roles. Furthermore, conventional measurements cannot provide detailed information on the dynamics of nano-particle formation and evolution, In this study, a sophisticated intrinsic char kinetics model that considers ash effects (including ash film formation, ash dilution, and ash vaporization acting in tandem), both oxidation and gasification by CO 2 and H 2O, homogeneous particle nucleation, heterogeneous vapor condensation, coagulation, and and coalescence mechanisms is developed and used to compare the temporal evolutionmore » of the number and size of nano-particles during coal char particle combustion as a function of char particle size, ash content, and oxygen content in O 2/N 2 and O 2/CO 2 atmospheres .« less

  8. Oxygen Vacancies in ZnO Nanosheets Enhance CO2 Electrochemical Reduction to CO.

    PubMed

    Geng, Zhigang; Kong, Xiangdong; Chen, Weiwei; Su, Hongyang; Liu, Yan; Cai, Fan; Wang, Guoxiong; Zeng, Jie

    2018-05-22

    As electron transfer to CO 2 is generally considered to be the critical step during the activation of CO 2 , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO 2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 2 activation by introducing oxygen vacancies into electrocatalysts with electronic-rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of -16.1 mA cm -2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO 2 . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO 2 and the eased CO 2 activation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar

    2015-11-01

    The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open

  10. Understanding the effects of cationic dopants on α-MnO 2 oxygen reduction reaction electrocatalysis

    DOE PAGES

    Lambert, Timothy N.; Vigil, Julian A.; White, Suzanne E.; ...

    2017-01-09

    Nickel-doped α-MnO 2 nanowires (Ni–α-MnO 2) were prepared with 3.4% or 4.9% Ni using a hydrothermal method. A comparison of the electrocatalytic data for the oxygen reduction reaction (ORR) in alkaline electrolyte versus that obtained with α-MnO 2 or Cu–α-MnO 2 is provided. In general, Ni-α-MnO 2 (e.g., Ni-4.9%) had higher n values (n = 3.6), faster kinetics (k = 0.015 cm s –1), and lower charge transfer resistance (R CT = 2264 Ω at half-wave) values than MnO 2 (n = 3.0, k = 0.006 cm s –1, R CT = 6104 Ω at half-wave) or Cu–α-MnO 2 (Cu-2.9%,more » n = 3.5, k = 0.015 cm s –1, R CT = 3412 Ω at half-wave), and the overall activity for Ni–α-MnO 2 trended with increasing Ni content, i.e., Ni-4.9% > Ni-3.4%. As observed for Cu–α-MnO 2, the increase in ORR activity correlates with the amount of Mn 3+ at the surface of the Ni–α-MnO 2 nanowire. Examining the activity for both Ni–α-MnO 2 and Cu–α-MnO 2 materials indicates that the Mn 3+ at the surface of the electrocatalysts dictates the activity trends within the overall series. Single nanowire resistance measurements conducted on 47 nanowire devices (15 of α-MnO 2, 16 of Cu–α-MnO 2-2.9%, and 16 of Ni–α-MnO 2-4.9%) demonstrated that Cu-doping leads to a slightly lower resistance value than Ni-doping, although both were considerably improved relative to the undoped α-MnO 2. As a result, the data also suggest that the ORR charge transfer resistance value, as determined by electrochemical impedance spectroscopy, is a better indicator of the cation-doping effect on ORR catalysis than the electrical resistance of the nanowire.« less

  11. Symmetry of the oxygen hole states in Bi 2Sr 2CaCu 2O 8 investigated by XAS

    NASA Astrophysics Data System (ADS)

    Kuiper, P.; Grioni, M.; Sawatzky, G. A.; Mitzi, D. B.; Kapitulnik, A.; Santaniello, A.; de Padova, P.; Thiry, P.

    1989-02-01

    We have observed strong polarization dependence in the X-ray absorption near the oxygen K edge in a single crystal of Bi 2Sr 2CaCu 2O 8 ( Tc=85 K). The results show that O-derived holes near the Fermi-level have p x, y (perpendicular to the c-axis) symmetry. Some consequences for models of superconductivity are discussed. The concentration of holes is estimated to be about equal to that in YBa 2Cu 3O 7.

  12. Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

    PubMed

    Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

    2015-08-14

    The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

  13. Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

    PubMed

    Haqq-Misra, Jacob; Kasting, James F; Lee, Sukyoung

    2011-05-01

    Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

  14. N2O emission from plant surfaces - light stimulated and a global phenomenon.

    NASA Astrophysics Data System (ADS)

    Mikkelsen, Teis; Bruhn, Dan; Ambus, Per

    2017-04-01

    Nitrous oxide (N2O) is an important long-lived greenhouse gas and precursor of stratospheric ozone depleting mono-nitrogen oxides. The atmospheric concentration of N2O is persistently increasing; however, large uncertainties are associated with the distinct source strengths. Here we investigate for the first time N2O emission from terrestrial vegetation in response to natural solar ultra violet radiation. We conducted field site measurements to investigate N2O atmosphere exchange from grass vegetation exposed to solar irradiance with and without UV-screening. Further laboratory tests were conducted with a range of species to study the controls and possible loci of UV-induced N2O emission from plants. Plants released N2O in response to natural sunlight at rates of c. 20-50 nmol m-2 h-1, mostly due to the UV component. The emission rate is temperature dependent with a rather high activation energy indicative for an abiotic process. The prevailing zone for the N2O formation appears to be at the very surface of leaves. However, only c. 26% of the UV-induced N2O appears to originate from plant-N. Further, the process is dependent on atmospheric oxygen concentration. Our work demonstrates that ecosystem emission of the important greenhouse gas, N2O, may be up to c. 30% higher than hitherto assumed. Literature: Mikkelsen TN, Bruhn D & Ambus P. (2016). Solar UV Irradiation-Induced Production of Greenhouse Gases from Plant Surfaces: From Leaf to Earth. Progress in Botany, DOI 10.1007/124_2016_10. Bruhn D, Albert KR, Mikkelsen TN & Ambus P. (2014). UV-induced N2O emission from plants. Atmospheric Environment 99, 206-214.

  15. The Mechanism of Low-Temperature Oxidation of Carbon Monoxide by Oxygen over the PdCl2–CuCl2/γ-Al2O3 Nanocatalyst

    PubMed Central

    Bruk, Lev; Titov, Denis; Ustyugov, Alexander; Chernikova, Valeriya; Tkachenko, Olga; Kustov, Leonid; Murzin, Vadim; Oshanina, Irina; Temkin, Oleg

    2018-01-01

    The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH)3 (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H2O vapor (without O2). It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1) and bridging (1928 cm−1) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas) mixtures in a flow reactor (steady state conditions). PMID:29614029

  16. Photoassisted Oxygen Reduction Reaction in H2 -O2 Fuel Cells.

    PubMed

    Zhang, Bingqing; Wang, Shengyang; Fan, Wenjun; Ma, Weiguang; Liang, Zhenxing; Shi, Jingying; Liao, Shijun; Li, Can

    2016-11-14

    The oxygen reduction reaction (ORR) is a key step in H 2 -O 2 fuel cells, which, however, suffers from slow kinetics even for state-of-the-art catalysts. In this work, by making use of photocatalysis, the ORR was significantly accelerated with a polymer semiconductor (polyterthiophene). The onset potential underwent a positive shift from 0.66 to 1.34 V, and the current was enhanced by a factor of 44 at 0.6 V. The improvement was further confirmed in a proof-of-concept light-driven H 2 -O 2 fuel cell, in which the open circuit voltage (V oc ) increased from 0.64 to 1.18 V, and the short circuit current (J sc ) was doubled. This novel tandem structure combining a polymer solar cell and a fuel cell enables the simultaneous utilization of photo- and electrochemical energy, showing promising potential for applications in energy conversion and storage. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Electrical properties of GaN-based metal-insulator-semiconductor structures with Al2O3 deposited by atomic layer deposition using water and ozone as the oxygen precursors

    NASA Astrophysics Data System (ADS)

    Kubo, Toshiharu; Freedsman, Joseph J.; Iwata, Yasuhiro; Egawa, Takashi

    2014-04-01

    Al2O3 deposited by atomic layer deposition (ALD) was used as an insulator in metal-insulator-semiconductor (MIS) structures for GaN-based MIS-devices. As the oxygen precursors for the ALD process, water (H2O), ozone (O3), and both H2O and O3 were used. The chemical characteristics of the ALD-Al2O3 surfaces were investigated by x-ray photoelectron spectroscopy. After fabrication of MIS-diodes and MIS-high-electron-mobility transistors (MIS-HEMTs) with the ALD-Al2O3, their electrical properties were evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements. The threshold voltage of the C-V curves for MIS-diodes indicated that the fixed charge in the Al2O3 layer is decreased when using both H2O and O3 as the oxygen precursors. Furthermore, MIS-HEMTs with the H2O + O3-based Al2O3 showed good dc I-V characteristics without post-deposition annealing of the ALD-Al2O3, and the drain leakage current in the off-state region was suppressed by seven orders of magnitude.

  18. Why O2 Is Required by Complex Life on Habitable Planets and the Concept of Planetary "Oxygenation Time"

    NASA Astrophysics Data System (ADS)

    Catling, David C.; Glein, Christopher R.; Zahnle, Kevin J.; McKay, Christopher P.

    2005-06-01

    Life is constructed from a limited toolkit: the Periodic Table. The reduction of oxygen provides the largest free energy release per electron transfer, except for the reduction of fluorine and chlorine. However, the bonding of O2 ensures that it is sufficiently stable to accumulate in a planetary atmosphere, whereas the more weakly bonded halogen gases are far too reactive ever to achieve significant abundance. Consequently, an atmosphere rich in O2 provides the largest feasible energy source. This universal uniqueness suggests that abundant O2 is necessary for the high-energy demands of complex life anywhere, i.e., for actively mobile organisms of ~10-1-100 m size scale with specialized, differentiated anatomy comparable to advanced metazoans. On Earth, aerobic metabolism provides about an order of magnitude more energy for a given intake of food than anaerobic metabolism. As a result, anaerobes do not grow beyond the complexity of uniseriate filaments of cells because of prohibitively low growth efficiencies in a food chain. The biomass cumulative number density, n, at a particular mass, m, scales as n (>m)~m-1 for aquatic aerobes, and we show that for anaerobes the predicted scaling is n~m -1.5, close to a growth-limited threshold. Even with aerobic metabolism, the partial pressure of atmospheric O2 (PO2) must exceed ~103 Pa to allow organisms that rely on O2 diffusion to evolve to a size ~10-3 m. PO2 in the range ~103-104 Pa is needed to exceed the threshold of ~10-2 m size for complex life with circulatory physiology. In terrestrial life, O2 also facilitates hundreds of metabolic pathways, including those that make specialized structural molecules found only in animals. The time scale to reach PO2 ~104 Pa, or "oxygenation time," was long on the Earth (~3.9 billion years), within almost a factor of 2 of the Sun's main sequence lifetime. Consequently, we argue that the oxygenation time is likely to be a key rate-limiting step in the evolution of complex life on

  19. Millimeter Detection Of AlO (X2Σ+) In The Oxygen-rich Envelope Of VY Canis Majoris

    NASA Astrophysics Data System (ADS)

    Tenenbaum, Emily D.; Ziurys, L. M.

    2009-05-01

    A new circumstellar molecule, the radical AlO (X 2Σ+), has been detected toward the envelope of the oxygen-rich supergiant star VY Canis Majoris (VY CMa) via three rotational emission lines. The N = 7 → 6 and 6 → 5 features of AlO were observed at 1 mm using the Arizona Radio Observatory Submillimeter Telescope (ARO SMT) and the N = 4 → 3 line was detected at 2 mm using the ARO 12 m dish. All lines exhibit noticeable hyperfine broadening due to the I = 5/2 spin of the aluminum nucleus. Based on simulations of the line profiles, AlO most likely arises from the dust-acceleration zone in the spherical outflow of VY CMa, with a source size of θs 0.5''. Given this source size, the column density of AlO was found to be Ntot 2 × 1015 cm-2 for Trot 230 K, with a fractional abundance, relative to H2, of 10-8. Gas-phase thermodynamic equilibrium chemistry is the likely formation mechanism for AlO in VY CMa, but shocks may disrupt the condensation process into Al2O3, allowing AlO to survive 20 stellar radii. The detection of AlO in VY CMa is additional evidence of an active gas-phase refractory chemistry in oxygen-rich envelopes, and suggests such objects may be fruitful sources for other new oxide identifications.

  20. Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

    DOEpatents

    Robinson, P.R.; Bamberger, C.E.

    1980-02-08

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  1. Excessive use of nitrogen in Chinese agriculture results in high N2O/(N2O+N2) product ratio of denitrification, primarily due to acidification of the soils

    PubMed Central

    Qu, Zhi; Wang, Jingguo; Almøy, Trygve; Bakken, Lars R

    2014-01-01

    China is the world's largest producer and consumer of fertilizer N, and decades of overuse has caused nitrate leaching and possibly soil acidification. We hypothesized that this would enhance the soils' propensity to emit N2O from denitrification by reducing the expression of the enzyme N2O reductase. We investigated this by standardized oxic/anoxic incubations of soils from five long-term fertilization experiments in different regions of China. After adjusting the nitrate concentration to 2 mM, we measured oxic respiration (R), potential denitrification (D), substrate-induced denitrification, and the denitrification product stoichiometry (NO, N2O, N2). Soils with a history of high fertilizer N levels had high N2O/(N2O+N2) ratios, but only in those field experiments where soil pH had been lowered by N fertilization. By comparing all soils, we found a strong negative correlation between pH and the N2O/(N2O+N2) product ratio (r2 = 0.759, P < 0.001). In contrast, the potential denitrification (D) was found to be a linear function of oxic respiration (R), and the ratio D/R was largely unaffected by soil pH. The immediate effect of liming acidified soils was lowered N2O/(N2O+N2) ratios. The results provide evidence that soil pH has a marginal direct effect on potential denitrification, but that it is the master variable controlling the percentage of denitrified N emitted as N2O. It has been known for long that low pH may result in high N2O/(N2O+N2) product ratios of denitrification, but our documentation of a pervasive pH-control of this ratio across soil types and management practices is new. The results are in good agreement with new understanding of how pH may interfere with the expression of N2O reductase. We argue that the management of soil pH should be high on the agenda for mitigating N2O emissions in the future, particularly for countries where ongoing intensification of plant production is likely to acidify the soils. PMID:24249526

  2. Interface properties of SiO2/GaN structures formed by chemical vapor deposition with remote oxygen plasma mixed with Ar or He

    NASA Astrophysics Data System (ADS)

    Truyen, Nguyen Xuan; Taoka, Noriyuki; Ohta, Akio; Makihara, Katsunori; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Shimizu, Mitsuaki; Miyazaki, Seiichi

    2018-06-01

    The impacts of noble gas species (Ar and He) on the formation of a SiO2/GaN structure formed by a remote oxygen plasma-enhanced chemical vapor deposition (ROPE-CVD) method were systematically investigated. Atomic force microscopy revealed that ROPE-CVD with He leads to a smooth SiO2 surface compared with the case of Ar. We found that no obvious oxidations of the GaN surfaces after the SiO2 depositions with the both Ar and He cases were observed. The capacitance–voltage (C–V) curves of the GaN MOS capacitors formed by ROPE-CVD with the Ar and He dilutions show good interface properties with no hysteresis and good agreement with the ideal C–V curves even after post deposition annealing at 800 °C. Besides, we found that the current density–oxide electric field characteristics shows a gate leakage current for the Ar case lower than the He case.

  3. N2/O2/H2 Dual-Pump Cars: Validation Experiments

    NASA Technical Reports Server (NTRS)

    OByrne, S.; Danehy, P. M.; Cutler, A. D.

    2003-01-01

    The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

  4. Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

    PubMed Central

    González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

    2017-01-01

    The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

  5. A determination of the oxygen non-stoichiometry of the oxygen storage material YBaMn{sub 2}O{sub 5+δ}

    SciTech Connect

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana

    2015-10-15

    The A-site ordered double-perovskite oxide, YBaMn{sub 2}O{sub 5+δ}, has been of recent interest for possible application as an oxygen storage material. In the present study, the oxygen non-stoichiometry of YBaMn{sub 2}O{sub 5+δ} has been determined as a function of pO{sub 2} at 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that this perovskite oxide has three distinct phases on oxidation/reduction with δ≈0, 0.5 and 1. The stabilities of the YBaMn{sub 2}O{sub 5+δ} phases span a wide range of oxygen partial pressures (∼10{sup −20}≤pO{sub 2}(atm)≤∼1 ) depending on temperature. The phases interconvert at higher pO{submore » 2} values at higher temperatures. The partial molar free energies (Δμ{sub O}) corresponding to the oxidation of YBaMn{sub 2}O{sub 5} to YBaMn{sub 2}O{sub 5.5} and of YBaMn{sub 2}O{sub 5.5} to YBaMn{sub 2}O{sub ∼6} were determined. The value of Δμ{sub O} in both oxidation steps becomes less negative with increasing temperature. At some T and pO{sub 2} conditions, YBaMn{sub 2}O{sub 5+δ} is unstable with respect to decomposition to BaMnO{sub 3−δ} and YMnO{sub 3}. This instability is anticipated from the previous studies of the synthesis of YBaMn{sub 2}O{sub 5+δ} but is more apparent in the present experiments which are necessarily slow in order to achieve equilibrium with respect to the oxygen content. - Highlights: • Determination of the oxygen non-stoichiometry of YBaMn{sub 2}O{sub 5+δ} as a function of pO{sub 2} and T. • Establishments of pO{sub 2} ranges of stability of O{sub 5} and O{sub 5.5} at 650 °C, 700 °C and 750 °C. • Discovery of the kinetic instability of YBaMn{sub 2}O{sub 5+δ} with respect to decomposition to BaMnO{sub 3}−{sub x} and YMnO{sub 3}. • Evaluation of the thermodynamics of the oxidation of YBaMnO{sub 5}.« less

  6. Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

    PubMed

    Shevela, Dmitriy; Koroidov, Sergey; Najafpour, M Mahdi; Messinger, Johannes; Kurz, Philipp

    2011-05-02

    Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Reaction of N2O5 with H2O on carbonaceous surfaces

    NASA Technical Reports Server (NTRS)

    Brouwer, L.; Rossi, M. J.; Golden, D. M.

    1986-01-01

    The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

  8. O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

    PubMed

    Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

    2017-10-05

    Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

  9. Oceanic nitrogen cycling and N2O flux perturbations in the Anthropocene

    NASA Astrophysics Data System (ADS)

    Landolfi, A.; Somes, C. J.; Koeve, W.; Zamora, L. M.; Oschlies, A.

    2017-08-01

    There is currently no consensus on how humans are affecting the marine nitrogen (N) cycle, which limits marine biological production and CO2 uptake. Anthropogenic changes in ocean warming, deoxygenation, and atmospheric N deposition can all individually affect the marine N cycle and the oceanic production of the greenhouse gas nitrous oxide (N2O). However, the combined effect of these perturbations on marine N cycling, ocean productivity, and marine N2O production is poorly understood. Here we use an Earth system model of intermediate complexity to investigate the combined effects of estimated 21st century CO2 atmospheric forcing and atmospheric N deposition. Our simulations suggest that anthropogenic perturbations cause only a small imbalance to the N cycle relative to preindustrial conditions (˜+5 Tg N y-1 in 2100). More N loss from water column denitrification in expanded oxygen minimum zones (OMZs) is counteracted by less benthic denitrification, due to the stratification-induced reduction in organic matter export. The larger atmospheric N load is offset by reduced N inputs by marine N2 fixation. Our model predicts a decline in oceanic N2O emissions by 2100. This is induced by the decrease in organic matter export and associated N2O production and by the anthropogenically driven changes in ocean circulation and atmospheric N2O concentrations. After comprehensively accounting for a series of complex physical-biogeochemical interactions, this study suggests that N flux imbalances are limited by biogeochemical feedbacks that help stabilize the marine N inventory against anthropogenic changes. These findings support the hypothesis that strong negative feedbacks regulate the marine N inventory on centennial time scales.

  10. Evaluation of the electrochemical O2 concentrator as an O2 compressor

    NASA Technical Reports Server (NTRS)

    Marshall, R. D.; Carlson, J. N.

    1975-01-01

    A program was successfully completed to analytically and experimentally evaluate the feasibility of using an electrochemical oxygen (O2) concentrator as an O2 compressor. The electrochemical O2 compressor (EOC) compresses 345 kN/sq m (50 psia) O2 generated on board the space vehicle by the water electrolysis subsystem (WES) in a single stage to 20,700 kN/sq m (3000 psia) to refill spent extravehicular equipment O2 bottles and to eliminate the need for high pressure O2 storage. The single cell EOC designed, fabricated, and used for the feasibility testing is capable of being tested at O2 pressures up to 41,400 kN/sq m (6000 psia). A ground support test facility to test the EOC cell was designed, fabricated, and used for the EOC feasibility testing. A product assurance program was established, implemented, and maintained which emphasized safety and materials compatibility associated with high pressure O2 operation. A membrane development program was conducted to develop a membrane for EOC application. Data obtained using a commercially available membrane were used to guide the development of the membranes fabricated specifically for an EOC. A total of 15 membranes were fabricated.

