WorldWideScience

Sample records for net oxygen evolution

  1. Oxygen evolution reaction catalysis

    Science.gov (United States)

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  2. Oxygen and Biological Evolution.

    Science.gov (United States)

    Baugh, Mark A.

    1990-01-01

    Discussed is the evolution of aerobic organisms from anaerobic organisms and the accompanying biochemistry that developed to motivate and enable this evolution. Uses of oxygen by aerobic organisms are described. (CW)

  3. Oxygen and Early Animal Evolution

    Science.gov (United States)

    Xiao, S.

    2012-12-01

    It is often hypothesized that the rise of animals was triggered by an increase in O2 levels in the atmosphere and oceans. However, this hypothesis is remarkably difficult to test, because the timing of animal divergences is poorly resolved, the physiology of early animals is often unknown, estimates of past pO2 levels come with large error bars, and causal relationships between oxygenation and animal evolution are difficult to establish. Nonetheless, existing phylogenetic, paleontological, and geochemical data indicate that the evolution of macroscopic animals and motile macrometazoans with energetically expensive lifestyles may be temporally coupled with ocean oxygenation events in the Ediacaran Period. Thus, it is plausible that ocean oxygenation may have been a limiting factor in the early evolution of macroscopic, complex, and metabolically aggressive animals (particularly bilaterian animals). However, ocean oxygenation and animal evolution were likely engaged in two-way interactions: Ediacaran oxygenation may have initially lifted a physiological barrier for the evolution of animal size, motility, and active lifestyles, but subsequent animal diversification in the Paleozoic may have also changed oceanic redox structures. Viewed in a broader context, the early evolutionary history of animals was contingent upon a series of events, including genetic preparation (developmental genetics), environmental facilitation (oceanic oxygenation), and ecological escalation (Cambrian explosion), but the rise of animals to ecological importance also had important geobiological impacts on oceanic redox structures, sedimentary fabrics, and global geochemical cycles.

  4. Mechanisms of oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Radmer, R; Cheniae, G

    1976-08-01

    The production of O/sub 2/ from water requires the collaboration of four oxidizing equivalents. When dark-adapted O/sub 2/ evolving photosynthetic material is illuminated by a sequence of short (less than 2 ..mu..sec) saturating flashes, the amount of O/sub 2/ evolved per flash oscillates with a period of four. This indicates that a charge-collector, operating with its own reaction center, successively collects and stores four oxidizing equivalents, which are used in a concerted oxidation of two water molecules. Luminescence, fluorescence, and pH changes also reflect this cycle of four. The O/sub 2/ precursor states are quite stable; under some conditions they can have a lifetime of several minutes. The O/sub 2/-yielding reactions and reactions associated with trap recovery are fast relative to the rate-limiting step of photosynthesis. The molecular identity of the charge-collector is unknown, but correlative evidence suggests that a manganese containing catalyst (approximately 4 Mn/charge collector) participates, possibly directly. Formation of the active Mn-containing catalyst occurs via a multi-quantum process occurring within the System II reaction center. The photoactivated catalyst, located on the inner face of the thylakoid membrane, remains permanently active and essentially inaccessible to chemicals other than analogs of H/sub 2/O (e.g., NH/sub 3/, NH/sub 2/OH). This O/sub 2/ evolving catalyst can be deactivated by a variety of treatments that do not alter the system II reaction center. Anions such as chloride seem to participate rather directly in the O/sub 2/ evolution process via unknown mechanism(s).

  5. The Evolution of the Actin Binding NET Superfamily

    Directory of Open Access Journals (Sweden)

    Tim eHawkins

    2014-06-01

    Full Text Available The arabidopsis Networked protein superfamily are plant-specific actin binding proteins which specifically label different membrane compartments and identify specialized sites of interaction between actin and membranes unique to plants. There are 13 members of the superfamily in arabidopsis which group into 4 distinct clades or subfamilies. NET homologues are absent from the genomes of metazoa and fungi, furthermore in Plantae NET sequences are also absent from the genome of mosses and more ancient extant plant clades. A single subfamily of the NET proteins are found encoded in the club moss genome; an extant species of the earliest vascular plants. Gymnosperms have examples from subfamilies 4 and 3 with a hybrid form of NET1 and 2 which shows characteristics of both NET1 and NET2. In addition to NET3 and 4 subfamilies, the NET1 and pollen-expressed NET2 subfamilies are only found as independent sequences in angiosperms. This is consistent with the divergence of reproductive actin. The four subfamilies are conserved across monocots and eudicots with the numbers of members of each clade expanding at this point due in part to regions of genome duplication. Since the emergence of the NET superfamily at the dawn of vascular plants they have continued to develop and diversify in a manner which has mirrored the divergence and complexity of plant species through evolution in the ‘March of Progress’.