  11. Electron holography on HfO2/HfO2-x bilayer structures with multilevel resistive switching properties

    NASA Astrophysics Data System (ADS)

    Niu, G.; Schubert, M. A.; Sharath, S. U.; Zaumseil, P.; Vogel, S.; Wenger, C.; Hildebrandt, E.; Bhupathi, S.; Perez, E.; Alff, L.; Lehmann, M.; Schroeder, T.; Niermann, T.

    2017-05-01

    Unveiling the physical nature of the oxygen-deficient conductive filaments (CFs) that are responsible for the resistive switching of the HfO2-based resistive random access memory (RRAM) devices represents a challenging task due to the oxygen vacancy related defect nature and nanometer size of the CFs. As a first important step to this goal, we demonstrate in this work direct visualization and a study of physico-chemical properties of oxygen-deficient amorphous HfO2-x by carrying out transmission electron microscopy electron holography as well as energy dispersive x-ray spectroscopy on HfO2/HfO2-x bilayer heterostructures, which are realized by reactive molecular beam epitaxy. Furthermore, compared to single layer devices, Pt/HfO2/HfO2-x /TiN bilayer devices show enhanced resistive switching characteristics with multilevel behavior, indicating their potential as electronic synapses in future neuromorphic computing applications.

  12. Regulating the active species of Ni(OH)2 using CeO2: 3D CeO2/Ni(OH)2/carbon foam as an efficient electrode for the oxygen evolution reaction.

    PubMed

    Liu, Zhengqing; Li, Na; Zhao, Hongyang; Zhang, Yi; Huang, Yunhui; Yin, Zongyou; Du, Yaping

    2017-04-01

    Three dimensional (3D) N, O and S doped carbon foam (NOSCF) is prepared as a substrate for in situ vertically grown Ni(OH) 2 nanosheets. As designed Ni(OH) 2 /NOSCF possesses strong electrostatic interactions with OH - ions due to many C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O groups existing in NOSCF, which can facilitate the formation of crucial NiOOH intermediates during the OER process. CeO 2 nanoparticles (NPs) of ∼3.3 nm in size are decorated on Ni(OH) 2 nanosheets to design a highly efficient CeO 2 /Ni(OH) 2 /NOSCF electrocatalyst for the oxygen evolution reaction (OER). The CeO 2 NP decorated Ni(OH) 2 /NOSCF not only exhibits a remarkably improved OER performance with an onset potential of 240 mV, outperforming most reported non-noble metal based OER electrocatalysts, but also possesses a small Tafel slope of 57 mV dec -1 and

  13. Retardation mechanism of ultrathin Al2O3 interlayer on Y2O3 passivated gallium nitride surface.

    PubMed

    Quah, Hock Jin; Cheong, Kuan Yew

    2014-05-28

    A systematic investigation was carried out by incorporating an ultrathin aluminum oxide (Al2O3) as an interlayer between yttrium oxide (Y2O3) passivation layer and GaN substrate. The sandwiched samples were then subjected to postdeposition annealing in oxygen ambient from 400 to 800 °C. The Al2O3 interlayer was discovered to play a significant role in slowing down inward diffusion of oxygen through the Y2O3 passivation layer as well as in impeding outward diffusion of Ga(3+) and N(3-) from the decomposed GaN surface. These beneficial effects have suppressed subsequent formation of interfacial layer. A mechanism in association with the function of Al2O3 as an interlayer was suggested and discussed. The mechanism was explicitly described on the basis of the obtained results from X-ray diffraction, X-ray photoelectron spectroscopy, energy-filtered transmission electron microscopy (TEM), high resolution TEM, and electron energy loss spectroscopy line scan. A correlation between the proposed mechanism and metal-oxide-semiconductor characteristics of Y2O3/Al2O3/GaN structure has been proposed.

  14. The diversity of the N2O reducers matters for the N2O:N2 denitrification end-product ratio across an annual and a perennial cropping system.

    PubMed

    Domeignoz-Horta, Luiz A; Spor, Aymé; Bru, David; Breuil, Marie-Christine; Bizouard, Florian; Léonard, Joël; Philippot, Laurent

    2015-01-01

    Agriculture is the main source of terrestrial emissions of N2O, a potent greenhouse gas and the main cause of ozone layer depletion. The reduction of N2O into N2 by microorganisms carrying the nitrous oxide reductase gene (nosZ) is the only biological process known to eliminate this greenhouse gas. Recent studies showed that a previously unknown clade of N2O-reducers was related to the capacity of the soil to act as an N2O sink, opening the way for new strategies to mitigate emissions. Here, we investigated whether the agricultural practices could differently influence the two N2O reducer clades with consequences for denitrification end-products. The abundance of N2O-reducers and producers was quantified by real-time PCR, and the diversity of both nosZ clades was determined by 454 pyrosequencing. Potential N2O production and potential denitrification activity were used to calculate the denitrification gaseous end-product ratio. Overall, the results showed limited differences between management practices but there were significant differences between cropping systems in both the abundance and structure of the nosZII community, as well as in the [rN2O/r(N2O+N2)] ratio. More limited differences were observed in the nosZI community, suggesting that the newly identified nosZII clade is more sensitive than nosZI to environmental changes. Potential denitrification activity and potential N2O production were explained mainly by the soil properties while the diversity of the nosZII clade on its own explained 26% of the denitrification end-product ratio, which highlights the importance of understanding the ecology of this newly identified clade of N2O reducers for mitigation strategies.

  15. Comparison and mechanism of photocatalytic activities of N-ZnO and N-ZrO2 for the degradation of rhodamine 6G.

    PubMed

    Sudrajat, Hanggara; Babel, Sandhya

    2016-05-01

    N-doped ZnO (N-ZnO) and N-doped ZrO2 (N-ZrO2) are synthesized by novel, simple thermal decomposition methods. The catalysts are evaluated for the degradation of rhodamine 6G (R6G) under visible and UV light. N-ZnO exhibits higher dye degradation under both visible and UV light compared to N-ZrO2 due to possessing higher specific surface area, lower crystalline size, and lower band gap. However, it is less reusable than N-ZrO2 and its photocatalytic activity is also deteriorated at low pH. At the same intensity of 3.5 W/m(2), UVC light is shown to be a better UV source for N-ZnO, while UVA light is more suitable for N-ZrO2. At pH 7 with initial dye concentration of 10 mg/L, catalyst concentration of 1 g/L, and UVC light, 94.3 % of R6G is degraded by N-ZnO within 2 h. Using UVA light under identical experimental conditions, 93.5 % degradation of R6G is obtained by N-ZrO2. Moreover, the type of light source is found to determine the reactive species produced in the R6G degradation by N-ZnO and N-ZrO2. Less oxidative reactive species such as superoxide radical and singlet oxygen play a major role in the degradation of R6G under visible light. On the contrary, highly oxidative hydroxyl radicals are predominant under UVC light. Based on the kinetic study, the adsorption of R6G on the catalyst surface is found to be the controlling step.

  16. Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

    PubMed

    Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

    2016-02-01

    This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

  17. Infrared spectra and tunneling dynamics of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O.

    PubMed

    Zhu, Yu; Zheng, Rui; Li, Song; Yang, Yu; Duan, Chuanxi

    2013-12-07

    The rovibrational spectra of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O have been measured in a supersonic slit jet expansion using a rapid-scan tunable diode laser spectrometer. Both a-type and b-type transitions were observed for these two complexes. All transitions are doubled, due to the heavy water tunneling within the complexes. Assuming the tunneling splittings are the same in K(a) = 0 and K(a) = 1, the band origins, all three rotational and several distortion constants of each tunneling state were determined for N2-D2O in the ground and excited vibrational states, and for OC-D2O in the excited vibrational state, respectively. The averaged band origin of OC-D2O is blueshifted by 2.241 cm(-1) from that of the v2 band of the D2O monomer, compared with 1.247 cm(-1) for N2-D2O. The tunneling splitting of N2-D2O in the ground state is 0.16359(28) cm(-1), which is about five times that of OC-D2O. The tunneling splittings decrease by about 26% for N2-D2O and 23% for OC-D2O, respectively, upon excitation of the D2O bending vibration, indicating an increase of the tunneling barrier in the excited vibrational state. The tunneling splittings are found to have a strong dependence on intramolecular vibrational excitation as well as a weak dependence on quantum number K(a).

  18. Triaqua-1κO,2κ2 O-bis­(2,2′-bipyridine)-1κ2 N,N′;2κ2 N,N′-chlorido-1κCl-μ-terephthalato-1:2κ2 O 1:O 4-dicopper(II) nitrate monohydrate

    PubMed Central

    Liu, Yang; Feng, Yong-Lan; Kuang, Dai-Zhi

    2012-01-01

    In the binuclear title compound, [Cu2(C8H4O4)Cl(C10H8N2)2(H2O)3]NO3·H2O, the two crystallographically independent CuII ions have similar coordination environments. One of the CuII ions has a square-pyramidal arrangement, which is defined by a water mol­ecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine mol­ecule, one carboxyl­ate O atom from a terephthalate ligand and one O atom from a water mol­ecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water mol­ecule. An O—H⋯O and O—H⋯Cl hydrogen-bonded three-dimensional network is formed between the components. PMID:22719307

  19. Crystal structure and optical property of complex perovskite oxynitrides ALi0.2Nb0.8O2.8N0.2, ANa0.2Nb0.8O2.8N0.2, and AMg0.2Nb0.8O2.6N0.4 (A = Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Moon, Keon Ho; Avdeev, Maxim; Kim, Young-Il

    2017-10-01

    Oxynitride type complex perovskites AM0.2Nb0.8O3-xNx (A = Sr, Ba; M = Li, Na, Mg) were newly synthesized by the solid state diffusion of Li+, Na+, or Mg2+ into the layered oxide, A5Nb4O15, with concurrent O/N substitution. Neutron and synchrotron X-ray Rietveld refinement showed that SrLi0.2Nb0.8O2.8N0.2, SrNa0.2Nb0.8O2.8N0.2, and SrMg0.2Nb0.8O2.6N0.4 had body-centered tetragonal symmetry (I4/mcm), while those with A = Ba had simple cubic symmetry (Pm 3 ̅ m). In the tetragonal Sr-compounds, the nitrogen atoms were localized on the c-axial 4a site. However, the octahedral cations, M/Nb (M = Li, Na, Mg) were distributed randomly in all six compounds. The lattice volume of AM0.2Nb0.8O3-xNx was dependent on various factors including the type of A and the electronegativity of M. Compared to the simple perovskites, ANbO2N (A = Sr, Ba), AM0.2Nb0.8O3-xNx had wider band gaps (1.76-2.15 eV for A = Sr and 1.65-2.10 eV for A = Ba), but significantly lower sub-gap absorption.

  20. Gas entrapment and microbial N2O reduction reduce N2O emissions from a biochar-amended sandy clay loam soil

    PubMed Central

    Harter, Johannes; Guzman-Bustamante, Ivan; Kuehfuss, Stefanie; Ruser, Reiner; Well, Reinhard; Spott, Oliver; Kappler, Andreas; Behrens, Sebastian

    2016-01-01

    Nitrous oxide (N2O) is a potent greenhouse gas that is produced during microbial nitrogen transformation processes such as nitrification and denitrification. Soils represent the largest sources of N2O emissions with nitrogen fertilizer application being the main driver of rising atmospheric N2O concentrations. Soil biochar amendment has been proposed as a promising tool to mitigate N2O emissions from soils. However, the underlying processes that cause N2O emission suppression in biochar-amended soils are still poorly understood. We set up microcosm experiments with fertilized, wet soil in which we used 15N tracing techniques and quantitative polymerase chain reaction (qPCR) to investigate the impact of biochar on mineral and gaseous nitrogen dynamics and denitrification-specific functional marker gene abundance and expression. In accordance with previous studies our results showed that biochar addition can lead to a significant decrease in N2O emissions. Furthermore, we determined significantly higher quantities of soil-entrapped N2O and N2 in biochar microcosms and a biochar-induced increase in typical and atypical nosZ transcript copy numbers. Our findings suggest that biochar-induced N2O emission mitigation is based on the entrapment of N2O in water-saturated pores of the soil matrix and concurrent stimulation of microbial N2O reduction resulting in an overall decrease of the N2O/(N2O + N2) ratio. PMID:28008997

  1. Reply to Comment on ‘Oxygen vacancy-induced magnetic moment in edge-sharing CuO2 chains of Li2CuO2-δ ’

    NASA Astrophysics Data System (ADS)

    Shu, G. J.; Tian, J. C.; Lin, C. K.; Hayashi, M.; Liou, S. C.; Chen, W. T.; Wong, Deniz P.; Liou, H. L.; Chou, F. C.

    2018-05-01

    In this reply to the comment on ‘Oxygen vacancy-induced magnetic moment in edge-sharing CuO2 chains of {{{Li}}}2{{{CuO}}}2-δ ’ (2017 New Journal of Physics 19 023206), we have clarified several key questions and conflicting results regarding the size of the intra-chain nearest neighbor coupling J 1 and the sign of the Weiss temperature Θ defined in the Curie–Weiss law of χ(T) = χ ◦ + C/(T ‑ Θ). Additional data analysis is conducted to verify the validity of the Curie–Weiss law fitting protocol, including the negative sign and size of Θ based on the high-temperature linear temperature dependence of 1/χ(T) for T > J 1 and \\tfrac{g{μ }B{SH}}{{k}BT}\\ll 1. The consistency between the magnetic antiferromagnetic (AF) ground state below T N and the negative sign of Θ in the high-temperature paramagnetic (PM) state is explained via the reduction of thermal fluctuation for a temperature-independent local field due to magnetic interaction of quantum nature. A magnetic dipole–dipole (MDD)-type interaction among FM chains is identified and proposed to be necessary for the 3D AF magnetic ground state formation, i.e., the Heisenberg model of an exchange-type interaction alone is not sufficient to fully describe the quasi-1D spin chain system of {{{Li}}}2{{{CuO}}}2. Several typical quasi-1D spin chain compounds, including {{{Li}}}2{{{CuO}}}2,{{{CuAs}}}2{{{O}}}4,{{{Sr}}}3{{{Fe}}}2{{{O}}}5, and CuGeO3, are compared to show why different magnetic ground states are achieved from the chemical bond perspective.

  2. Oxygen-vacancy behavior in La2-xSrxCuO4-y by positron annihilation and oxygen diffusion

    NASA Astrophysics Data System (ADS)

    Smedskjaer, L. C.; Routbort, J. L.; Flandermeyer, B. K.; Rothman, S. J.; Legnini, D. G.; Baker, J. E.

    1987-09-01

    Oxygen-diffusion and positron-annihilation results for La2-xSrxCuO4-y compounds are reported. A qualitative explanation of the observed results is given on the basis of a model in which the oxygen-vacancy concentration in La2-xSrxCuO4-y is determined by Sr2+ ion clustering on the La sublattice. This model also leads to a maximum in the Cu3+ ion concentration as a function of the Sr2+ ion concentration.

  3. Analysis of oxygen potential of (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x based on point defect chemistry

    NASA Astrophysics Data System (ADS)

    Kato, Masato; Konashi, Kenji; Nakae, Nobuo

    2009-06-01

    Stoichiometries in (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x were analyzed with the experimental data of oxygen potential based on point defect chemistry. The relationship between the deviation x of stoichiometric composition and the oxygen partial pressure P was evaluated using a Kröger-Vink diagram. The concentrations of the point defects in uranium and plutonium mixed oxide (MOX) were estimated from the measurement data of oxygen potentials as functions of temperature and P. The analysis results showed that x was proportional to PO2±1/2 near the stoichiometric region of both (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x, which suggested that intrinsic ionization was the dominant defect. A model to calculate oxygen potential was derived and it represented the experimental data accurately. Further, the model estimated the thermodynamic data, ΔH and ΔS, of stoichiometric (U 0.7Pu 0.3)O 2.00 and (U 0.8Pu 0.2)O 2.00 as -552.5 kJ·mol -1 and -149.7 J·mol -1, and -674.0 kJ · mol -1 and -219.4 J · mol -1, respectively.

  4. Electrochemical oxygen intercalation into Sr2IrO4

    NASA Astrophysics Data System (ADS)

    Fruchter, L.; Brouet, V.; Colson, D.; Moussy, J.-B.; Forget, A.; Li, Z. Z.

    2018-01-01

    Oxygen was electrochemically intercalated into Sr2IrO4 sintered samples, single crystals and a thin film. We estimate the diffusion length to a few μm and the concentration of the intercalated oxygen to δ ≃ 0.01. The latter is thus much smaller than for the cuprate and nickelate parent compounds, for which δ > 0.1 is obtained, which could be a consequence of larger steric effects. The influence of the oxygen doping state on resistivity is small, indicating also a poor charge transfer to the conduction band. It is shown that electrochemical intercalation of oxygen may also contribute to doping, when gating thin films with ionic liquid in the presence of water.

  5. Synthesis and characterization of stabilized oxygen-releasing CaO2 nanoparticles for bioremediation.

    PubMed

    Yeh, Chia-Shen; Wang, Reuben; Chang, Wen-Chi; Shih, Yang-Hsin

    2018-04-15

    Bioremediation is one of the general methods to treat pollutants in soil, sediment, and groundwater. However, the low concentration and restricted dispersion of dissolved oxygen (DO) in these areas have limited the efficiency of remediation especially for microorganisms that require oxygen to grow. Calcium peroxide (CaO 2 ) is one of the oxygen-releasing compounds and has been applied to magnify the remediation efficacy of polluting areas. In this study, CaO 2 nanoparticles (NPs) were synthesized and evaluated by wet chemistry methods as well as dry and wet grinding processes. The characteristics of CaO 2 particles and NPs were analyzed and compared by dynamic light scattering, transmission electron microscopy, scanning electron microscopy, and X-ray powder diffraction. Our results showed that wet-grinded CaO 2 NPs had an average particle size of around 110 nm and were more stable compared to other particles from aggregation and sedimentation tests. In addition, we also observed that CaO 2 NPs had better DO characteristics and patterns; these NPs generated higher DO levels than their non-grinded form. Accordingly, our results suggested that wet-grinding CaO 2 particles to nanoscale could benefit their usage in bioremediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. N2O and NO emissions during autotrophic nitrogen removal in a granular sludge reactor--a simulation study.

    PubMed

    Van Hulle, S W H; Callens, J; Mampaey, K E; van Loosdrecht, M C M; Volcke, E I P

    2012-01-01

    This contribution deals with NO and N2O emissions during autotrophic nitrogen removal in a granular sludge reactor. Two possible model scenarios describing this emission by ammonium- oxidizing biomass have been compared in a simulation study of a granular sludge reactor for one-stage partial nitritation--Anammox. No significant difference between these two scenarios was noticed. The influence of the bulk oxygen concentration, granule size, reactor temperature and ammonium load on the NO and N2O emissions has been assessed. The simulation results indicate that emission maxima of NO and N2O coincide with the region for optimal Anammox conversion. Also, most of the NO and N2O are present in the off-gas, owing to the limited solubility of both gases. The size of granules needs to be large enough not to limit optimal Anammox activity, but not too large as this implies an elevated production of N2O. Temperature has a significant influence on N2O emission, as a higher temperature results in a better N-removal efficiency and a lowered N2O production. Statistical analysis of the results showed that there is a strong correlation between nitrite accumulation and N2O production. Further, three regions of operation can be distinguished: a region with high N2O, NO and nitrite concentration; a region with high N2 concentrations and, as such, high removal percentages; and a region with high oxygen and nitrate concentrations. There is some overlap between the first two regions, which is in line with the fact that maximum emission of NO and N2O coincides with the region for optimal Anammox conversion.

  7. Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

    PubMed

    Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

    2002-09-11

    We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

  8. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO 2 (111) surfaces

    DOE PAGES

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; ...

    2016-05-12

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO 2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO 2(111) surface was obtained by annealing the thin film under 2.0 × 10 –5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO 2(111) surface, the thin film was annealed under ~5.0 × 10 –10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface.more » The saturated TMAA coverage on the CeO 2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO 2–δ(111) surface through dissociative adsorption.« less

  9. AC Glow Discharge Plasma in N2O

    SciTech Connect

    Yousif, F. B.; Martinez, H.; Robledo-Martinez, A.

    2006-12-04

    This paper considers the optical and electrical characterization of AC glow discharge plasma in the abnormal glow mode used for optical emission spectroscopy. The total discharge current and applied voltage are measured using conventional techniques. The electrical characteristics of the planer-cathode glow discharge confirmed that the plasma is operating at abnormal discharge mode characterized by the increases in the operating voltage as the current was raised under given pressure. Optical emission spectroscopy was used to determine the main emission lines of the glow discharge plasma of N2O at pressures between 0.5 and 4.0 Torr. It shows that the discharge emissionmore » range is mainly within 300-400 nm. The emission lines correspond to NO, O2, and O{sub 2}{sup +} are the dominant lines in the glow discharge plasma in the present study. Intensity of the emission lines show linear increase with the discharge current up to 0.4 A followed by saturation at higher currents. No emission lines were observed in this work corresponding to atomic oxygen or nitrogen.« less

  10. Electrical characteristics and interface properties of ALD-HfO2/AlGaN/GaN MIS-HEMTs fabricated with post-deposition annealing

    NASA Astrophysics Data System (ADS)

    Kubo, Toshiharu; Egawa, Takashi

    2017-12-01

    HfO2/AlGaN/GaN metal-insulator-semiconductor (MIS)-type high electron mobility transistors (HEMTs) on Si substrates were fabricated by atomic layer deposition of HfO2 layers and post-deposition annealing (PDA). The current-voltage characteristics of the MIS-HEMTs with as-deposited HfO2 layers showed a low gate leakage current (I g) despite the relatively low band gap of HfO2, and a dynamic threshold voltage shift (ΔV th) was observed. After PDA above 500 °C, ΔV th was reduced from 2.9 to 0.7 V with an increase in I g from 2.2 × 10-7 to 4.8 × 10-2 mA mm-1. Effects of the PDA on the HfO2 layer and the HfO2/AlGaN interface were investigated by x-ray photoelectron spectroscopy (XPS) using synchrotron radiation. XPS data showed that oxygen vacancies exist in the as-deposited HfO2 layers and they disappeared with an increase in the PDA temperature. These results indicate that the deep electron traps that cause ΔV th are related to the oxygen vacancies in the HfO2 layers.

  11. Annual dynamics of N2O, CH4 and CO2 fluxes from the agricultural irrigation watersheds in southeast China

    NASA Astrophysics Data System (ADS)

    Wu, S.; Zou, J.; Liu, S.; Chen, J.; Kong, D.; Geng, Y.

    2017-12-01

    Agricultural irrigation watershed covers a large area in southeast of China and is a potentially important source of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). However, the flux magnitudes contribution to the overall catchment greenhouse gas (GHGs) fluxes and their drivers of seasonal variability are limited in agricultural irrigation watersheds. An in-situ observation was performed to measure annual CO2, CH4 and N2O fluxes from an agricultural irrigation watershed in southeast of China from September 2014 to September 2016. GHGs fluxes were measured using floating chambers and a gas exchange model was also used to predict CH4 and N2O fluxes. All GHGs showed varied seasonally with highest fluxes in early summer (July) and lowest in winter. Estimated seasonal CH4-C fluxes (11.5-97.6 mg m-2 hr-1) and N2O-N fluxes (2.8-80.8μg m-2 hr-1) were in relative agreement with measured CH4-C fluxes (0.05-74.9mg m-2 hr-1) and N2O-N fluxes (3.9-68.7μg m-2 hr-1) fluxes using floating chambers. Both CH4 and N2O fluxes were positively related to water temperature. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to sediment dissolved organic carbon (DOC). The N2O fluxes were positively related to water NH4+ and NO3-. The calculated EF5-r value in this study (mean = 0.0016; range = 0.0013-0.0018) was below the current IPCC (2006) default value of 0.0025. This implied that IPCC methodology may over estimates of N2O emissions associated with nitrogen leaching and runoff from agriculture.

  12. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

    2015-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model

  13. Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

    PubMed

    Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

    2018-01-23

    The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

  14. Complete Decomposition of Li2CO3 in Li-O2 Batteries Using Ir/B4C as Noncarbon-Based Oxygen Electrode.

    PubMed

    Song, Shidong; Xu, Wu; Zheng, Jianming; Luo, Langli; Engelhard, Mark H; Bowden, Mark E; Liu, Bin; Wang, Chong-Min; Zhang, Ji-Guang

    2017-03-08

    Instability of carbon-based oxygen electrodes and incomplete decomposition of Li 2 CO 3 during charge process are critical barriers for rechargeable Li-O 2 batteries. Here we report the complete decomposition of Li 2 CO 3 in Li-O 2 batteries using the ultrafine iridium-decorated boron carbide (Ir/B 4 C) nanocomposite as a noncarbon based oxygen electrode. The systematic investigation on charging the Li 2 CO 3 preloaded Ir/B 4 C electrode in an ether-based electrolyte demonstrates that the Ir/B 4 C electrode can decompose Li 2 CO 3 with an efficiency close to 100% at a voltage below 4.37 V. In contrast, the bare B 4 C without Ir electrocatalyst can only decompose 4.7% of the preloaded Li 2 CO 3 . Theoretical analysis indicates that the high efficiency decomposition of Li 2 CO 3 can be attributed to the synergistic effects of Ir and B 4 C. Ir has a high affinity for oxygen species, which could lower the energy barrier for electrochemical oxidation of Li 2 CO 3 . B 4 C exhibits much higher chemical and electrochemical stability than carbon-based electrodes and high catalytic activity for Li-O 2 reactions. A Li-O 2 battery using Ir/B 4 C as the oxygen electrode material shows highly enhanced cycling stability than those using the bare B 4 C oxygen electrode. Further development of these stable oxygen-electrodes could accelerate practical applications of Li-O 2 batteries.

  15. Desorption of oxygen from YBa2Cu3O6+x films studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Bock, A.; Kürsten, R.; Brühl, M.; Dieckmann, N.; Merkt, U.

    1996-08-01

    Phonons of laser-deposited YBa2Cu3O6+x films on MgO(100) substrates are investigated in a Raman setup as a function of laser power density. Investigations of YBa2Cu3O7 films allow us to study oxygen out-diffusion, where the onset of out-diffusion is indicated by the appearance of disorder-induced modes in the Raman spectra. At a pressure of 5×10-6 mbar the temperature threshold of the out-diffusion is (490+/-15) K. With increasing oxygen pressure the observed temperature thresholds rise only moderately in contrast to the behavior expected from the pox-T phase diagram of YBa2Cu3O6+x. Even at 1 bar oxygen partial pressure out-diffusion is observed and tetragonal sites with x=0 develop. These observations can be explained by photon-stimulated desorption of oxygen. Investigations of YBa2Cu3O6 films allow us to study oxygen in-diffusion. In 1 bar oxygen we observe competing oxygen fluxes due to thermally activated diffusion and photon-stimulated desorption. From these measurements we determine an upper bound of the thermal activation energy of the oxygen in-diffusion into YBa2Cu3O6 films of (0.19+/-0.01) eV.

  16. Enhanced O-2 Selectivity versus N-2 by Partial Metal Substitution in Cu-BTC

    SciTech Connect

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.

    2015-03-24

    Here, we describe the homogeneous substitution of Mn, Fe, and Co at various levels into a prototypical metal organic framework (MOP), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O-2/N-2 selectivities determined experimentally at 77 K and the difference in O-2 and N-2 binding energies calculated from DFTmore » modeling data: Mn > Fe Co >> Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273-298 K) as compared to all other metals studied, indicative of favorable interactions between N-2 and coordinatively unsaturated Fe metal centers. Interestingly, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

  17. Enhanced O 2 selectivity versus N 2 by partial metal substitution in Cu-BTC

    DOE PAGES

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; ...

    2015-03-05

    Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O 2/N 2 selectivities determined experimentally at 77 K and the difference in O 2 and N 2 binding energiesmore » calculated from DFT modeling data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N 2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

  18. Structural and spectral analyses of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide)

    NASA Astrophysics Data System (ADS)

    Yıldırım, Sema Öztürk; Büyükmumcu, Zeki; Pekdur, Özlem Savaş; Butcher, Ray J.; Doǧan, Şengül Dilem

    2018-02-01

    In this study we report structure determination of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide). 2,2'-Dithiobis(benzamide) derivatives have been reported to possess important biological properties such as antibacterial, antifungal activities and inhibition of blood platelet aggregation and redeterrmined at 100(2)K from the data published by Raftery, Lallbeeharry, Bhowon, Laulloo & Joulea [Acta Cryst. 2009, E65, o16]. 2,2'-Dithiobis(N-butyl-benzamide) has been reported to be useful as an antiseptic for cosmetics. The structural properties of the compound have been characterized by using 1H NMR and the structure were determined by single-crystal X-ray diffraction. Molecular structure crystallizes in triclinic form, space group with a = 9.6396(7) Å, b = 9.9115(7) Å, c = 12.0026(8) Å, α = 109.743(6)°, β = 103.653(6)°, γ = 104.633(6)° and V = 977.15(13) Å3. In the solid state of the molecular structure N-H…S, N-H…O and C-H…O, type interactions provide for stabilization. The geometries of the title compound have been optimized using density functional theory (DFT) method. The calculated values were found to be in agreement with the experimental data.

  19. FiO2 delivered by a turbine portable ventilator with an oxygen concentrator in an Austere environment.

    PubMed

    Bordes, Julien; Erwan d'Aranda; Savoie, Pierre-Henry; Montcriol, Ambroise; Goutorbe, Philippe; Kaiser, Eric

    2014-09-01

    Management of critically ill patients in austere environments is a logistic challenge. Availability of oxygen cylinders for the mechanically ventilated patient may be difficult in such a context. A solution is to use a ventilator able to function with an oxygen concentrator. We tested the SeQual Integra™ (SeQual, San Diego, CA) 10-OM oxygen concentrator paired with the Pulmonetic System(®) LTV 1000 ventilator (Pulmonetic Systems, Minneapolis, MN) and evaluated the delivered fraction of inspired oxygen (FiO2) across a range of minute volumes and combinations of ventilator settings. Two LTV 1000 ventilators were tested. The ventilators were attached to a test lung and FiO2 was measured by a gas analyzer. Continuous-flow oxygen was generated by the OC from 0.5 L/min to 10 L/min and injected into the oxygen inlet port of the LTV 1000. Several combinations of ventilator settings were evaluated to determine the factors affecting the delivered FiO2. The LTV 1000 ventilator is a turbine ventilator that is able to deliver high FiO2 when functioning with an oxygen concentrator. However, modifications of the ventilator settings such as increase in minute ventilation affect delivered FiO2 even if oxygen flow is constant on the oxygen concentrator. The ability of an oxygen concentrator to deliver high FiO2 when used with a turbine ventilator makes this method of oxygen delivery a viable alternative to cylinders in austere environments when used with a turbine ventilator. However, FiO2 has to be monitored continuously because delivered FiO2 decreases when minute ventilation is increased. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Influence of Microstructure and Surface Activation of Dual-Phase Membrane Ce 0.8 Gd 0.2 O 2-δ -FeCo 2 O 4 on Oxygen Permeation

    DOE PAGES

    Ramasamy, Madhumidha; Baumann, Stefan; Palisaitis, Justinas; ...

    2015-09-24

    In dual-phase oxygen transport membranes we noticed that there is fast-growing interest in research for oxyfuel combustion process application. One such potential candidate is CGO-FCO (60wt% Ce 0.8Gd 0.2O 2-δ-40wt% FeCo 2O4) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO-FCO membranes of 1mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one-pot method (modified Pechini process) at 1200 degrees C for 10h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. We also identified that the spinel phase tends to form an oxygen deficientmore » phase at the grain boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) porous layer coating over the composite. Moreover, the oxygen permeation flux of the CGO-FCO screen printed with a porous layer of 10mthick LSCF is 0.11mL/cm 2 per minute at 850 degrees C with argon as sweep and air as feed gas at the rates of 50 and 250mL/min.« less

  1. trans-Bis(azido-kappaN)bis(pyridine-2-carboxamide-kappa2N1,O2)nickel(II).

    PubMed

    Daković, Marijana; Popović, Zora

    2007-11-01

    In the title compound, [Ni(N(3))(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N-H...N hydrogen bonds.

  2. Effects of N2-O2 and CO2-O2 tensions on growth of fungi isolated from damaged flue-cured tobacco.

    PubMed

    Yang, H; Lucas, G B

    1970-02-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N(2)-O(2) or CO(2)-O(2). A 1 to 5% concentration of O(2) in an N(2) atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O(2) for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O(2). High O(2) concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O(2) in the N(2) atmosphere, furrows formed in mycelial mats between 5 and 40% O(2) in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O(2) decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO(2)-O(2) mixtures radial growth of all species increased with each quantitative decrease of CO(2). All species except A. niger grew faster in air than in 10% CO(2). In contrast to N(2)-O(2) mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O(2) concentrations.

  3. A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

    PubMed

    Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

    2013-03-01

    The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

  4. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    PubMed

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. C=C bond cleavage on neutral VO3(V2O5)n clusters.

    PubMed

    Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

    2009-01-28

    The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

  6. [Selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalysts].

    PubMed

    Sun, Hong; Quan, Xie; Zhang, Yao-bin; Zhao, Ya-zhi

    2008-06-01

    Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst was prepared by sol-gel and impregnation. Furthermore, selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst with propylene under lean burn condition was studied. The effects of the concentration of tetra-n-butyl titanate and dipcoat cycles on TiO2 washcoat were studied by SEM, and the effects of Pd concentration, O2 concentration and gas velocity on catalytic activity were investigated. The experimental results showed that the TiO2 washcoat on wire-mesh support is even and crack-free when the support is impregnated in 20.0% tetra- n-butyl titanate sol for 2 cycles. The NOx conversion decreases with Pd concentration increase. When Pd concentration is 0.23%, NOx conversion is highest. NOx conversion increases with oxygen concentration increase in the range of 1.5%-6.0%. However, when oxygen concentration is higher than 6.0%, NOx conversion decreases with increasing oxygen concentration. The NOx conversion decreases with gas velocity increase and its effect is severer at high temperature than low temperature.

  7. Study of low resistivity and high work function ITO films prepared by oxygen flow rates and N2O plasma treatment for amorphous/crystalline silicon heterojunction solar cells.

    PubMed

    Hussain, Shahzada Qamar; Oh, Woong-Kyo; Kim, Sunbo; Ahn, Shihyun; Le, Anh Huy Tuan; Park, Hyeongsik; Lee, Youngseok; Dao, Vinh Ai; Velumani, S; Yi, Junsin

    2014-12-01

    Pulsed DC magnetron sputtered indium tin oxide (ITO) films deposited on glass substrates with lowest resistivity of 2.62 x 10(-4) Ω x cm and high transmittance of about 89% in the visible wavelength region. We report the enhancement of ITO work function (Φ(ITO)) by the variation of oxygen (O2) flow rate and N2O surface plasma treatment. The Φ(ITO) increased from 4.43 to 4.56 eV with the increase in O2 flow rate from 0 to 4 sccm while surface treatment of N2O plasma further enhanced the ITO work function to 4.65 eV. The crystallinity of the ITO films improved with increasing O2 flow rate, as revealed by XRD analysis. The ITO work function was increased by the interfacial dipole resulting from the surface rich in O- ions and by the dipole moment formed at the ITO surface during N2O plasma treatment. The ITO films with high work functions can be used to modify the front barrier height in heterojunction with intrinsic thin layer (HIT) solar cells.

  8. The cumulative influence of hyperoxia and hypercapnia on blood oxygenation and R2*

    PubMed Central

    Faraco, Carlos C; Strother, Megan K; Siero, Jeroen CW; Arteaga, Daniel F; Scott, Allison O; Jordan, Lori C; Donahue, Manus J

    2015-01-01

    Cerebrovascular reactivity (CVR)-weighted blood-oxygenation-level-dependent magnetic resonance imaging (BOLD-MRI) experiments are frequently used in conjunction with hyperoxia. Owing to complex interactions between hyperoxia and hypercapnia, quantitative effects of these gas mixtures on BOLD responses, blood and tissue R2*, and blood oxygenation are incompletely understood. Here we performed BOLD imaging (3 T; TE/TR=35/2,000 ms; spatial resolution=3 × 3 × 3.5 mm3) in healthy volunteers (n=12; age=29±4.1 years) breathing (i) room air (RA), (ii) normocapnic–hyperoxia (95% O2/5% N2, HO), (iii) hypercapnic–normoxia (5% CO2/21% O2/74% N2, HC-NO), and (iv) hypercapnic–hyperoxia (5% CO2/95% O2, HC-HO). For HC-HO, experiments were performed with separate RA and HO baselines to control for changes in O2. T2-relaxation-under-spin-tagging MRI was used to calculate basal venous oxygenation. Signal changes were quantified and established hemodynamic models were applied to quantify vasoactive blood oxygenation, blood–water R2*, and tissue–water R2*. In the cortex, fractional BOLD changes (stimulus/baseline) were HO/RA=0.011±0.007; HC-NO/RA=0.014±0.004; HC-HO/HO=0.020±0.008; and HC-HO/RA=0.035±0.010; for the measured basal venous oxygenation level of 0.632, this led to venous blood oxygenation levels of 0.660 (HO), 0.665 (HC-NO), and 0.712 (HC-HO). Interleaving a HC-HO stimulus with HO baseline provided a smaller but significantly elevated BOLD response compared with a HC-NO stimulus. Results provide an outline for how blood oxygenation differs for several gas stimuli and provides quantitative information on how hypercapnic BOLD CVR and R2* are altered during hyperoxia. PMID:26174329

  9. Controlling interface oxygen for forming Ag ohmic contact to semi-polar (1 1 -2 2) plane p-type GaN

    NASA Astrophysics Data System (ADS)

    Park, Jae-Seong; Han, Jaecheon; Seong, Tae-Yeon

    2014-11-01

    Low-resistance Ag ohmic contacts to semi-polar (1 1 -2 2) p-GaN were developed by controlling interfacial oxide using a Zn layer. The 300 °C-annealed Zn/Ag samples showed ohmic behavior with a contact resistivity of 6.0 × 10-4 Ω cm2 better than that of Ag-only contacts (1.0 × 10-3 Ω cm2). The X-ray photoemission spectroscopy (XPS) results showed that annealing caused the indiffusion of oxygen at the contact/GaN interface, resulting in the formation of different types of interfacial oxides, viz. Ga-oxide and Ga-doped ZnO. Based on the XPS and electrical results, the possible mechanisms underlying the improved electrical properties of the Zn/Ag samples are discussed.

  10. Structural, electronic, and magnetic properties of Y(n)O (n=2-14) clusters: Density functional study.

    PubMed

    Yang, Zhi; Xiong, Shi-Jie

    2008-09-28

    The geometries stability, electronic properties, and magnetism of Y(n)O clusters up to n=14 are systematically studied with density functional theory. In the lowest-energy structures of Y(n)O clusters, the equilibrium site of the oxygen atom gradually moves from an outer site of the cluster, via a surface site, and finally, to an interior site as the number of the Y atoms increases from 2 to 14. Starting from n=12, the O atom falls into the center of the cluster with the Y atoms forming the outer frame. The results show that clusters with n=2, 4, 8, and 12 are more stable than their respective neighbors, and that the total magnetic moments of Y(n)O clusters are all quite small except Y(12)O cluster. The lowest-energy structure of Y(12)O cluster is a perfect icosahedron with a large magnetic moment 6mu(B). In addition, we find that the total magnetic moments are quenched for n=2, 6, and 8 due to the closed-shell electronic configuration. The calculated ionization potentials and electron affinities are in good agreement with the experimental results, which imply that the present theoretical treatments are satisfactory.

  11. Uncertainties in United States agricultural N2O emissions: comparing forward model simulations to atmospheric N2O data.

    NASA Astrophysics Data System (ADS)

    Nevison, C. D.; Saikawa, E.; Dlugokencky, E. J.; Andrews, A. E.; Sweeney, C.