  6. Covalency-reinforced oxygen evolution reaction catalyst

    National Research Council Canada - National Science Library

    Yagi, Shunsuke; Yamada, Ikuya; Tsukasaki, Hirofumi; Seno, Akihiro; Murakami, Makoto; Fujii, Hiroshi; Chen, Hungru; Umezawa, Naoto; Abe, Hideki; Nishiyama, Norimasa; Mori, Shigeo

    2015-01-01

    The oxygen evolution reaction that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal-air batteries and direct solar water splitting...

  7. Timescales of Oxygenation Following the Evolution of Oxygenic Photosynthesis.

    Science.gov (United States)

    Ward, Lewis M; Kirschvink, Joseph L; Fischer, Woodward W

    2016-03-01

    Among the most important bioenergetic innovations in the history of life was the invention of oxygenic photosynthesis-autotrophic growth by splitting water with sunlight-by Cyanobacteria. It is widely accepted that the invention of oxygenic photosynthesis ultimately resulted in the rise of oxygen by ca. 2.35 Gya, but it is debated whether this occurred more or less immediately as a proximal result of the evolution of oxygenic Cyanobacteria or whether they originated several hundred million to more than one billion years earlier in Earth history. The latter hypothesis involves a prolonged period during which oxygen production rates were insufficient to oxidize the atmosphere, potentially due to redox buffering by reduced species such as higher concentrations of ferrous iron in seawater. To examine the characteristic timescales for environmental oxygenation following the evolution of oxygenic photosynthesis, we applied a simple mathematical approach that captures many of the salient features of the major biogeochemical fluxes and reservoirs present in Archean and early Paleoproterozoic surface environments. Calculations illustrate that oxygenation would have overwhelmed redox buffers within ~100 kyr following the emergence of oxygenic photosynthesis, a geologically short amount of time unless rates of primary production were far lower than commonly expected. Fundamentally, this result arises because of the multiscale nature of the carbon and oxygen cycles: rates of gross primary production are orders of magnitude too fast for oxygen to be masked by Earth's geological buffers, and can only be effectively matched by respiration at non-negligible O2 concentrations. These results suggest that oxygenic photosynthesis arose shortly before the rise of oxygen, not hundreds of millions of years before it.

  8. The origin and evolution of atmospheric oxygen

    Science.gov (United States)

    Levine, Joel S.

    1988-01-01

    This paper discusses the chemical processes involved in the evolution of the earth's atmospheric oxygen and ozone, as well as the sources, sinks, and transfer rates of oxygen in the present atmosphere. Special attention is given the evolution of atmospheric O3 as a function of the buildup of O2, with the results of calculations presented as the vertical profiles of O3, in terms of the present atmospheric level (PAL) oxygen values. Calculations show that the total O3 column density that is approximately half of the present level was reached when atmospheric oxygen level reached 0.1 PAL. At this level of ozone, the biological shielding of the earth's surface from the UV radiation is believed to have been achieved.

  9. Evolution, atmospheric oxygen, and complex disease.

    Science.gov (United States)

    Koch, Lauren Gerard; Britton, Steven L

    2007-08-20

    If evolution is an accurate statement of our biology, then disease must be tightly associated with its patterns. We considered selection for more optimal capacity for energy transfer as the most general pattern of evolution. From this, we propose that the etiology of complex disease is linked tightly to the evolutionary transition to cellular complexity that was afforded by the steep thermodynamic gradient of an oxygen atmosphere. In accord with this thesis, clinical studies reveal a strong statistical link between low aerobic capacity and all-cause mortality. In addition, large-scale unbiased network analyses demonstrate the pivotal role of oxygen metabolism in cellular function. The demonstration that multiple disease risks segregated during two-way artificial selection for low and high aerobic capacity in rats provides a remote test of these possible connections between evolution, oxygen metabolism, and complex disease. Even more broadly, an atmosphere with oxygen may be uniquely essential for development of complex life anywhere because oxygen is stable as a diatomic gas, is easily transported, and has a high electronegativity for participation in energy transfer via redox reactions.