    2014-12-01

    Atmospheric N2O concentrations have increased from 275 ppb in the preindustrial to about 325 ppb in recent years, a ~20% increase with important implications for both anthropogenic greenhouse forcing and stratospheric ozone recovery. This increase has been driven largely by synthetic fertilizer production and other perturbations to the global nitrogen cycle associated with human agriculture. Several recent regional atmospheric inversion studies have quantified North American agricultural N2O emissions using top-down constraints based on atmospheric N2O data from the National Oceanic and Atmospheric Administration (NOAA) Global Greenhouse Gas Reference Network, including surface, aircraft and tall tower platforms. These studies have concluded that global N2O inventories such as EDGAR may be underestimating the true U.S. anthropogenic N2O source by a factor of 3 or more. However, simple back-of-the-envelope calculations show that emissions of this magnitude are difficult to reconcile with the basic constraints of the global N2O budget. Here, we explore some possible reasons why regional atmospheric inversions might overestimate the U.S. agricultural N2O source. First, the seasonality of N2O agricultural sources is not well known, but can have an important influence on inversion results, particularly when the inversions are based on data that are concentrated in the spring/summer growing season. Second, boundary conditions can strongly influence regional inversions but the boundary conditions used may not adequately account for remote influences on surface data such as the seasonal stratospheric influx of N2O-depleted air. We will present a set of forward model simulations, using the Community Land Model (CLM) and two atmospheric chemistry tracer transport models, MOZART and the Whole Atmosphere Community Climate Model (WACCM), that examine the influence of terrestrial emissions and atmospheric chemistry and dynamics on atmospheric variability in N2O at U.S. and

  12. Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

    PubMed

    Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

    2007-02-15

    In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

  13. High-resolution 17O double-rotation NMR characterization of ring and non-ring oxygen in vitreous B2O3.

    PubMed

    Wong, Alan; Howes, Andy P; Parkinson, Ben; Anupõld, Tiit; Samoson, Ago; Holland, Diane; Dupree, Ray

    2009-08-28

    The application of double rotation (DOR) NMR to crystalline materials (both inorganic and organic) has made tremendous strides in providing site-specific information about materials in recent years. However (17)O DOR has yet to demonstrate its potential in disordered materials such as glasses. In the present study, we have successfully recorded high resolution (17)O DOR spectra of vitreous B(2)O(3) (v-B(2)O(3)), a highly effective glass-forming oxide of considerable technological importance. Two distinct oxygen sites are resolved and a complete set of (17)O NMR parameters were determined from the DOR spectra. These were assigned to oxygen atoms in the planar boroxol ring [B(3)O(6)] and in the non-boroxol [BO(3)] groups which share oxygen with the ring boron atoms. This assignment was based on the similarity of all of their (17)O parameters with those found by DFT calculation for caesium enneaborate, Cs(2)O.9B(2)O(3), which has two boroxol rings in its structure. The boroxol ring oxygens have a more positive chemical shift, a larger shift anisotropy and a smaller electric field gradient than non ring oxygens (O(R): delta(iso) = 100 +/- 1 ppm, span = 180 +/- 20 ppm, skew = -0.4 +/- 0.1, P(q) = 5.0 +/- 0.2 MHz; O(NR): delta(iso) = 86 +/- 1 ppm, span = 100 +/- 20 ppm, skew = 0.1 +/- 0.1, P(q) = 5.7 +/- 0.2 MHz). The relative proportions of the two sites in v-B(2)O(3) are approximately 1 : 1, as expected if all three boron atoms in the boroxol ring are each connected to one oxygen in a linking [BO(3)] group and there are very few [BO(3)]-[BO(3)] linkages. We see no evidence for a third oxygen site such as has been reported in an earlier study of v-B(2)O(3). This work demonstrates the potential of (17)O DOR to provide site-specific information in disordered materials.

  14. Role of oxygen vacancies in HfO2-based gate stack breakdown

    NASA Astrophysics Data System (ADS)

    Wu, X.; Migas, D. B.; Li, X.; Bosman, M.; Raghavan, N.; Borisenko, V. E.; Pey, K. L.

    2010-04-01

    We study the influence of multiple oxygen vacancy traps in the percolated dielectric on the postbreakdown random telegraph noise (RTN) digital fluctuations in HfO2-based metal-oxide-semiconductor transistors. Our electrical characterization results indicate that these digital fluctuations are triggered only beyond a certain gate stress voltage. First-principles calculations suggest the oxygen vacancies to be responsible for the formation of a subband in the forbidden band gap region, which affects the triggering voltage (VTRIG) for the RTN fluctuations and leads to a shrinkage of the HfO2 band gap.

  15. Interfacial RhO{sub x}/CeO{sub 2} sites as locations for low temperature N{sub 2}O dissociation

    SciTech Connect

    Cunningham, J.; Hickey, J.N.; Soria, J.

    Temperatures required for extensive N{sub 2}O dissociation to N{sub 2}, or to N{sub 2} plus O{sub 2}, over 0.5% RhO{sub x}/CeO{sub 2} materials, and over polycrystalline Rh{sub 2}O{sub 3} or CeO{sub 2}, are compared for preoxidised and for prereduced samples on the basis of conversions achieved in pulsed-reactant, continuous-flow and recirculatory microcatalytic reactors. Influences of sample prereduction or preoxidation upon those measurements and upon results from parallel ESR and FTIR studies of N{sub 2}O interactions with such materials are presented and compared. Over partially reduced 0.5% RhO{sub x}/CeO{sub 2} materials complete dissociation of N{sub 2}O pulses to N{sub 2} plusmore » O{sub 2} is obtained at temperatures 50-100{degrees} lower than those required for extensive dissociation over prereduced Rh{sub 2}O{sub 3}. Furthermore, N{sub 2} was the sole product from the latter. Higher ongoing N{sub 2}O conversions to N{sub 2} plus O{sub 2} at 623 K over 0.5% Rh/CeO{sub 2} in pulsed-reactant than in continuous-flow mode point to regeneration of active sites under helium flushing between pulses. The TPD profile for dioxygen release from Rhodia containing samples at temperatures 350-550 K is presented. ESR measurements reveal complementary effects of outgassings at temperatures, T{sub v}, {ge} 573 K upon the availability at RhO{sub x}/CeO{sub 2} surfaces of electron-excess sites reactive towards N{sub 2}O. Differences from observations over Rh{sub 2}O{sub 3} and CeO{sub 2} can be understood by attributing the low-temperature activity of RhO{sub x}/CeO{sub 2} to electron excess sites at microinterfaces between the dispersed Rhodia component and the Ceria support.« less

  16. Site-specific 15N isotopic signatures of abiotically produced N2O

    NASA Astrophysics Data System (ADS)

    Heil, Jannis; Wolf, Benjamin; Brüggemann, Nicolas; Emmenegger, Lukas; Tuzson, Béla; Vereecken, Harry; Mohn, Joachim

    2014-08-01

    Efficient nitrous oxide (N2O) mitigation strategies require the identification of the main source and sink processes and their contribution to total soil N2O production. Several abiotic reactions of nitrification intermediates leading to N2O production are known, but their contribution to total N2O production in soils is uncertain. As the site preference (SP) of 15N in N2O is a promising tool to give more insight into N2O production processes, we investigated the SP of N2O produced by different abiotic reactions in a laboratory study. All reactions involved the nitrification intermediate hydroxylamine (NH2OH) in combination with nitrite (NO2-), Fe3+, Fe2+ and Cu2+, reactants commonly or potentially found in soils, at different concentrations and pH values. N2O production and its four main isotopic species (14N14N16O, 15N14N16O, 14N15N16O, and 14N14N18O) were quantified simultaneously and online at high temporal resolution using quantum cascade laser absorption spectroscopy. Thereby, our study presents the first continuous analysis of δ18O in N2O. The experiments revealed the possibility of purely abiotic reactions over a wide range of acidity (pH 3-8) by different mechanisms. All studied abiotic pathways produced N2O with a characteristic SP in the range of 34-35‰, unaffected by process conditions and remaining constant over the course of the experiments. These findings reflect the benefit of continuous N2O isotopic analysis by laser spectroscopy, contribute new information to the challenging source partitioning of N2O emissions from soils, and emphasize the potentially significant role of coupled biotic-abiotic reactions in soils.

  17. Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

    SciTech Connect

    Liu, Bin; Xu, Wu; Zheng, Jianming

    The temperature dependence of the oxygen reduction mechanism in Li-O 2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O 2 batteries decreases from 7,492 mAh g -1 at 40C to 2,930 mAh g -1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g -1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C tomore » 40C, the morphologies of the Li 2O 2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O 2 battery and will enable a more rational design of Li-O 2 batteries.« less

  18. Structure of (Ga2O3)2(ZnO)13 and a unified description of the homologous series (Ga2O3)2(ZnO)(2n + 1).

    PubMed

    Michiue, Yuichi; Kimizuka, Noboru; Kanke, Yasushi; Mori, Takao

    2012-06-01

    The structure of (Ga(2)O(3))(2)(ZnO)(13) has been determined by a single-crystal X-ray diffraction technique. In the monoclinic structure of the space group C2/m with cell parameters a = 19.66 (4), b = 3.2487 (5), c = 27.31 (2) Å, and β = 105.9 (1)°, a unit cell is constructed by combining the halves of the unit cell of Ga(2)O(3)(ZnO)(6) and Ga(2)O(3)(ZnO)(7) in the homologous series Ga(2)O(3)(ZnO)(m). The homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) is derived and a unified description for structures in the series is presented using the (3+1)-dimensional superspace formalism. The phases are treated as compositely modulated structures consisting of two subsystems. One is constructed by metal ions and another is by O ions. In the (3 + 1)-dimensional model, displacive modulations of ions are described by the asymmetric zigzag function with large amplitudes, which was replaced by a combination of the sawtooth function in refinements. Similarities and differences between the two homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) and Ga(2)O(3)(ZnO)(m) are clarified in (3 + 1)-dimensional superspace. The validity of the (3 + 1)-dimensional model is confirmed by the refinements of (Ga(2)O(3))(2)(ZnO)(13), while a few complex phenomena in the real structure are taken into account by modifying the model.

  19. Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

    NASA Technical Reports Server (NTRS)

    Camy-Peyret, C.; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

    1993-01-01

    Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44 N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/cm band. Assuming a total intensity of 4.32 x 10 exp -17 cm/molecule/sq cm independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv, interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated 1-sigma uncertainty including the error in the total band intensity. The retrieved profiles are compared with previous measurements and photochemical model results.

  20. Microhabitat Effects on N2O Emissions from Floodplain Soils under Controlled Conditions

    NASA Astrophysics Data System (ADS)

    Ley, Martin; Lehmann, Moritz F.; Niklaus, Pascal A.; Kuhn, Thomas; Luster, Jörg

    2016-04-01

    Semi-terrestrial soils such as floodplain soils are considered to be potential hotspots of nitrous oxide (N2O) emissions. The quantitative assessment of N2O release from these hotspots under field conditions, and of the microbial pathways that underlie net N2O production (ammonium oxidation, nitrifier-denitrification, and denitrification) is challenging because of their high spatial and temporal variability. The production and consumption of N2O appears to be linked to the presence or absence of micro-niches, providing specific conditions that may be favorable to either of the relevant microbial pathways. Flood events have been shown to trigger moments of enhanced N2O emission through a close coupling of niches with high and low oxygen availabilities. This coupling might be modulated by microhabitat effects related to soil aggregate formation, root soil interactions and the degradation of organic matter accumulations. In order to assess how these factors can modulate N2O production and consumption under simulated flooding/drying conditions, we have set up a mesocosm experiment with N-rich floodplain soils comprising different combinations of soil aggregate size classes and inert matrix material. These model soils were either planted with basket willow (Salix viminalis L.), mixed with leaf litter, or left untreated. Throughout a simulated flood event, we repeatedly measured the net N2O production rate. In addition, soil water content, redox potential, as well as C and N substrate availability were monitored. In order to gain insight into the sources of, and biogeochemical controls on N2O production, we also measured the bulk δ15N signature of the produced N2O, as well as its intramolecular 15N site preference (SP). In this presentation we focus on a period of enhanced N2O emission during the drying phase after 48 hrs of flooding. We will discuss the observed emission patterns in the context of possible treatment effects. Soils with large aggregates showed a

  1. Effects of oxygen vacancies on the structural and optical properties of β-Ga2O3

    PubMed Central

    Dong, Linpeng; Jia, Renxu; Xin, Bin; Peng, Bo; Zhang, Yuming

    2017-01-01

    The structural, electronic, and optical properties of β-Ga2O3 with oxygen vacancies are studied by employing first-principles calculations based on density function theory. Based on the defects formation energies, we conclude the oxygen vacancies are most stable in their fully charge states. The electronic structures and optical properties of β-Ga2O3 are calculated by Generalized Gradient Approximation + U formalisms with the Hubbard U parameters set 7.0 eV and 8.5 eV for Ga and O ions, respectively. The calculated bandgap is 4.92 eV, which is consistent with the experimental value. The static real dielectric constants of the defective structures are increased compared with the intrinsic one, which is attributed to the level caused by the Ga-4s states in the bandgap. Extra peaks are introduced in the absorption spectra, which are related to Ga-4s and O-2p states. Experimentally, β-Ga2O3 films are deposited under different O2 volume percentage with ratio-frequency magnetron sputtering method. The measured results indicate that oxygen vacancies can induce extra emission peaks in the photoluminescence spectrum, the location of these peaks are close to the calculated results. Extra O2 can increase the formation energies of oxygen vacancies and thus reduce oxygen vacancies in β-Ga2O3. PMID:28065936

  2. Effects of oxygen vacancies on the structural and optical properties of β-Ga2O3.

    PubMed

    Dong, Linpeng; Jia, Renxu; Xin, Bin; Peng, Bo; Zhang, Yuming

    2017-01-09

    The structural, electronic, and optical properties of β-Ga 2 O 3 with oxygen vacancies are studied by employing first-principles calculations based on density function theory. Based on the defects formation energies, we conclude the oxygen vacancies are most stable in their fully charge states. The electronic structures and optical properties of β-Ga 2 O 3 are calculated by Generalized Gradient Approximation + U formalisms with the Hubbard U parameters set 7.0 eV and 8.5 eV for Ga and O ions, respectively. The calculated bandgap is 4.92 eV, which is consistent with the experimental value. The static real dielectric constants of the defective structures are increased compared with the intrinsic one, which is attributed to the level caused by the Ga-4s states in the bandgap. Extra peaks are introduced in the absorption spectra, which are related to Ga-4s and O-2p states. Experimentally, β-Ga 2 O 3 films are deposited under different O 2 volume percentage with ratio-frequency magnetron sputtering method. The measured results indicate that oxygen vacancies can induce extra emission peaks in the photoluminescence spectrum, the location of these peaks are close to the calculated results. Extra O 2 can increase the formation energies of oxygen vacancies and thus reduce oxygen vacancies in β-Ga 2 O 3 .

  3. N2O emissions from a nitrogen-enriched river

    USGS Publications Warehouse

    McMahon, P.B.; Dennehy, K.F.

    1999-01-01

    Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994- 1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2 x 1013-6 x 1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal wastewater treatment processes in the United States (1). Results from this study indicate that N-enriched rivers could be important anthropogenic sources of N2O to the atmosphere. However, N2O emission measurements from other N-enriched rivers are needed to better quantify this source.Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994-1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2??1013-6??1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal

  4. Stratospheric N2O5, CH4, and N2O Profiles from IR Solar Occultation Spectra

    NASA Technical Reports Server (NTRS)

    Peyeret, C. Camy; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

    1993-01-01

    Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/ cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur I'Adour, France (44 deg N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/ cm band. Assuming a total intensity of 4.32 x 10(exp 17)cm(exp -1) molecule sq cm(exp -2) independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv (parts per billion by volume, 10(exp -9)), interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated I-sigma uncertainty including the error in the total band intensity (+/- 20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.

  5. Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

    NASA Astrophysics Data System (ADS)

    Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

    2012-08-01

    Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the

  6. Overlap corrections for emissivity calculations of H2O-CO2-CO-N2 mixtures

    NASA Astrophysics Data System (ADS)

    Alberti, Michael; Weber, Roman; Mancini, Marco

    2018-01-01

    Calculations of total gas emissivities of gas mixtures containing several radiatively active species require corrections for band overlapping. In this paper, we generate such overlap correction charts for H2O-CO2-N2, H2O-CO-N2, and CO2-CO-N2 mixtures. These charts are applicable in the 0.1-40 bar total pressure range and in the 500 K-2500 K temperature range. For H2O-CO2-N2 mixtures, differences between our charts and Hottel's graphs as well as models of Leckner and Modak are highlighted and analyzed.

  7. Intermixing and thermal oxidation of ZrO2 thin films grown on a-Si, SiN, and SiO2 by metallic and oxidic mode magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Coloma Ribera, R.; van de Kruijs, R. W. E.; Sturm, J. M.; Yakshin, A. E.; Bijkerk, F.

    2017-03-01

    The initial growth of DC sputtered ZrO2 on top of a-Si, SiN, and SiO2 layers has been studied by in vacuo high-sensitivity low energy ion scattering for two gas deposition conditions with different oxygen contents (high-O and low-O conditions). This unique surface sensitive technique allowed the determination of surface composition and thicknesses required to close the ZrO2 layer on all three substrates for both conditions. The ZrO2 layer closes similarly on all substrates due to more favorable enthalpies of formation for ZrO2 and ZrSiO4, resulting in passivation of the Si from the substrate. However, this layer closes at about half of the thickness (˜1.7 nm) for low-O conditions due to less oxidative conditions and less energetic particles arriving at the sample, which leads to less intermixing via silicate formation. In contrast, for high-O conditions, there is more ZrSiO4 and/or SiOx formation, giving more intermixing (˜3.4 nm). In vacuo X-ray photoelectron spectroscopy (XPS) measurements revealed similar stoichiometric ZrO2 layers deposited by both conditions and a higher interaction of the ZrO2 layer with the underlying a-Si for high-O conditions. In addition, oxygen diffusion through low-O ZrO2 films on a-Si has been investigated by ex situ angular-resolved XPS of samples annealed in atmospheric oxygen. For temperatures below 400 °C, no additional oxidation of the underlying a-Si was observed. This, together with the amorphous nature and smoothness of these samples, makes ZrO2 a good candidate as an oxidation protective layer on top of a-Si.

  8. Properties of Structurally Excellent N-doped TiO2 Rutile

    SciTech Connect

    Chambers, Scott A.; Cheung, Sau H.; Shutthanandan, V.

    2007-10-15

    We have used plasma-assisted molecular beam epitaxy to synthesize structurally near-perfect crystalline films of TiO2-xNx rutile for the first time. These materials allow the properties of TiO2-xNx to be elucidated without the interfering effects of oxygen vacancy defects. In the absence of such defects, the extent of N incorporation in the lattice is limited to 2 ± 1 at. % of the anions. Substitutional N (NO) exhibits a -3 formal charge due to charge transfer from shallow-donor interstitial Ti(III), which forms during epitaxial growth. Hybridization between NO and adjacent lattice Ti ions occurs, resulting in new states off the topmore » of the rutile valence band and an apparent band gap reduction of ~ 0.5 eV. It is not yet known if these new states result in mobile electron-hole pair creation upon irradiation, but experiments are planned to answer this important question.« less

  9. Measurements of Enthalpy of Sublimation of Ne, N2, O2, Ar, CO2, Kr, Xe, and H2O using a Double Paddle Oscillator.

    PubMed

    Shakeel, Hamza; Wei, Haoyan; Pomeroy, Joshua M

    2018-03-01

    We report precise experimental values of the enthalpy of sublimation (Δ H s ) of quenched condensed films of neon (Ne), nitrogen (N 2 ), oxygen (O 2 ), argon (Ar), carbon dioxide (CO 2 ), krypton (Kr), xenon (Xe), and water (H 2 O) vapor using a single consistent measurement platform. The experiments are performed well below the triple point temperature of each gas and fall in the temperature range where existing experimental data is very limited. A 6 cm 2 and 400 µm thick double paddle oscillator (DPO) with high quality factor (Q ≈ 4 × 10 5 at 298K) and high frequency stability (33 parts per billion) is utilized for the measurements. The enthalpies of sublimation are derived by measuring the rate of mass loss during temperature programmed desorption. The mass change is detected due to change in the resonance frequency of the self-tracking oscillator. Our measurements typically remain within 10% of the available literature, theory, and National Institute of Standards and Technology (NIST) Web Thermo Tables ( WTT ) values, but are performed using an internally consistent method across different gases.

  10. Effects of N2-O2 and CO2-O2 Tensions on Growth of Fungi Isolated from Damaged Flue-Cured Tobacco 1

    PubMed Central

    Yang, H.; Lucas, G. B.

    1970-01-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N2-O2 or CO2-O2. A 1 to 5% concentration of O2 in an N2 atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O2 for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O2. High O2 concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O2 in the N2 atmosphere, furrows formed in mycelial mats between 5 and 40% O2 in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O2 decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO2-O2 mixtures radial growth of all species increased with each quantitative decrease of CO2. All species except A. niger grew faster in air than in 10% CO2. In contrast to N2-O2 mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O2 concentrations. PMID:5461786

  11. Oxidation of primary amines to oximes with molecular oxygen using 1,1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts.

    PubMed

    Suzuki, Ken; Watanabe, Tomonari; Murahashi, Shun-Ichi

    2013-03-15

    The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.

  12. Heterojunction p-Cu2O/n-Ga2O3 diode with high breakdown voltage

    NASA Astrophysics Data System (ADS)

    Watahiki, Tatsuro; Yuda, Yohei; Furukawa, Akihiko; Yamamuka, Mikio; Takiguchi, Yuki; Miyajima, Shinsuke

    2017-11-01

    Heterojunction p-Cu2O/n-β-Ga2O3 diodes were fabricated on an epitaxially grown β-Ga2O3(001) layer. The reverse breakdown voltage of these p-n diodes reached 1.49 kV with a specific on-resistance of 8.2 mΩ cm2. The leakage current of the p-n diodes was lower than that of the Schottky barrier diode due to the higher barrier height against the electron. The ideality factor of the p-n diode was 1.31. It indicated that some portion of the recombination current at the interface contributed to the forward current, but the diffusion current was the dominant. The forward current more than 100 A/cm2 indicated the lower conduction band offset at the hetero-interface between Cu2O and Ga2O3 layers than that predicted from the bulk properties, resulting in such a high forward current without limitation. These results open the possibility of advanced device structures for wide bandgap Ga2O3 to achieve higher breakdown voltage and lower on-resistance.

  13. Fundamental Insulation Characteristics of Air, N2, CO2, N2/O2 and SF6/N2 Mixed Gases

    NASA Astrophysics Data System (ADS)

    Rokunohe, Toshiaki; Yagihashi, Yoshitaka; Endo, Fumihiro; Oomori, Takashi

    SF6 gas has excellent dielectric strength and interruption performance. For these reasons, it has been widely used for gas insulated switchgear (GIS). However, use of SF6 gas has become regulated under agreements set at the 1997 COP3. Presently, development of a gas circuit breaker (GCB) using CO2 gas and development of a high voltage vacuum circuit breaker (VCB) are being pursued. GIS consists of disconnectors (DS), earthing switches (ES) and buses in addition to GCB. Since the interruption performance is not an important requirement for DS, ES and BUS, use of a gas with high dielectric strength is better than use of a gas with good interruption performance. Air and N2 are not greenhouse gases, and their dielectric strengths are higher than those of other SF6 alternative gases, but only about one-third of the dielectric strength of SF6 gas. This paper deals with a suitable insulation gas which has no greenhouse effect as an SF6 alternative gas. The N2/O2 mixed gas was investigated by changing the ratio of O2. Moreover, the effect of an insulation coating was investigated and compared with the dielectric strength of SF6/N2 mixed gas. The dielectric strength of air under the coating condition was equal to that of 10%SF6/N2 mixed gas.

  14. Carbon-doped boron nitride nanosheet as a promising catalyst for N2O reduction by CO or SO2 molecule: A comparative DFT study

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Saeidi, Nasibeh

    2018-06-01

    We report for the first time, the catalytic activity of the experimentally available carbon-doped boron nitride nanosheet (C-BNNS) towards the reduction of N2O in the presence of CO or SO2 molecule. According to our density functional theory calculations, C-doping can introduce high spin density into BN monolayer which is mainly localized over the C and its neighboring N atoms. The Hirshfeld charge density analysis reveals that the electron-rich C-BNNS acts as an electron donating support to activate N2O molecule which is an important step in the reduction of N2O. The N2O reduction reaction starts with the dissociative adsorption of N2O over the C-BNNS surface, yielding the N2 molecule and an activated oxygen moiety (Oads) adsorbed over the C atom. The reaction then proceeds via the elimination of Oads by a CO or SO2 molecule. The obtained low activation energies clearly indicate that the metal-free C-BNNS surface can be regarded as a highly active catalyst for the reduction of N2O. The results of this study may open new avenues in searching low cost and highly active BN-based catalysts for low temperature reduction of N2O.

  15. N2O fluxes at the soil-atmosphere interface in various ecosystems and the global N2O budget

    NASA Technical Reports Server (NTRS)

    Banin, Amos

    1987-01-01

    The overall purpose of this research task is to study the effects of soil properties and ecosystem variables on N2O exchanges at the soil-atmosphere interface, and to assess their effects on the globle N2O budget. Experimental procedures are implemented in various sites to measure the source/sink relations of N2O at the soil-atmosphere interface over prolonged periods of time as part of the research of biogeochemical cycling in terrestrial ecosystems. A data-base for establishing quantitative correlations between N2O fluxes and soil and environmental parameters that are of potential use for remote sensing, is being developed.

  16. Detection of interstellar N2O: A new molecule containing an N-O bond

    NASA Technical Reports Server (NTRS)

    Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

    1994-01-01

    A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is N(sub tot) approx. 10(exp 15)/sq. cm, which corresponds to a fractional abundance of approx. 10(exp -9), relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

  17. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  18. Study of the Photodynamic Activity of N-Doped TiO2 Nanoparticles Conjugated with Aluminum Phthalocyanine

    PubMed Central

    Pan, Xiaobo; Liang, Xinyue; Yao, Longfang; Wang, Xinyi; Jing, Yueyue; Fei, Yiyan; Chen, Li

    2017-01-01

    TiO2 nanoparticles modified with phthalocyanines (Pc) have been proven to be a potential photosensitizer in the application of photodynamic therapy (PDT). However, the generation of reactive oxygen species (ROS) by TiO2 nanoparticles modified with Pc has not been demonstrated clearly. In this study, nitrogen-doped TiO2 conjugated with Pc (N-TiO2-Pc) were studied by means of monitoring the generation of ROS. The absorbance and photokilling effect on HeLa cells upon visible light of different regions were also studied and compared with non-doped TiO2-Pc and Pc. Both N-TiO2-Pc and TiO2-Pc can be activated by visible light and exhibited much higher photokilling effect on HeLa cells than Pc. In addition, nitrogen-doping can greatly enhance the formation of 1O2 and •O2−, while it suppresses the generation of OH•. This resulted in significant photodynamic activity. Therefore, N-TiO2-Pc can be an excellent candidate for a photosensitizer in PDT with wide-spectrum visible irradiation. PMID:29053580

  19. Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

    PubMed

    Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

    2018-03-27

    Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all

  20. Multi-yolk-shell SnO2/Co3Sn2@C Nanocubes with High Initial Coulombic Efficiency and Oxygen Reutilization for Lithium Storage.

    PubMed

    Su, Liwei; Xu, Yawei; Xie, Jian; Wang, Lianbang; Wang, Yuanhao

    2016-12-28

    The challenging problems of SnO 2 anode material for lithium ion batteries are the poor electronic conductivity and the low oxygen reutilization due to the irreversibility of Li 2 O generated in the initial discharge leading to a theoretical initial Coulombic efficiency (ICE) of only 52.4%. Different from these strategies, this work proposes a novel strategy to level up the oxygen reutilization in SnO 2 by introducing Co 3 Sn 2 nanoalloys which can release Co atoms to reversibly react with Li 2 O instead. According to this protocol, multi-yolk-shell SnO 2 /Co 3 Sn 2 @C nanocubes are designed and successfully prepared using hollow CoSn(OH) 6 nanocubes as precursors followed a hydrothermal carbon coating and calcination treatment. The unique multi-yolk-shell nanostructure offers adequate breathing space for the volumetric deformation during long-term cycling. Moreover, the removal of Li 2 O allows a high electronic conductivity and resultant rate performance. As a result, the efficient reutilization of oxygen enables a high ICE of 71.7% and a reversible capacity of 1003 mA h g -1 after 200 cycles at 100 mA g -1 . Cyclic voltammetry, cycling performance at different voltage windows, and X-ray photoelectron spectroscopy confirm the proposed mechanism. This strategy employing oxygen-poor metals or alloys provides a novel approach to enhance the oxygen reutilization in SnO 2 for higher reversibility.

  1. A photoelectron spectroscopy and quantum chemical study on ternary Al-B-O clusters: AlnBO2- and AlnBO2 (n = 2, 3).

    PubMed

    Ou, Ting; Feng, Yuan; Tian, Wen-Juan; Zhao, Li-Juan; Kong, Xiang-Yu; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin

    2018-02-14

    Both B and Al have high oxygen affinity and their oxidation processes are highly exothermic, hinting at intriguing physical chemistry in ternary Al-B-O clusters. We report a combined photoelectron spectroscopy and density-functional study on the structural, electronic, and bonding properties of Al n BO 2 - and Al n BO 2 (n = 2, 3) clusters. Ground-state vertical detachment energies (VDEs) are measured to be 2.83 and 2.24 eV for Al 2 BO 2 - and Al 3 BO 2 - , respectively. A weak isomer is also observed for Al 3 BO 2 - with a VDE of 1.31 eV. Coalescence-kick global searches allow the identification of candidate structures, confirmed via comparisons with experiment. The Al 2 BO 2 - anion is V-shaped in geometry, C s ( 1 A'), with an Al center connecting to OB and OAl terminals. It can be viewed alternatively as the fusion of BOAl and AlOAl by sharing an Al atom. Al 3 BO 2 - has a C s ( 2 A'') global minimum in which an Al 2 dimer interacts with bridging boronyl (BO) and an OAl unit, as well as a low-lying C 2v ( 2 B 2 ) isomer consisting of boronyl and OAl that are doubly bridged by two Al atoms. The BO 2 block (linear O[double bond, length as m-dash]B[double bond, length as m-dash]O chain) is nonexistent in any of the anion and neutral species. Chemical bonding in these Al-B-O clusters is elucidated via canonical molecular orbitals and adaptive natural density partitioning. The cluster structures are also rationalized using the concept of sequential and competitive oxidation of B versus Al centers in Al n B. The first O atom prefers to oxidize B and form BO, whereas the second O atom has options to interact with a fresh Al/Al n /Al n B unit or a BO group. The former route wins thermodynamically, leading to the observed geometries.

  2. 2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

    SciTech Connect

    Prhavc, M.; Prakash, T.P.; Minasov, G.

    Oligonucleotides with a novel, 2'-O-[2-[2-(N,N-dimethylamino)ethoxy]ethyl] (2'-O-DMAEOE) modification have been synthesized. This modification, a cationic analogue of the 2'-O-(2-methoxyethyl) (2'-O-MOE) modification, exhibits high binding affinity to target RNA (but not to DNA) and exceptional resistance to nuclease degradation. Analysis of the crystal structure of a self-complementary oligonucleotide containing a single 2'-O-DMAEOE modification explains the importance of charge factors and gauche effects on the observed antisense properties. 2'-O-DMAEOE modified oligonucleotides are ideal candidates for antisense drugs.

  3. Facile Aluminum Reduction Synthesis of Blue TiO2 with Oxygen Deficiency for Lithium-Ion Batteries.

    PubMed

    Zheng, Jing; Ji, Guangbin; Zhang, Peng; Cao, Xingzhong; Wang, Baoyi; Yu, Linghui; Xu, Zhichuan J

    2015-12-07

    An ultrafacile aluminum reduction method is reported herein for the preparation of blue TiO2 nanoparticles (donated as Al-TiO2 , anatase phase) with abundant oxygen deficiency for lithium-ion batteries. Under aluminum reduction, the morphology of the TiO2 nanosheets changes from well-defined rectangular into uniform round or oval nanoparticles and the particle size also decreases from 60 to 31 nm, which can aggressively accelerate the lithium-ion diffusion. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) results reveal that plentiful oxygen deficiencies relative to the Ti(3+) species were generated in blue Al-TiO2 ; this effectively enhances the electron conductivity of the TiO2 . X-ray photoelectron spectrometry (XPS) analysis indicates that a small peak is observed for the Al-O bond, which probably plays a very important role in the stabilization of the oxygen deficiencies/Ti(3+) species. As a result, the blue Al-TiO2 possesses significantly higher capacity, better rate performance, and a longer cycle life than the white pure TiO2 . Such improvements can be attributed to the decreased particle size, as well as the existence of the oxygen deficiencies/Ti(3+) species. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr)

    SciTech Connect

    Jeamjumnunja, Kannika; Gong, Wenquan; Makarenko, Tatyana

    The A-site ordered double-perovskite oxides, LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn{sub 2}O{sub 5+δ}. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn{sub 2}O{sub 5+δ}. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln{sup 3+} ions larger than Y{sup 3+}. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn{submore » 2}O{sub 5} and fully-oxidized LnBaMn{sub 2}O{sub 6} during changes of the oxygen partial pressure between air and 1.99% H{sub 2}/Ar. In addition, the oxygen non-stoichiometries of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} were determined as a function of pO{sub 2} at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching ~6. The stabilities of the LnBaMn{sub 2}O{sub 5+δ} phases extend over a wide range of oxygen partial pressures (∼10{sup −25}≤pO{sub 2} (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln{sup 3+} cation the lower pO{sub 2} for phase conversion. At some temperatures and pO{sub 2} conditions, the LnBaMn{sub 2}O{sub 5+δ} compounds are unstable with respect to decomposition to BaMnO{sub 3−δ} and LnMnO{sub 3}. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions. - Graphical abstract: Structure of Ln

  5. Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2.

    PubMed

    Perevalov, T V; Islamov, D R; Gritsenko, V A; Prosvirin, I P

    2018-05-11

    The electronic structure of oxygen-deficient Hf 0.5 Zr 0.5 O 2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf 0.5 Zr 0.5 O 2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf 0.5 Zr 0.5 O 2 : an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf 0.5 Zr 0.5 O 2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

  6. Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2

    NASA Astrophysics Data System (ADS)

    Perevalov, T. V.; Islamov, D. R.; Gritsenko, V. A.; Prosvirin, I. P.

    2018-05-01

    The electronic structure of oxygen-deficient Hf0.5Zr0.5O2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf0.5Zr0.5O2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf0.5Zr0.5O2: an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf0.5Zr0.5O2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

  7. Thermal O-H Bond Activation of Water as Mediated by Heteronuclear [Al2Mg2O5]•+: Evidence for Oxygen-Atom Scrambling.

    PubMed

    Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schwarz, Helmut

    2018-06-25

    Mechanistic insight into the thermal O-H bond activation of water by the cubane-like, prototypical heteronuclear oxide cluster [Al 2 Mg 2 O 5 ] •+ has been derived from a combined experimental/computational study. Experiments in the highly diluted gas phase using Fourier transform ion-cyclotron resonance mass spectrometry show that hydrogen-atom abstraction from water by the cluster cation [Al 2 Mg 2 O 5 ] •+ occurs at ambient conditions accompanied by the liberation of an OH • radical. Due to a complete randomization of all oxygen atoms prior to fragmentation about 83% of the oxygen atoms of the hydroxyl radical released originate from the oxide cluster itself. The experimental findings are supported by detailed high-level quantum chemical calculations. The theoretical analysis reveals that the transfer of a formal hydrogen atom from water to the metal-oxide cation can proceed mechanistically via proton- or hydrogen-atom transfer exploiting different active sites of the cluster oxide. In addition to the unprecedented oxygen-atom scrambling, one of the more general and quite unexpected findings concerns the role of spin density at the hydrogen-acceptor oxide atom. While this feature is so crucial for [M-O] + /CH 4 couples, it is much less important in the O-H bond activation of water.

  8. Burning of CP Titanium (Grade 2) in Oxygen-Enriched Atmospheres

    NASA Technical Reports Server (NTRS)

    Stoltzfus, Joel M.; Jeffers, Nathan; Gallus, Timothy D.

    2012-01-01

    The flammability in oxygen-enriched atmospheres of commercially pure (CP) titanium rods as a function of diameter and test gas pressure was determined. Test samples of varying diameters were ignited at the bottom and burned upward in 70% O2/balance N2 and in 99.5+% O2 at various pressures. The burning rate of each ignited sample was determined by observing the apparent regression rate of the melting interface (RRMI) of the burning samples. The burning rate or RRMI increased with decreasing test sample diameter and with increasing test gas pressure and oxygen concentration

  9. Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

    NASA Astrophysics Data System (ADS)

    Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

    2018-06-01

    Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

  10. Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

    PubMed

    Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

    2010-02-28

    A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

  11. FeO2 and FeOOH under deep lower-mantle conditions and Earth's oxygen-hydrogen cycles.

    PubMed

    Hu, Qingyang; Kim, Duck Young; Yang, Wenge; Yang, Liuxiang; Meng, Yue; Zhang, Li; Mao, Ho-Kwang

    2016-06-09

    The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.

  12. Photocatalytic hydrogen production from water-methanol mixtures using N-doped Sr2Nb2O7 under visible light irradiation: effects of catalyst structure.

    PubMed

    Ji, Sang Min; Borse, Pramod H; Kim, Hyun Gyu; Hwang, Dong Won; Jang, Jum Suk; Bae, Sang Won; Lee, Jae Sung

    2005-03-21

    Nitrogen-doped perovskite type materials, Sr2Nb2O7-xNx (0, 1.5 < x < 2.8), have been studied as visible light-active photocatalysts for hydrogen production from methanol-water mixtures. Nitrogen doping in Sr2Nb2O7 red-shifted the light absorption edge into the visible light range and induced visible light photocatalytic activity. There existed an optimum amount of nitrogen doping that showed the maximum rate of hydrogen production. Among the potential variables that might cause this activity variation, the crystal structure appeared to be the most important. Thus, as the extent of N-doping increased, the original orthorhombic structure of the layered perovskite was transformed into an unlayered cubic oxynitride structure. The most active catalytic phase was an intermediate phase still maintaining the original layered perovskite structure, but with a part of its oxygen replaced by nitrogen and oxygen vacancy to adjust the charge difference between oxygen and doped nitrogen. These experimental observations were explained by density functional theory calculations. Thus, in Sr2Nb2O7-xNx, N2p orbital was the main contributor to the top of the valence band, causing band gap narrowing while the bottom of conduction band due to Nb 4d orbital remained almost unchanged.

  13. Ab initio molecular dynamics determination of competitive O 2 vs. N 2 adsorption at open metal sites of M 2 (dobdc)

    DOE PAGES

    Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; ...

    2016-04-04

    The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O 2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O 2 and N 2 in the M 2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize themore » process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.« less

  14. Detection of interstellar N2O: A new molecule containing an N-O bond

    NASA Astrophysics Data System (ADS)

    Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

    1994-12-01

    A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is Ntot approx. 1015/sq. cm, which corresponds to a fractional abundance of approx. 10-9, relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

  15. A novel 15N tracer approach for the quantification of N2 and N2O emissions from soil incubations in a completely automated laboratory set up

    NASA Astrophysics Data System (ADS)

    Scheer, Clemens; Dannenmann, Michael; Meier, Rudolf

    2015-04-01

    The microbial mediated production of nitrous oxide (N2O) and its reduction to dinitrogen (N2) via denitrification represents a loss of nitrogen (N) from fertilised agro-ecosystems to the atmosphere. Although denitrification has received great interest by biogeochemists in the last decades, the magnitude of N2lossesand related N2:N2O ratios from soils still are largely unknown due to methodical constraints. We present a novel 15N tracer approach, based on a previous developed tracer method to study denitrification in pure bacterial cultures which was modified for the use on soil incubations in a completely automated laboratory set up. The method uses a background air in the incubation vessels that is replaced with a helium-oxygen gas mixture with a 50-fold reduced N2 background (2 % v/v). This method allows for a direct and sensitive quantification of the N2 and N2O emissions from the soil with isotope-ratio mass spectrometry after 15N labelling of denitrification N substrates and minimises the sensitivity to the intrusion of atmospheric N2 at the same time. The incubation set up was used to determine the influence of different soil moisture levels on N2 and N2O emissions from a sub-tropical pasture soil in Queensland/Australia. The soil was labelled with an equivalent of 50 μg-N per gram dry soil by broadcast application of KNO3solution (4 at.% 15N) and incubated for 3 days at 80% and 100% water filled pore space (WFPS), respectively. The headspace of the incubation vessel was sampled automatically over 12hrs each day and 3 samples (0, 6, and 12 hrs after incubation start) of headspace gas analysed for N2 and N2O with an isotope-ratio mass spectrometer (DELTA V Plus, Thermo Fisher Scientific, Bremen, Germany(. In addition, the soil was analysed for 15N NO3- and NH4+ using the 15N diffusion method, which enabled us to obtain a complete N balance. The method proved to be highly sensitive for N2 and N2O emissions detecting N2O emissions ranging from 20 to 627 μN kg

  16. Effects of Carbon and Cover Crop Residues on N2O and N2 Emissions

    NASA Astrophysics Data System (ADS)

    Burger, M.; Cooperman, Y.; Horwath, W. R.

    2016-12-01

    In Mediterranean climate, nitrous oxide emissions occurring with the first rainfall after the dry summer season can contribute up to 50% of agricultural systems' total annual emissions, but the drivers of these emissions have not been clearly identified, and there are only few measurements of atmospheric nitrogen (N2) production (denitrification) during these events. In lab incubations, we investigated N2O and N2 production, gross ammonification and nitrification, and microbial N immobilization with wet-up in soil from a vineyard that was previously fallow or where cover crop residue had been incorporated the previous spring. Before the first rainfall, we measured 120 mg dissolved organic carbon (DOC-C) kg-1 soil in the 0-5 cm layer of this vineyard, and after the rain 10 mg DOC-C kg-1, while nitrate levels before the rain were <5 mg N kg-1 in fallow and <10 mg N kg-1 in previously cover cropped soil. The N2O/N2 production was 2, 7, 9, and 86% in fallow, legume-grass mixture, rye, and legume cover cropped soil. The N2O/N2 ratio tended to increase with lower DOC (post-rain) levels in the soil. The results suggest that accumulated carbon in dry surface soil is the main driving factor of N2O and N2 emissions through denitrification with the first rainfall after prolonged dry periods.

  17. Oxygen mobility in CeO{sub 2} and Ce{sub x}Zr({sub 1-x})O{sub 2} compounds: Study by CO transient oxidation and {sup 18}O/{sup 16}O isotopic exchange

    SciTech Connect

    Madier, Y.; Descorme, C.; Govic, A.M. Le

    Cerium-zirconium mixed oxides (Ce{sub x}Zr{sub 1{minus}x}O{sub 2}), precalcined at 900 C in dry air, were supplied by Rhodia Terres Rares as monophasic solid solutions. Introduction of some zirconium atoms in the ceria lattice by isomorphous substitution clearly influences the final properties of these materials as long as the cubic structure of ceria is maintained. Modifications in oxygen storage capacity (OSC measurements), redox properties (CO TPR), and oxygen exchange processes (TPIE) were studied. Ce{sub 0.63}Zr{sub 0.37}O{sub 2} was shown to have the most promising properties with the largest OSC at 400 C and the highest reactivity in O{sub 2} exchange. Allmore » mixed oxides are able to exchange very large amounts of oxygen compared to ceria, implying the participation of bulk oxygen. Furthermore, on Ce{sub x}Zr{sub (1{minus}x)}O{sub 2} samples, oxygen is predominantly exchanged via a multiple heteroexchange mechanism involving surface dioxygen species as superoxides or peroxides.« less

  18. In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

    PubMed

    Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

    2018-06-13

    We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

  19. Equation of state for Eu-doped SrSi2O2N2

    NASA Astrophysics Data System (ADS)

    Ermakova, Olga; Paszkowicz, Wojciech; Kaminska, Agata; Barzowska, Justyna; Szczodrowski, Karol; Grinberg, Marek; Minikayev, Roman; Nowakowska, Małgorzata; Carlson, Stefan; Li, Guogang; Liu, Ru-Shi; Suchocki, Andrzej

    2014-07-01

    α-SrSi2O2N2 is one of the recently studied oxonitridosilicates applicable in optoelectronics, in particular in white LEDs. Its elastic properties remain unknown. A survey of literature shows that, up to now, nine oxonitridosilicate materials have been identified. For most of these compounds, doped with rare earths and manganese, a luminescence has been reported at a wavelength characteristic for the given material; all together cover a broad spectral range. The present study focuses on the elastic properties of one of these oxonitridosilicates, the Eu-doped triclinic α-SrSi2O2N2. High-pressure powder diffraction experiments are used in order to experimentally determine, for the first time, the equation of state of this compound. The in situ experiment was performed for pressures ranging up to 9.65 GPa, for Eu-doped α-SrSi2O2N2 sample mounted in a diamond anvil cell ascertaining the hydrostatic compression conditions. The obtained experimental variation of volume of the triclinic unit cell of α-SrSi2O2N2:Eu with rising pressure served for determination of the Birch-Murnaghan equation of state. The determined above quoted bulk modulus is 103(5) GPa, its first derivative is 4.5(1.1). The above quoted bulk modulus value is found to be comparable to that of earlier reported oxynitrides of different composition.

  20. Effect of watershed urbanization on N2O emissions from the Chongqing metropolitan river network, China

    NASA Astrophysics Data System (ADS)

    He, Yixin; Wang, Xiaofeng; Chen, Huai; Yuan, Xingzhong; Wu, Ning; Zhang, Yuewei; Yue, Junsheng; Zhang, Qiaoyong; Diao, Yuanbin; Zhou, Lilei

    2017-12-01

    Watershed urbanization, an integrated anthropogenic perturbation, is another considerable global concern in addition to that of global warming and may significantly enrich the N loadings of watersheds, which then greatly influences the nitrous oxide (N2O) production and fluxes of these aquatic systems. However, little is known about the N2O dynamics in human-dominated metropolitan river networks. In this study, we present the temporal and spatial variations in N2O saturation and emission in the Chongqing metropolitan river network, which is undergoing intensified urbanization. The N2O saturation and fluxes at 84 sampling sites ranged from 126% to 10536% and from 4.5 to 1566.8 μmol N2O m-2 d-1, with means of 1780% and 261 μmol N2O m-2 d-1. The riverine N2O saturation and fluxes increased along with the urbanization gradient and urbanization rate, with disproportionately higher values in urban rivers due to the N2O-rich sewage inputs and enriched in situ N substrates. We found a clear seasonal pattern of N2O saturation, which was co-regulated by both water temperature and precipitation. Regression analysis indicated that the N substrates and dissolved oxygen (DO) that controlled nitrogen metabolism acted as good predictors of the N2O emissions of urban river networks. Particularly, phosphorus (P) and hydromorphological factors (water velocity, river size and bottom substrate) had stronger relationships with the N2O saturation and could also be used to predict the N2O emission hotspots in regions with rapid urbanization. In addition, the default emission factors (EF5-r) used in the Intergovernmental Panel on Climate Change (IPCC) methodology may need revision given the differences among the physical and chemical factors in different rivers, especially urban rivers.

  1. Complete Decomposition of Li 2 CO 3 in Li–O 2 Batteries Using Ir/B 4 C as Noncarbon-Based Oxygen Electrode

    SciTech Connect

    Song, Shidong; Xu, Wu; Zheng, Jianming

    Incomplete decomposition of Li2CO3 during charge process is a critical barrier for rechargeable Li-O2 batteries. Here we report complete decomposition of Li2CO3 in Li-O2 batteries using ultrafine iridium-decorated boron carbide (Ir/B4C) nanocomposite as oxygen electrode. The systematic investigation on charging the Li2CO3 preloaded Ir/B4C electrode in an ether-based electrolyte demonstrates that Ir/B4C electrode can decompose Li2CO3 with an efficiency close to 100% at below 4.37 V. In contrast, the bare B4C without Ir electrocatalyst can only decompose 4.7% of preloaded Li2CO3. The reaction mechanism of Li2CO3 decomposition in the presence of Ir/B4C electrocatalyst has been further investigated. A Li-O2 batterymore » using Ir/B4C as oxygen electrode material shows highly enhanced cycling stability than that using bare B4C oxygen electrode. These results clearly demonstrate that Ir/B4C is an effecitive oxygen electrode amterial to completely decompose Li2CO3 at relatively low charge voltages and is of significant importance in improving the cycle performanc of aprotic Li-O2 batteries.« less

  2. Reductive Activation of O2 by Non-Heme Iron(II) Benzilate Complexes of N4 Ligands: Effect of Ligand Topology on the Reactivity of O2-Derived Oxidant.

    PubMed

    Chakraborty, Biswarup; Jana, Rahul Dev; Singh, Reena; Paria, Sayantan; Paine, Tapan Kanti

    2017-01-03

    A series of iron(II) benzilate complexes (1-7) with general formula [(L)Fe II (benzilate)] + have been isolated and characterized to study the effect of supporting ligand (L) on the reactivity of metal-based oxidant generated in the reaction with dioxygen. Five tripodal N 4 ligands (tris(2-pyridylmethyl)amine (TPA in 1), tris(6-methyl-2-pyridylmethyl)amine (6-Me 3 -TPA in 2), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (iso-BPMEN in 3), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -iso-BPMEN in 4), and tris(2-benzimidazolylmethyl)amine (TBimA in 7)) along with two linear tetradentate amine ligands (N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (BPMEN in 5) and N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -BPMEN in 6)) were employed in the study. Single-crystal X-ray structural studies reveal that each of the complex cations of 1-3 and 5 contains a mononuclear six-coordinate iron(II) center coordinated by a monoanionic benzilate, whereas complex 7 contains a mononuclear five-coordinate iron(II) center. Benzilate binds to the iron center in a monodentate fashion via one of the carboxylate oxygens in 1 and 7, but it coordinates in a bidentate chelating mode through carboxylate oxygen and neutral hydroxy oxygen in 2, 3, and 5. All of the iron(II) complexes react with dioxygen to exhibit quantitative decarboxylation of benzilic acid to benzophenone. In the decarboxylation pathway, dioxygen becomes reduced on the iron center and the resulting iron-oxygen oxidant shows versatile reactivity. The oxidants are nucleophilic in nature and oxidize sulfide to sulfoxide and sulfone. Furthermore, complexes 2 and 4-6 react with alkenes to produce cis-diols in moderate yields with the incorporation of both the oxygen atoms of dioxygen. The oxygen atoms of the nucleophilic oxidants do not exchange with water. On the basis of interception studies, nucleophilic

  3. N2 triplet band systems and atomic oxygen in the dayglow

    NASA Astrophysics Data System (ADS)

    Broadfoot, A. L.; Hatfield, D. B.; Anderson, E. R.; Stone, T. C.; Sandel, B. R.; Gardner, J. A.; Murad, E.; Knecht, D. J.; Pike, C. P.; Viereck, R. A.

    1997-06-01

    New spectrographic observations of the Earth's dayglow have been acquired by the Arizona Airglow Experiment (GLO) flown on the space shuttle. GLO is an imaging spectrograph that records simultaneous vertical profiles of prominent Earth limb emissions occurring at wavelengths between 115 and 900 nm. This study addresses the measured emissions from the N2 triplet states (first positive, second positive, and Vegard-Kaplan band systems) and their excitation by the local photoelectron flux. The triplet state population distributions modeled for aurora by Cartwright [1978] are modified for dayglow conditions by changing to a photoelectron-flux energy distribution and including resonance scattering by the first positive system. Modeled and observed intensities are in excellent agreement, in contrast to the well-studied auroral case. This work concentrates on dayglow conditions at 200 km altitude near the subsolar point. Parameters to infer the local photoelectron flux from the emission band intensities are provided. Several atomic oxygen dayglow emission features were analyzed to complement the N2 analysis. The photoelectron-excited O I(135.6, 777.4 nm) lines were found to be 3 to 4 times weaker than predicted while the O I(630.0, 844.6 nm) lines were in close agreement with the model prediction.

  4. Oxygen Sensitivity of Anammox and Coupled N-Cycle Processes in Oxygen Minimum Zones

    PubMed Central

    Kalvelage, Tim; Jensen, Marlene M.; Contreras, Sergio; Revsbech, Niels Peter; Lam, Phyllis; Günter, Marcel; LaRoche, Julie; Lavik, Gaute; Kuypers, Marcel M. M.

    2011-01-01

    Nutrient measurements indicate that 30–50% of the total nitrogen (N) loss in the ocean occurs in oxygen minimum zones (OMZs). This pelagic N-removal takes place within only ∼0.1% of the ocean volume, hence moderate variations in the extent of OMZs due to global warming may have a large impact on the global N-cycle. We examined the effect of oxygen (O2) on anammox, NH3 oxidation and NO3 − reduction in 15N-labeling experiments with varying O2 concentrations (0–25 µmol L−1) in the Namibian and Peruvian OMZs. Our results show that O2 is a major controlling factor for anammox activity in OMZ waters. Based on our O2 assays we estimate the upper limit for anammox to be ∼20 µmol L−1. In contrast, NH3 oxidation to NO2 − and NO3 − reduction to NO2 − as the main NH4 + and NO2 − sources for anammox were only moderately affected by changing O2 concentrations. Intriguingly, aerobic NH3 oxidation was active at non-detectable concentrations of O2, while anaerobic NO3 − reduction was fully active up to at least 25 µmol L−1 O2. Hence, aerobic and anaerobic N-cycle pathways in OMZs can co-occur over a larger range of O2 concentrations than previously assumed. The zone where N-loss can occur is primarily controlled by the O2-sensitivity of anammox itself, and not by any effects of O2 on the tightly coupled pathways of aerobic NH3 oxidation and NO3 − reduction. With anammox bacteria in the marine environment being active at O2 levels ∼20 times higher than those known to inhibit their cultured counterparts, the oceanic volume potentially acting as a N-sink increases tenfold. The predicted expansion of OMZs may enlarge this volume even further. Our study provides the first robust estimates of O2 sensitivities for processes directly and indirectly connected with N-loss. These are essential to assess the effects of ocean de-oxygenation on oceanic N-cycling. PMID:22216239

  5. Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

    PubMed

    Pramana, Stevin S; Klooster, Wim T; White, T J

    2007-08-01

    Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

  6. Technical Note: Simultaneous measurement of sedimentary N2 and N2O production and a modified 15N isotope pairing technique

    NASA Astrophysics Data System (ADS)

    Hsu, T.-C.; Kao, S.-J.

    2013-12-01

    Dinitrogen (N2) and/or nitrous oxide (N2O) are produced through denitrification, anaerobic ammonium oxidation (anammox) or nitrification in sediments, of which entangled processes complicate the absolute rate estimations of gaseous nitrogen production from individual pathways. The classical isotope pairing technique (IPT), the most common 15N nitrate enrichment method to quantify denitrification, has recently been modified by different researchers to (1) discriminate between the N2 produced by denitrification and anammox or to (2) provide a more accurate denitrification rate under considering production of both N2O and N2. In case 1, the revised IPT focused on N2 production being suitable for the environments of a low N2O-to-N2 production ratio, while in case 2, anammox was neglected. This paper develops a modified method to refine previous versions of IPT. Cryogenic traps were installed to separately preconcentrate N2 and N2O, thus allowing for subsequent measurement of the two gases generated in one sample vial. The precision is better than 2% for N2 (m/z 28, m/z 29 and m/z 30), and 1.5% for N2O (m/z 44, m/z 45 and m/z 46). Based on the six m/z peaks of the two gases, the 15N nitrate traceable processes including N2 and N2O from denitrification and N2 from anammox were estimated. Meanwhile, N2O produced by nitrification was estimated via the production rate of unlabeled 44N2O. To validate the applicability of our modified method, incubation experiments were conducted using sediment cores taken from the Danshuei Estuary in Taiwan. Rates of the aforementioned nitrogen removal processes were successfully determined. Moreover, N2O yield was as high as 66%, which would significantly bias previous IPT approaches if N2O was not considered. Our modified method not only complements previous versions of IPT but also provides more comprehensive information to advance our understanding of nitrogen dynamics of the water-sediment interface.

  7. Waiting for O2

    NASA Astrophysics Data System (ADS)

    Zahnle, K. J.; Catling, D. C.; Claire, M.

    2011-12-01

    Oxygenic photosynthesis appears to be a necessary condition for the creation of an oxygen-rich atmosphere like Earth's. But available geological and geochemical evidence suggests that oxygenic photosynthesis appeared hundreds of millions of years before the oxygen-rich atmosphere was fully established. The interregnum implies that at least one other necessary condition for O2 had to be met. Here we argue that the second condition was the irreversible oxidation of the surface and crust by hydrogen escape. This is the same cause as it is for other planets with oxidized surfaces, such as Mars. The link between hydrogen escape and oxygen is direct because the primary process in oxygenic photosynthesis is splitting H2O into hydrogen and O2. Gradual oxidation of the surface and crust eventually brought Earth to a tipping point where free O2 became more stable than competing reduced gases such as CH4; or put another way, the system evolved to the point where surface oxidation under a reducing atmosphere could not keep pace with hydrogen escape. Because hydrogen escape is no faster than other geological processes that govern the long-term redox budget of the atmosphere, the approach to oxygen's final triumph would have been fitful and punctuated by episodes of oxygenation, as the record suggests was the case. The duration of the interregnum was determined by the rate of hydrogen escape and by the size of the reduced reservoir that needed to be oxidized before O2 became favored. If hydrogen escape was responsible for O2, it may be possible to account for the rough constancy of del 13C as a rough constancy of the H2/CO2 ratio in volcanic gases that follows from the constancy of the mantle's oxygen fugacity and a rough constancy in the H2O/CO2 ratio in subducted materials.

  8. Projections of oceanic N2O emissions in the 21st century using the IPSL Earth system model

    NASA Astrophysics Data System (ADS)

    Martinez-Rey, J.; Bopp, L.; Gehlen, M.; Tagliabue, A.; Gruber, N.

    2015-07-01

    The ocean is a substantial source of nitrous oxide (N2O) to the atmosphere, but little is known about how this flux might change in the future. Here, we investigate the potential evolution of marine N2O emissions in the 21st century in response to anthropogenic climate change using the global ocean biogeochemical model NEMO-PISCES. Assuming nitrification as the dominant N2O formation pathway, we implemented two different parameterizations of N2O production which differ primarily under low-oxygen (O2) conditions. When forced with output from a climate model simulation run under the business-as-usual high-CO2 concentration scenario (RCP8.5), our simulations suggest a decrease of 4 to 12 % in N2O emissions from 2005 to 2100, i.e., a reduction from 4.03/3.71 to 3.54/3.56 TgN yr-1 depending on the parameterization. The emissions decrease strongly in the western basins of the Pacific and Atlantic oceans, while they tend to increase above the oxygen minimum zones (OMZs), i.e., in the eastern tropical Pacific and in the northern Indian Ocean. The reduction in N2O emissions is caused on the one hand by weakened nitrification as a consequence of reduced primary and export production, and on the other hand by stronger vertical stratification, which reduces the transport of N2O from the ocean interior to the ocean surface. The higher emissions over the OMZ are linked to an expansion of these zones under global warming, which leads to increased N2O production, associated primarily with denitrification. While there are many uncertainties in the relative contribution and changes in the N2O production pathways, the increasing storage seems unequivocal and determines largely the decrease in N2O emissions in the future. From the perspective of a global climate system, the averaged feedback strength associated with the projected decrease in oceanic N2O emissions amounts to around -0.009 W m-2 K-1, which is comparable to the potential increase from terrestrial N2O sources. However

  9. Characterization of remote O2-plasma-enhanced CVD SiO2/GaN(0001) structure using photoemission measurements

    NASA Astrophysics Data System (ADS)

    Truyen, Nguyen Xuan; Ohta, Akio; Makihara, Katsunori; Ikeda, Mitsuhisa; Miyazaki, Seiichi

    2018-01-01

    The control of chemical composition and bonding features at a SiO2/GaN interface is a key to realizing high-performance GaN power devices. In this study, an ∼5.2-nm-thick SiO2 film has been deposited on an epitaxial GaN(0001) surface by remote O2-plasma-enhanced chemical vapor deposition (O2-RPCVD) using SiH4 and Ar/O2 mixture gases at a substrate temperature of 500 °C. The depth profile of chemical structures and electronic defects of the O2-RPCVD SiO2/GaN structures has been evaluated from a combination of SiO2 thinning examined by X-ray photoelectron spectroscopy (XPS) and the total photoelectron yield spectroscopy (PYS) measurements. As a highlight, we found that O2-RPCVD is effective for fabricating an abrupt SiO2/GaN interface.

  10. The influence of ionic strength and organic compounds on nanoparticle TiO2 (n-TiO2) aggregation.

    PubMed

    Lee, Jaewoong; Bartelt-Hunt, Shannon L; Li, Yusong; Gilrein, Erica Jeanne

    2016-07-01

    This study investigated the aggregation of n-TiO2 in the presence of humic acid (HA) and/or 17β-estradiol (E2) under high ionic strength conditions simulating levels detected in landfill leachate. Aggregation of n-TiO2 was strongly influenced by ionic strength as well as ionic valence in that divalent cations (Ca(2+)) were more effective than monovalent (Na(+)) at the surface modification. HA or E2 enhanced aggregation of n-TiO2 in 20 mM CaCl2, however little aggregation was observed in 100 mM NaCl. Similarly, we observed only the increased aggregation of n-TiO2 in the presence of HA/E2. These results showed the critical role of particles' surface charges on the aggregation behaviors of n-TiO2 that HA plays more significantly than E2. However, the slightly increased zeta potential and aggregation of n-TiO2 in the combination of HA and E2 at both 20 mM CaCl2 and 100 mM NaCl means that E2 has influenced on the surface modification of n-TiO2 by adsorption. Based on the aggregation of n-TiO2 under high ionic strength with HA and/or E2, we simulated the mobility of aggregated n-TiO2 in porous media. As a result, we observed that the mobility distance of aggregated n-TiO2 was dramatically influenced by the surface modification with both HA and/or E2 between particles and media. Furthermore, larger mobility distance was observed with larger aggregation of n-TiO2 particles that can be explained by clean bed filtration (CFT) theory. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films

    NASA Astrophysics Data System (ADS)

    Gao, Lingyuan; Yalon, Eilam; Chew, Annabel R.; Deshmukh, Sanchit; Salleo, Alberto; Pop, Eric; Demkov, Alexander A.

    2017-06-01

    The effect of strain and oxygen deficiency on the Raman spectrum of monoclinic HfO2 is investigated theoretically using first-principles calculations. 1% in-plane compressive strain applied to a and c axes is found to blue shift the phonon frequencies, while 1% tensile strain does the opposite. The simulations are compared, and good agreement is found with the experimental results of Raman frequencies greater than 110 cm-1 for 50 nm HfO2 thin films. Several Raman modes measured below 110 cm-1 and previously assigned to HfO2 are found to be rotational modes of gases present in air ambient (nitrogen and oxygen). However, localized vibrational modes introduced by threefold-coordinated oxygen (O3) vacancies are identified at 96.4 cm-1 computationally. These results are important for a deeper understanding of vibrational modes in HfO2, which has technological applications in transistors and particularly in resistive random-access memory whose operation relies on oxygen-deficient HfOx.

  12. Spectroscopic and optical properties of the VO2+ ion doped TeO2-TiO2-ZnO-Nb2O5 glass system

    NASA Astrophysics Data System (ADS)

    Swapna; Upender, G.; Sreenivasulu, V.; Prasad, M.

    2016-04-01

    Studies such as optical absorption, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Electron paramagnetic resonance (EPR) spectroscopy and Differential scanning calorimetry (DSC) were carried out on VO2+ ion doped TeO2-TiO2-ZnO-Nb2O5 glass system. Raman and FTIR spectra of the glasses revealed the presence of [TeO3], [TeO4] and [NbO6] structural units in the glass network. The Urbach energy (Δ E), cut-off wavelength (λ c ), optical band gap ( E opt ), optical basicity (Λ) and electron polarizability ( α) of the glasses were determined from optical absorption studies. The density ( ρ), molar volume ( V m ), oxygen molar volume ( V o ) and refractive index ( n) were also measured. Spin-Hamiltonian parameters were calculated from the EPR studies. When Nb2O5 was increased at the expense of ZnO, the density, optical band gap and Urbach energy of the glasses increased, and the electronic polarizability and optical basicity decreased. The EPR spectra clearly showed that vanadium was in the glass as VO2+ and occupied octahedral sites with tetrahedral compression. Spin-Hamiltonian parameters g‖ and g⊥ decreased as Nb2O5 content increased in the glass. The glass transition temperature ( T g ) also increased with increasing Nb2O5 content in the glass.

  13. Mathematical modeling of nitrous oxide (N2O) emissions from full-scale wastewater treatment plants.

    PubMed

    Ni, Bing-Jie; Ye, Liu; Law, Yingyu; Byers, Craig; Yuan, Zhiguo

    2013-07-16

    Mathematical modeling of N2O emissions is of great importance toward understanding the whole environmental impact of wastewater treatment systems. However, information on modeling of N2O emissions from full-scale wastewater treatment plants (WWTP) is still sparse. In this work, a mathematical model based on currently known or hypothesized metabolic pathways for N2O productions by heterotrophic denitrifiers and ammonia-oxidizing bacteria (AOB) is developed and calibrated to describe the N2O emissions from full-scale WWTPs. The model described well the dynamic ammonium, nitrite, nitrate, dissolved oxygen (DO) and N2O data collected from both an open oxidation ditch (OD) system with surface aerators and a sequencing batch reactor (SBR) system with bubbling aeration. The obtained kinetic parameters for N2O production are found to be reasonable as the 95% confidence regions of the estimates are all small with mean values approximately at the center. The model is further validated with independent data sets collected from the same two WWTPs. This is the first time that mathematical modeling of N2O emissions is conducted successfully for full-scale WWTPs. While clearly showing that the NH2OH related pathways could well explain N2O production and emission in the two full-scale plants studied, the modeling results do not prove the dominance of the NH2OH pathways in these plants, nor rule out the possibility of AOB denitrification being a potentially dominating pathway in other WWTPs that are designed or operated differently.

  14. Two-Dimensional Superconductivity Emerged at Monatomic Bi(2-) Square Net in Layered Y2O2Bi via Oxygen Incorporation.

    PubMed

    Sei, Ryosuke; Kitani, Suguru; Fukumura, Tomoteru; Kawaji, Hitoshi; Hasegawa, Tetsuya

    2016-09-07

    Discovery of layered superconductors such as cuprates and iron-based compounds has unveiled new science and compounds. In these superconductors, quasi-two-dimensional layers including transition metal cations play principal role in the superconductivity via carrier doping by means of aliovalent-ion substitution. Here, we report on a two-dimensional superconductivity at 2 K in ThCr2Si2-type layered oxide Y2O2Bi possessing conducting monatomic Bi(2-) square net, possibly associated with an exotic superconductivity. The superconductivity emerges only in excessively oxygen-incorporated Y2O2Bi with expanded inter-net distance, in stark contrast to nonsuperconducting pristine Y2O2Bi reported previously. This result suggests that the element incorporation into hidden interstitial site could be an alternative approach to conventional substitution and intercalation methods for search of novel superconductors.

  15. Influence of oxygen vacancies in ALD HfO2-x thin films on non-volatile resistive switching phenomena with a Ti/HfO2-x/Pt structure

    NASA Astrophysics Data System (ADS)

    Sokolov, Andrey Sergeevich; Jeon, Yu-Rim; Kim, Sohyeon; Ku, Boncheol; Lim, Donghwan; Han, Hoonhee; Chae, Myeong Gyoon; Lee, Jaeho; Ha, Beom Gil; Choi, Changhwan

    2018-03-01

    We report a modulation of oxygen vacancies profile in atomic layer deposition (ALD) HfO2-x thin films by reducing oxidant pulse time (0.7 s-0.1 s) and study its effect on resistive switching behavior with a Ti/HfO2-x/Pt structure. Hf 4f spectra of x-ray photoelectron microscopy (XPS) and depth profile confirm varied oxygen vacancies profiles by shifts of binding energies of Hf 4f5/2 and Hf 4f7/2 main peaks and its according HfO2-x sub-oxides for each device. The ultraviolet photoelectron spectroscopy (UPS) confirms different electron affinity (χ) of HfO2 and HfO2-x thin films, implying that barrier height at Ti/oxide interface is reduced. Current transport mechanism is dictated by Ohmic conduction in fully oxidized HfO2 thin films - Device A (0.7 s) and by Trap Filled Space Charge Limited Conduction (TF-SCLC) in less oxidized HfO2-x thin films - Device B (0.3 s) and Device C (0.1 s). A switching mechanism related to the oxygen vacancies modulation in Ti/HfO2-x/Pt based resistive random access memory (RRAM) devices is used to explain carefully notified current transport mechanism variations from device-to-device. A proper endurance and long-time retention characteristics of the devices are also obtained.

  16. Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

    NASA Astrophysics Data System (ADS)

    Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

    2017-09-01

    The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

  17. H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways.

    PubMed

    Aceituno, Mónica; Stalikas, Constantine D; Lunar, Loreto; Rubio, Soledad; Pérez-Bendito, Dolores

    2002-08-01

    The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.

  18. Synthesis and Characterization of LaTiO2N

    NASA Astrophysics Data System (ADS)

    Rugen, Evan E.

    Photocatalysts offer an excellent opportunity to shift the global energy landscape from a fossil fuel-dependent paradigm to sustainable and carbon-neutral solar fuels. Oxynitride materials such as LaTiO2N are potential photocatalysts for the water splitting reaction due to their high oxidative stability and their narrow band gaps, which are suitable for visible light absorption. However, facile synthetic routes to metal oxynitrides with controlled morphologies are rare, and the local structures of these materials are under-characterized. Ultrasonic spray synthesis (USS) offers a facile method toward complex metal oxides which can potentially be converted to oxynitrides with preservation of the microsphere structures that typify the products from such aerosol routes. Here, La-Ti-O microspheres were facilely produced by USS and converted by ammonolysis to LaTiO2N microspheres with porous shells and hollow interiors. This particle architecture is accounted for by coupling suitable combustion chemistry with the aerosol technique, producing precursor particles where the La3+ and Ti4+ are well-mixed at small length scales; this feature enables preservation of the microsphere morphology during nitridation despite the crystallographic changes that occur. The LaTiO2N microspheres are comparable oxygen evolving photocatalysts to samples produced by conventional solid state methods. Pair distribution function (PDF) analysis is a local probe designed to examine the structure of disordered crystalline materials, and is an ideal technique for characterizing the ordering of anions in oxynitrides. Preliminary studies using PDF analysis to determine the presence of anion ordering and local structure in LaTiO2N produced by solid state methods are presented here. Future experiments are proposed that will grant detailed insight into the factors driving the degree of anion ordering in these types of materials. These results demonstrate the utility of USS as a facile, potentially

  19. Oxygen Reduction Reaction on Graphene in an Electro-Fenton System: In Situ Generation of H2 O2 for the Oxidation of Organic Compounds.

    PubMed

    Chen, Chen-Yu; Tang, Cheng; Wang, Hao-Fan; Chen, Cheng-Meng; Zhang, Xiaoyuan; Huang, Xia; Zhang, Qiang

    2016-05-23

    Fenton oxidation using an aqueous mixture of Fe(2+) and H2 O2 is a promising environmental remediation strategy. However, the difficulty of storage and shipment of concentrated H2 O2 and the generation of iron sludge limit its broad application. Therefore, highly efficient and cost-effective electrocatalysts are in great need. Herein, a graphene catalyst is proposed for the electro-Fenton process, in which H2 O2 is generated in situ by the two-electron reduction of the dissolved O2 on the cathode and then decomposes to generate (.) OH in acidic solution with Fe(2+) . The π bond of the oxygen is broken whereas the σ bond is generally preserved on the metal-free reduced graphene oxide owing to the high free energy change. Consequently, the oxygen is reduced to H2 O2 through a two-electron pathway. The thermally reduced graphene with a high specific surface area (308.8 m(2)  g(-1) ) and a large oxygen content (10.3 at %) exhibits excellent reactivity for the two-electron oxygen reduction reaction to H2 O2 . A highly efficient peroxide yield (64.2 %) and a remarkable decolorization of methylene blue (12 mg L(-1) ) of over 97 % in 160 min are obtained. The degradation of methylene blue with hydroxyl radicals generated in situ is described by a pseudo first-order kinetics model. This provides a proof-of-concept of an environmentally friendly electro-Fenton process using graphene for the oxygen reduction reaction in an acidic solution to generate H2 O2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Production of simplex RNS and ROS by nanosecond pulse N2/O2 plasma jets with homogeneous shielding gas for inducing myeloma cell apoptosis

    NASA Astrophysics Data System (ADS)

    Liu, Zhijie; Xu, Dehui; Liu, Dingxin; Cui, Qingjie; Cai, Haifeng; Li, Qiaosong; Chen, Hailan; Kong, Michael G.

    2017-05-01

    In this paper, atmospheric pressure N2/O2 plasma jets with homogeneous shielding gas excited by nanosecond pulse are obtained to generate simplex reactive nitrogen species (RNS) and reactive oxygen species (ROS), respectively, for the purpose of studying the simplex RNS and ROS to induce the myeloma cell apoptosis with the same discharge power. The results reveal that the cell death rate by the N2 plasma jet with N2 shielding gas is about two times that of the O2 plasma jet with O2 shielding gas for the equivalent treatment time. By diagnosing the reactive species of ONOO-, H2O2, OH and \\text{O}2- in medium, our findings suggest the cell death rate after plasma jets treatment has a positive correlation with the concentration of ONOO-. Therefore, the ONOO- in medium is thought to play an important role in the process of inducing myeloma cell apoptosis.

  1. Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

    PubMed Central

    T. Weller, Mark

    2018-01-01

    Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

  2. Fluorite Ce0.8Sm0.2O2- δ porous layer coating to enhance the oxygen permeation behavior of a BaCo0.7Fe0.2Nb0.1O3- δ mixed conductor

    NASA Astrophysics Data System (ADS)

    Wang, Tai-he; Song, Wei-jia; Li, Rong; Zhen, Qiang

    2016-06-01

    Fluorite Ce0.8Sm0.2O2- δ (SDC) nanopowder with a crystallite size of 15 nm was synthesized by a co-precipitation method. An SDC porous layer was coated onto a BaCo0.7Fe0.2Nb0.1O3- δ (BCFN) mixed conductor to improve its oxygen transport behavior. The results show that the SDC-coated BCFN membrane exhibits a remarkably higher oxygen permeation flux ({J_{{O_2}}}) than the uncoated BCFN in the partial oxidation of coke oven gas (COG). The maximum {J_{{O_2}}} value of the SDC-coated BCFN is 18.28 mL·min-1·cm-2 under a COG/air flux of 177 mL·min-1/353 mL·min-1 at 875°C when the thickness of the BCFN membrane is 1 mm; this {J_{{O_2}}} value is 23% higher than that of the uncoated BCFN membrane. This enhancement is likely because of the higher oxygen ionic conductivity of SDC, which supplies oxygen vacancies and accelerates oxygen exchange on the membrane/coating layer/gas three-phase boundary.

  3. Simple synthesis of highly catalytic carbon-free MnCo2O4@Ni as an oxygen electrode for rechargeable Li–O2 batteries with long-term stability

    PubMed Central

    Kalubarme, Ramchandra S.; Jadhav, Harsharaj S.; Ngo, Duc Tung; Park, Ga-Eun; Fisher, John G.; Choi, Yun-Il; Ryu, Won-Hee; Park, Chan-Jin

    2015-01-01

    An effective integrated design with a free standing and carbon-free architecture of spinel MnCo2O4 oxide prepared using facile and cost effective hydrothermal method as the oxygen electrode for the Li–O2 battery, is introduced to avoid the parasitic reactions of carbon and binder with discharge products and reaction intermediates, respectively. The highly porous structure of the electrode allows the electrolyte and oxygen to diffuse effectively into the catalytically active sites and hence improve the cell performance. The amorphous Li2O2 will then precipitate and decompose on the surface of free-standing catalyst nanorods. Electrochemical examination demonstrates that the free-standing electrode without carbon support gives the highest specific capacity and the minimum capacity fading among the rechargeable Li–O2 batteries tested. The Li-O2 cell has demonstrated a cyclability of 119 cycles while maintaining a moderate specific capacity of 1000 mAh g−1. Furthermore, the synergistic effect of the fast kinetics of electron transport provided by the free-standing structure and the high electro-catalytic activity of the spinel oxide enables excellent performance of the oxygen electrode for Li-O2 cells. PMID:26292965

  4. Effect of TiO2 on the Gas Sensing Features of TiO2/PANi Nanocomposites

    PubMed Central

    Huyen, Duong Ngoc; Tung, Nguyen Trong; Thien, Nguyen Duc; Thanh, Le Hai

    2011-01-01

    A nanocomposite of titanium dioxide (TiO2) and polyaniline (PANi) was synthesized by in-situ chemical polymerization using aniline (ANi) monomer and TiCl4 as precursors. SEM pictures show that the nanocomposite was created in the form of long PANi chains decorated with TiO2 nanoparticles. FTIR, Raman and UV-Vis spectra reveal that the PANi component undergoes an electronic structure modification as a result of the TiO2 and PANi interaction. The electrical resistor of the nanocomposite is highly sensitive to oxygen and NH3 gas, accounting for the physical adsorption of these gases. A nanocomposite with around 55% TiO2 shows an oxygen sensitivity of 600–700%, 20–25 times higher than that of neat PANi. The n-p contacts between TiO2 nanoparticles and PANi matrix give rise to variety of shallow donors and acceptor levels in the PANi band gap which enhance the physical adsorption of gas molecules. PMID:22319389

  5. Effect of Si3N4 powder reactivity on the preparation of the Si2N2O-Al2O3 silicon aluminum oxynitride solid solution

    NASA Technical Reports Server (NTRS)

    Sekercioglu, I.; Wills, R. R.

    1979-01-01

    Dense high-purity silicon aluminum oxynitride was prepared by reactive hot-pressing of an Si3N4-Al2O3-SiO2 mixture. The formation of a single-phase material was found to be critically dependent on the Si3N4 powder in the starting mixture. It is suggested that evolution of a chlorine- and nitrogen-containing species may enhance the reactivity of Si3N4 in this reaction. Densities of O prime sialons are very similar to that of Si2N2O, the widely quoted value in the ceramics literature of 3.1 g/cu cm for the density of Si2N2O being incorrect.

  6. Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

    PubMed Central

    Paschalidis, Damianos G.; Harrison, William T. A.

    2016-01-01

    The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

  7. Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

    NASA Astrophysics Data System (ADS)

    Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

    2016-04-01

    The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

  8. Oxygen vacancy rich Cu2O based composite material with nitrogen doped carbon as matrix for photocatalytic H2 production and organic pollutant removal.

    PubMed

    Lu, Lele; Xu, Xinxin; Yan, Jiaming; Shi, Fa-Nian; Huo, Yuqiu

    2018-02-06

    A nitrogen doped carbon matrix supported Cu 2 O composite material (Cu/Cu2O@NC) was fabricated successfully with a coordination polymer as precursor through calcination. In this composite material, Cu 2 O particles with a size of about 6-10 nm were dispersed evenly in the nitrogen doped carbon matrix. After calcination, some coordinated nitrogen atoms were doped in the lattice of Cu 2 O and replace oxygen atoms, thus generating a large number of oxygen vacancies. In Cu/Cu2O@NC, the existence of oxygen vacancies has been confirmed by electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS). Under visible light irradiation, Cu/Cu2O@NC exhibits excellent H 2 production with the rate of 379.6 μmol h -1 g -1 . Its photocatalytic activity affects organic dyes, such as Rhodamine B (RhB) and methyl orange (MO). In addition to photocatalysis, Cu/Cu2O@NC also exhibits striking catalytic activity in reductive conversion of 4-nitrophenol to 4-aminophenol with in presence of sodium borohydride (NaBH 4 ). The conversion efficiency reaches almost 100% in 250 s with the quantity of Cu/Cu2O@NC as low as 5 mg. The outstanding H 2 production and organic pollutants removal are attributed to the oxygen vacancy. We expect that Cu/Cu2O@NC will find its way as a new resource for hydrogen energy as well as a promising material in water purification.

  9. Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

    SciTech Connect

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

    2015-03-15

    Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

  10. Atomic resolution chemical bond analysis of oxygen in La2CuO4

    NASA Astrophysics Data System (ADS)

    Haruta, M.; Nagai, T.; Lugg, N. R.; Neish, M. J.; Nagao, M.; Kurashima, K.; Allen, L. J.; Mizoguchi, T.; Kimoto, K.

    2013-08-01

    The distorted CuO6 octahedron in La2CuO4 was studied using aberration-corrected scanning transmission electron microscopy at atomic resolution. The near-edge structure in the oxygen K-edge electron energy-loss spectrum was recorded as a function of the position of the electron probe. After background subtraction, the measured spectrum image was processed using a recently developed inversion process to remove the mixing of signals on the atomic columns due to elastic and thermal scattering. The spectra were then compared with first-principles band structure calculations based on the local-density approximation plus on-site Coulomb repulsion (LDA + U) approach. In this article, we describe in detail not only anisotropic chemical bonding of the oxygen 2p state with the Cu 3d state but also with the Cu 4p and La 5d/4f states. Furthermore, it was found that buckling of the CuO2 plane was also detectable at the atomic resolution oxygen K-edge. Lastly, it was found that the effects of core-hole in the O K-edge were strongly dependent on the nature of the local chemical bonding, in particular, whether it is ionic or covalent.

  11. Substitutional Cd and Cd-Oxygen Vacancy Complexes in ZrO2 and Ce-doped ZrO_2

    NASA Astrophysics Data System (ADS)

    Zacate, Matthew O.; Karapetrova, E.; Platzer, R.; Gardner, J. A.; Evenson, W. E.; Sommers, J. A.

    1996-03-01

    We are using Perturbed Angular Correlation Spectroscopy (PAC) to study oxygen vacancy (V_O) dynamics in tetragonal ZrO2 and Ce-doped ZrO_2. PAC requires a radioactive probe atom, Cd in this study, which sits substitutionally for a Zr ion. Cd is doubly-negatively charged relative to the lattice and attracts doubly-positively charged V_Os. Pure tetragonal zirconia exists only above 950 ^circC and in this temperature range, the V_Os are very mobile. Above 950 ^circC we observe V_Os rapidly hopping about the Cd allowing us to determine the VO concentration and the trapping energy. We have been Ce-doping to stabilize the tetragonal phase to lower temperature to determine the electric field gradient the Cd experiences due to a stationary V_O. As a consequence of the Ce-doping, we observe a local lattice distortion about the Cd which increases with Ce-doping.

  12. Interface formation of epitaxial MgO/Co2MnSi(001) structures: Elemental segregation and oxygen migration

    NASA Astrophysics Data System (ADS)

    McFadden, Anthony; Wilson, Nathaniel; Brown-Heft, Tobias; Pennachio, Daniel; Pendharkar, Mihir; Logan, John A.; Palmstrøm, Chris J.

    2017-12-01

    The interface formation in epitaxial MgO /Co2MnSi (001) films was studied using in-situ X-ray photoelectron spectroscopy (XPS). MgO was deposited on single crystal Co2MnSi (001) layers using e-beam evaporation: a technique which is expected to oxidize the Co2MnSi layer somewhat due to the rise in oxygen partial pressure during MgO deposition while leaving the deposited MgO oxygen deficient. Not unexpectedly, we find that e-beam evaporation of MgO raises the oxygen background in the deposition chamber to a level that readily oxidizes the Co2MnSi surface, with oxygen bonding preferentially to Mn and Si over Co. Interestingly, this oxidation causes an elemental segregation, with Mn-Si effectively moving toward the surface, resulting in an MgO /Co2MnSi interface with a composition significantly differing from the original surface of the unoxidized Co2MnSi film. As MgO is deposited on the oxidized Co2MnSi , the Mn-oxides are reduced, while the Si oxide remains, and is only somewhat reduced after additional annealing in ultrahigh vacuum. Annealing after the MgO is grown on Co2MnSi causes oxygen to move away from the oxidized Co2MnSi interface toward the surface and into the MgO. This observation is consistent with an increase in the tunneling magnetoresistance ratio with post-growth annealing measured in fabricated magnetic tunnel junctions (MTJs). The findings are discussed in light of fabrication of MgO/Heusler based MTJs, where the exponential decay of tunneling probability with contact separation exemplifies the importance of the ferromagnet/tunnel barrier interface.

  13. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  14. Assessment of N2O emission from a photobioreactor treating ammonia-rich swine wastewater digestate.

    PubMed

    Mezzari, Melissa P; da Silva, Márcio L B; Nicoloso, Rodrigo S; Ibelli, Adriana M G; Bortoli, Marcelo; Viancelli, Aline; Soares, Hugo M

    2013-12-01

    This study investigated the interactions between naturally occurring bacteria and the microalgae Chlorella vulgaris within a lab scale photobioreactor treating ammonia-rich swine wastewater digestate effluent. Nitrification and denitrification were assessed by targeting ammonia monoxygenases (amoA), nitrate (narG), nitrite (nirS), nitric oxide (norB) and nitrous oxide (nosZ) reductases genes. Oxygen produced from microalgae photosynthesis stimulated nitrification. Under limiting carbon availability (i.e., <1.44 for mg TOC/mg NO2-N and 1.72 for mg TOC/mg NO3-N), incomplete denitrification led to accumulation of NO2 and NO3. Significant N2O emission (up to 118 μg N2O-N) was linked to NO2 metabolism in Chlorella. The addition of acetate as external carbon source recovered heterotrophic denitrification activity suppressing N2O emission. Effluent methane concentrations trapped within photobioreactor was removed concomitantly with ammonia. Overall, closed photobioreactors can be built to effectively remove nitrogen and mitigate simultaneously greenhouse gases emissions that would occur otherwise in open microalgae-based wastewater treatment systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. The role of oxygen vacancies in resistive switching behavior of organic-TiO2 hybrid composite

    NASA Astrophysics Data System (ADS)

    Zhang, Jiahua; Chen, Da; Huang, Shihua

    2017-10-01

    Effects of polyethylene glycol (PEG) on resistive switching behaviors and mechanisms in organic-TiO2 hybrid composites were investigated. The reversed current-voltage curves in the negative bias during the initial voltage sweeps were first observed in the composites annealed at 150, 200 and 250 °C, which is ascribed to the accumulation of oxygen vacancies and the inhibition effect of polarities of PEG chains. In addition, the volatility of composites with relatively high content of PEG is caused by the inhibition effect of PEG on creating oxygen vacancies. The formation and rupture of oxygen-vacancy filaments was considered as the resistive switching mechanism. Finally, the charging and discharging process in PEG-TiO2 composite annealed at 150 °C results in the instability of the electron-occupied oxygen vacancies and the inhibition of PEG chains. This study demonstrates a new way to investigate the interaction between polymers and TiO2 for understanding the resistive switching mechanism of TiO2-based memories.

  16. Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

    NASA Astrophysics Data System (ADS)

    Martin, T. S.; Casciotti, K. L.

    2017-03-01

    The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

  17. N2O production, a widespread trait in fungi

    NASA Astrophysics Data System (ADS)

    Maeda, Koki; Spor, Aymé; Edel-Hermann, Véronique; Heraud, Cécile; Breuil, Marie-Christine; Bizouard, Florian; Toyoda, Sakae; Yoshida, Naohiro; Steinberg, Christian; Philippot, Laurent

    2015-04-01

    N2O is a powerful greenhouse gas contributing both to global warming and ozone depletion. While fungi have been identified as a putative source of N2O, little is known about their production of this greenhouse gas. Here we investigated the N2O-producing ability of a collection of 207 fungal isolates. Seventy strains producing N2O in pure culture were identified. They were mostly species from the order Hypocreales order--particularly Fusarium oxysporum and Trichoderma spp.--and to a lesser extent species from the orders Eurotiales, Sordariales, and Chaetosphaeriales. The N2O 15N site preference (SP) values of the fungal strains ranged from 15.8‰ to 36.7‰, and we observed a significant taxa effect, with Penicillium strains displaying lower SP values than the other fungal genera. Inoculation of 15 N2O-producing strains into pre-sterilized arable, forest and grassland soils confirmed the ability of the strains to produce N2O in soil with a significant strain-by-soil effect. The copper-containing nitrite reductase gene (nirK) was amplified from 45 N2O-producing strains, and its genetic variability showed a strong congruence with the ITS phylogeny, indicating vertical inheritance of this trait. Taken together, this comprehensive set of findings should enhance our knowledge of fungi as a source of N2O in the environment.

  18. N2O production, a widespread trait in fungi.

    PubMed

    Maeda, Koki; Spor, Aymé; Edel-Hermann, Véronique; Heraud, Cécile; Breuil, Marie-Christine; Bizouard, Florian; Toyoda, Sakae; Yoshida, Naohiro; Steinberg, Christian; Philippot, Laurent

    2015-04-20

    N2O is a powerful greenhouse gas contributing both to global warming and ozone depletion. While fungi have been identified as a putative source of N2O, little is known about their production of this greenhouse gas. Here we investigated the N2O-producing ability of a collection of 207 fungal isolates. Seventy strains producing N2O in pure culture were identified. They were mostly species from the order Hypocreales order-particularly Fusarium oxysporum and Trichoderma spp.-and to a lesser extent species from the orders Eurotiales, Sordariales, and Chaetosphaeriales. The N2O (15)N site preference (SP) values of the fungal strains ranged from 15.8‰ to 36.7‰, and we observed a significant taxa effect, with Penicillium strains displaying lower SP values than the other fungal genera. Inoculation of 15 N2O-producing strains into pre-sterilized arable, forest and grassland soils confirmed the ability of the strains to produce N2O in soil with a significant strain-by-soil effect. The copper-containing nitrite reductase gene (nirK) was amplified from 45 N2O-producing strains, and its genetic variability showed a strong congruence with the ITS phylogeny, indicating vertical inheritance of this trait. Taken together, this comprehensive set of findings should enhance our knowledge of fungi as a source of N2O in the environment.

  19. Optimization of photoelectrochemical performance in Pt-modified p-Cu2O/n-Cu2O nanocomposite

    NASA Astrophysics Data System (ADS)

    Wang, Yichen; Lou, Zirui; Niu, Wenzhe; Ye, Zhizhen; Zhu, Liping

    2018-04-01

    As it is expected to be one of the most promising materials for utilizing solar energy, Cu2O has attracted considerable attention with respect to the achievement of solar energy conversion. Until now, the photocurrent densities of all planar structure of the Cu2O photocathode have not even come close to the theoretical value of -14.7 mA cm-2 due to the incompatible light absorption and charge carrier diffusion lengths. Here, we have fabricated p-n Cu2O homojunction nanocomposite by multiple steps of electrochemical deposition processing with the optimization of deposition periods. The p-Cu2O/n-Cu2O nanocomposite fabricated by optimized pH (4.9) and deposition time (4 min) exhibited double the photocurrent density of that of the bare p-Cu2O photocathode. And the highest photocurrent density of nanostructured p-n Cu2O nanorod homojunction photocathode with a p-Cu2O blocking layer reached -10.0 mA cm-2 at 0 V versus the reversible hydrogen electrode under simulated AM 1.5G illumination (100 mW cm-2).

  20. Amelioration of rCBF and PbtO2 following TBI at high altitude by hyperbaric oxygen pre-conditioning.

    PubMed

    Hu, Shengli; Li, Fei; Luo, Haishui; Xia, Yongzhi; Zhang, Jiuquan; Hu, Rong; Cui, Gaoyu; Meng, Hui; Feng, Hua

    2010-03-01

    Hypobaric hypoxia at high altitude can lead to brain damage and pre-conditioning with hyperbaric oxygen (HBO) can reduce ischemic/hypoxic brain injury. This study investigates the effects of high altitude on traumatic brain injury (TBI) and examines the neuroprotection provided by HBO preconditioning against TBI. Rats were randomly divided into four groups: HBO pre-conditioning group (HBOP, n=10), high altitude group (HA, n=10), plain control group (PC, n=10) and plain sham operation group (sham, n=10). All groups were subjected to head trauma by weight drop device except for the sham group. Rats from each group were examined for neurological function, regional cerebral blood flow (rCBF) and brain tissue oxygen pressure (PbtO(2)) and were killed for analysis by transmission electron microscope. The score of neurological deficits in the HA group was highest, followed by the HBOP group and the PC group, respectively. Both rCBF and PbtO(2) were the lowest in the HA group. Brain morphology and structure seen via the transmission electron microscope was diminished in the HA group, while fewer pathological injuries occurred in the HBOP and PC groups. High altitude aggravates TBI significantly and HBO pre-conditioning can attenuate TBI in rats at high altitude by improvement of rCBF and PbtO(2). Pre-treatment with HBO might be beneficial for people traveling to high altitude locations.

  1. The δ15N and δ18O values of N2O produced during the co-oxidation of ammonia by methanotrophic bacteria

    USGS Publications Warehouse

    Mandernack, Kevin W.; Mills, Christopher T.; Johnson, Craig A.; Rahn, Thomas; Kinney, Chad

    2009-01-01

    In order to determine if the δ15N and δ18O values of N2O produced during co-oxidation of NH4+ by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N2O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH4Cl as an oxidation substrate. The N2O produced during NH4+ oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH4+ and N2ON2O–NH4+) of − 48 and − 55‰ for Methylomonas methanica and Methylosinus trichosporium, OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N2O formation by multiple rate limiting steps that include NH4+oxidation by the methane monooxygenase enzyme and reduction of NO2− to N2O. Consequently, N2O formed by NH4+ oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ15NN2O values than that formed by denitrificaiton, although this also depends on the variability of δ15N of available nitrogen sources (e.g., NH4+, NO3−, NO2−). Additional incubations with M. trichosporium OB3b at high and low CH4 conditions in waters of different δ18O values revealed that 19–27% of the oxygen in N2O was derived from O2 with the remainder from water. The biochemical mechanisms that could explain this amount of O2 incorporation are discussed. The δ18O of N2O formed under high CH4 conditions was ~ + 15‰ more positive than that formed under lower CH4 conditions. This enrichment resulted in part from the incorporation of O2 into N2O that was enriched in 18O due to an isotope fractionation effect of − 16.1 ± 2.0‰ and − 17.5 ± 5.4‰ associated with O2 consumption during the high and low methane concentration incubations, respectively. Therefore, N2O formed by NH4+

  2. [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

    PubMed Central

    Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

    2010-01-01

    Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

  3. Oxygen Isotopic Fractionation During Evaporation of SiO2 in Vacuum and in H Gas

    NASA Astrophysics Data System (ADS)

    Nagahara, H.; Young, E. D.; Hoering, T. C.; Mysen, B. O.

    1993-07-01

    Chondritic components, chondrules, CAIs, and some parts of the matrix are believed to have formed and/or thermally processed in the solar nebula. If this scenario is the case, they should be fractionated for major and minor elements and isotopes according to the formation temperature. This is true for major and trace elements, but is not the case for isotopes. Differences in oxygen isotopic composition among meteorite groups are interpreted to be the results of mixing of gas and dust from different oxygen reservoirs, and the effect of isotopic fractionation is negligible for most meteorites except for rare CAIs. Davis et al. [1] studied the isotopic fractionation of SiO2, MgO, and forsterite and showed that oxygen isotopic fractionation from solid materials is very small, but that from liquid is significant. Evaporation in the solar nebula should, however, be in hydrogen gas, which is reactive with silicates. Therefore, the effect of hydrogen gas on the evaporation behaviors of silicates, including mode of evaporation, evaporation rate, and compositional and isotopic fractionation, should be studied. Nagahara [2] studied the evaporation rate of SiO2 in equilibrium, in constant evacuation (free evaporation), and in hydrogen, and showed that the rate in hydrogen gas is orders of magnitude larger than that in vacuum; the mode of evaporation also differs from that in vacuum. Oxygen isotopic fractionation during evaporation of SiO2 in constant evacuation and in hydrogen gas at two different total pressures are studied in the present study. The starting material is a single crystal of natural quartz, which should transform into high cristobalite at experimental conditions. The powdered starting material was kept in a graphite capsule without a cap and set in a vacuum chamber with and without hydrogen gas flow. Experimental temperature was 1600 degrees C. Oxygen isotopic compositions (^18O/^16O) were measured with the CO2laser heating fluorination technique. Oxygen

  4. N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

    PubMed

    Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

    2015-01-01

    A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Effect of administration of water enriched in O2 by injection or electrolysis on transcutaneous oxygen pressure in anesthetized pigs.

    PubMed

    Charton, Antoine; Péronnet, François; Doutreleau, Stephane; Lonsdorfer, Evelyne; Klein, Alexis; Jimenez, Liliana; Geny, Bernard; Diemunsch, Pierre; Richard, Ruddy

    2014-01-01

    Oral administration of oxygenated water has been shown to improve blood oxygenation and could be an alternate way for oxygen (O2) supply. In this experiment, tissue oxygenation was compared in anesthetized pigs receiving a placebo or water enriched in O2 by injection or a new electrolytic process. Forty-two pigs randomized in three groups received either mineral water as placebo or water enriched in O2 by injection or the electrolytic process (10 mL/kg in the stomach). Hemodynamic parameters, partial pressure of oxygen in the arterial blood (PaO2), skin blood flow, and tissue oxygenation (transcutaneous oxygen pressure, or TcPO2) were monitored during 90 minutes of general anesthesia. Absorption and tissue distribution of the three waters administered were assessed using dilution of deuterium oxide. Mean arterial pressure, heart rate, PaO2, arteriovenous oxygen difference, and water absorption from the gut were not significantly different among the three groups. The deuterium to protium ratio was also similar in the plasma, skin, and muscle at the end of the protocol. Skin blood flow decreased in the three groups. TcPO2 slowly decreased over the last 60 minutes of the experiment in the three groups, but when compared to the control group, the values remained significantly higher in animals that received the water enriched in O2 by electrolysis. In this protocol, water enriched in O2 by electrolysis lessened the decline of peripheral tissue oxygenation. This observation is compatible with the claim that the electrolytic process generates water clathrates which trap O2 and facilitate O2 diffusion along pressure gradients. Potential applications of O2-enriched water include an alternate method of oxygen supply.

  6. Effect of administration of water enriched in O2 by injection or electrolysis on transcutaneous oxygen pressure in anesthetized pigs

    PubMed Central

    Charton, Antoine; Péronnet, François; Doutreleau, Stephane; Lonsdorfer, Evelyne; Klein, Alexis; Jimenez, Liliana; Geny, Bernard; Diemunsch, Pierre; Richard, Ruddy

    2014-01-01

    Background Oral administration of oxygenated water has been shown to improve blood oxygenation and could be an alternate way for oxygen (O2) supply. In this experiment, tissue oxygenation was compared in anesthetized pigs receiving a placebo or water enriched in O2 by injection or a new electrolytic process. Methods Forty-two pigs randomized in three groups received either mineral water as placebo or water enriched in O2 by injection or the electrolytic process (10 mL/kg in the stomach). Hemodynamic parameters, partial pressure of oxygen in the arterial blood (PaO2), skin blood flow, and tissue oxygenation (transcutaneous oxygen pressure, or TcPO2) were monitored during 90 minutes of general anesthesia. Absorption and tissue distribution of the three waters administered were assessed using dilution of deuterium oxide. Results Mean arterial pressure, heart rate, PaO2, arteriovenous oxygen difference, and water absorption from the gut were not significantly different among the three groups. The deuterium to protium ratio was also similar in the plasma, skin, and muscle at the end of the protocol. Skin blood flow decreased in the three groups. TcPO2 slowly decreased over the last 60 minutes of the experiment in the three groups, but when compared to the control group, the values remained significantly higher in animals that received the water enriched in O2 by electrolysis. Conclusions In this protocol, water enriched in O2 by electrolysis lessened the decline of peripheral tissue oxygenation. This observation is compatible with the claim that the electrolytic process generates water clathrates which trap O2 and facilitate O2 diffusion along pressure gradients. Potential applications of O2-enriched water include an alternate method of oxygen supply. PMID:25210438

  7. Insulator-semiconductor interface fixed charges in AlGaN/GaN metal-insulator-semiconductor devices with Al2O3 or AlTiO gate dielectrics

    NASA Astrophysics Data System (ADS)

    Le, Son Phuong; Nguyen, Duong Dai; Suzuki, Toshi-kazu

    2018-01-01

    We have investigated insulator-semiconductor interface fixed charges in AlGaN/GaN metal-insulator-semiconductor (MIS) devices with Al2O3 or AlTiO (an alloy of Al2O3 and TiO2) gate dielectrics obtained by atomic layer deposition on AlGaN. Analyzing insulator-thickness dependences of threshold voltages for the MIS devices, we evaluated positive interface fixed charges, whose density at the AlTiO/AlGaN interface is significantly lower than that at the Al2O3/AlGaN interface. This and a higher dielectric constant of AlTiO lead to rather shallower threshold voltages for the AlTiO gate dielectric than for Al2O3. The lower interface fixed charge density also leads to the fact that the two-dimensional electron concentration is a decreasing function of the insulator thickness for AlTiO, whereas being an increasing function for Al2O3. Moreover, we discuss the relationship between the interface fixed charges and interface states. From the conductance method, it is shown that the interface state densities are very similar at the Al2O3/AlGaN and AlTiO/AlGaN interfaces. Therefore, we consider that the lower AlTiO/AlGaN interface fixed charge density is not owing to electrons trapped at deep interface states compensating the positive fixed charges and can be attributed to a lower density of oxygen-related interface donors.

  8. High thermal stability of abrupt SiO2/GaN interface with low interface state density

    NASA Astrophysics Data System (ADS)

    Truyen, Nguyen Xuan; Taoka, Noriyuki; Ohta, Akio; Makihara, Katsunori; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Shimizu, Mitsuaki; Miyazaki, Seiichi

    2018-04-01

    The effects of postdeposition annealing (PDA) on the interface properties of a SiO2/GaN structure formed by remote oxygen plasma-enhanced chemical vapor deposition (RP-CVD) were systematically investigated. X-ray photoelectron spectroscopy clarified that PDA in the temperature range from 600 to 800 °C has almost no effects on the chemical bonding features at the SiO2/GaN interface, and that positive charges exist at the interface, the density of which can be reduced by PDA at 800 °C. The capacitance-voltage (C-V) and current density-SiO2 electric field characteristics of the GaN MOS capacitors also confirmed the reduction in interface state density (D it) and the improvement in the breakdown property of the SiO2 film after PDA at 800 °C. Consequently, a high thermal stability of the SiO2/GaN structure with a low fixed charge density and a low D it formed by RP-CVD was demonstrated. This is quite informative for realizing highly robust GaN power devices.

  9. Lysozyme oxidation by singlet molecular oxygen: Peptide characterization using [18 O]-labeling oxygen and nLC-MS/MS.

    PubMed

    Marques, Emerson Finco; Medeiros, Marisa H G; Di Mascio, Paolo

    2017-11-01

    Singlet molecular oxygen ( 1 O 2 ) is generated in biological systems and reacts with different biomolecules. Proteins are a major target for 1 O 2 , and His, Tyr, Met, Cys, and Trp are oxidized at physiological pH. In the present study, the modification of lysozyme protein by 1 O 2 was investigated using mass spectrometry approaches. The experimental findings showed methionine, histidine, and tryptophan oxidation. The experiments were achieved using [ 18 O]-labeled 1 O 2 released from thermolabile endoperoxides in association with nano-scale liquid chromatography coupled to electrospray ionization mass spectrometry. The structural characterization by nLC-MS/MS of the amino acids in the tryptic peptides of the proteins showed addition of [ 18 O]-labeling atoms in different amino acids. Copyright © 2017 John Wiley & Sons, Ltd.

  10. Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

    NASA Astrophysics Data System (ADS)

    Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

    1983-12-01

    Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

  11. Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

    PubMed Central

    Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

    2016-01-01

    A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries. PMID:27074882

  12. The Effects of Flame Structure on Extinction of CH4-O2-N2 Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Du, J.; Axelbaum, R. L.; Gokoglu, S. (Technical Monitor)

    1996-01-01

    The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.

  13. Wavelength-dependent UV photodesorption of pure N2 and O2 ices

    NASA Astrophysics Data System (ADS)

    Fayolle, E. C.; Bertin, M.; Romanzin, C.; Poderoso, H. A. M.; Philippe, L.; Michaut, X.; Jeseck, P.; Linnartz, H.; Öberg, K. I.; Fillion, J.-H.

    2013-08-01

    Context. Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims: N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods: Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results: N2 photodesorption mainly occurs through excitation of the b1Πu state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7-13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions: Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10-3 and 10-2 photodesorbed molecules per incoming photon.