  10. Software Evolution in the context of .Net Framework

    OpenAIRE

    Walid, Rohaimi

    2007-01-01

    This paper discusses the process of software evolution and especially software migration in the context of .NET Technologies. Actually most of the companies that uses legacy systems implemented with procedural languages as C, Visual Basic and so on, meet some problems when new requirement specifications have to be integrated. One possibility to deal with this situation is to choose a good migration strategy from these legacy systems towards new Object Oriented design. There are some migration...

  11. Evolution of factors affecting placental oxygen transfer.

    Science.gov (United States)

    Carter, A M

    2009-03-01

    A review is given of the factors determining placental oxygen transfer and the oxygen supply to the fetus. In the case of continuous variables, such as the rate of placental blood flow, it is not possible to trace evolutionary trends. Discontinuous variables, for which we can define character states, are more amenable to analysis. This is exemplified by factors contributing, respectively, to blood oxygen affinity and placental diffusing capacity. Comparative genomics has given fresh insight into the evolution of the beta-globin gene complex. In higher primates, duplication of an embryonic gene yielded HBG-T2, a gene that is expressed in the fetus and confers high oxygen affinity on its haemoglobin. A separate event in ruminants involved duplication of an adult gene, again resulting in a fetally expressed variant (HBB-T3) that conveys high oxygen affinity. In rodents and lagomorphs, where fetal and adult haemoglobin are not different, developmental regulation of 2, 3-diphosphoglycerate ensures the high oxygen affinity of fetal blood. Oxygen diffusing capacity is dependent on diffusion distance, which may vary with the type of interhaemal barrier. It has been shown that epitheliochorial placentation is a derived state and that the common ancestor of placental mammals probably had a placenta of the endotheliochorial type. Where evolutionary trends are implied for mammals as a whole or within orders such as primates they often accompany a switch in reproductive strategy that is manifested in a change of newborn state from poorly developed (altricial) to well developed (precocial).

  12. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis

    National Research Council Canada - National Science Library

    Song, Fang; Hu, Xile

    2014-01-01

    The oxygen evolution reaction is a key reaction in water splitting. The common approach in the development of oxygen evolution catalysts is to search for catalytic materials with new and optimized chemical compositions and structures...

  13. Evolution of factors affecting placental oxygen transfer

    DEFF Research Database (Denmark)

    Carter, A M

    2009-01-01

    states, are more amenable to analysis. This is exemplified by factors contributing, respectively, to blood oxygen affinity and placental diffusing capacity. Comparative genomics has given fresh insight into the evolution of the beta-globin gene complex. In higher primates, duplication of an embryonic...... that epitheliochorial placentation is a derived state and that the common ancestor of placental mammals probably had a placenta of the endotheliochorial type. Where evolutionary trends are implied for mammals as a whole or within orders such as primates they often accompany a switch in reproductive strategy...

  14. Photosynthetic efficiency and oxygen evolution of Chlamydomonas reinhardtii under continuous and flashing light.

    Science.gov (United States)

    Vejrazka, Carsten; Janssen, Marcel; Benvenuti, Giulia; Streefland, Mathieu; Wijffels, René H

    2013-02-01

    As a result of mixing and light attenuation in a photobioreactor (PBR), microalgae experience light/dark (L/D) cycles that can enhance PBR efficiency. One parameter which characterizes L/D cycles is the duty cycle; it determines the time fraction algae spend in the light. The objective of this study was to determine the influence of different duty cycles on oxygen yield on absorbed light energy and photosynthetic oxygen evolution. Net oxygen evolution of Chlamydomonas reinhardtii was measured for four duty cycles (0.05, 0.1, 0.2, and 0.5) in a biological oxygen monitor (BOM). Oversaturating light flashes were applied in a square-wave fashion with four flash frequencies (5, 10, 50, and 100 Hz). Algae were precultivated in a turbidostat and acclimated to a low photon flux density (PFD). A photosynthesis-irradiance (PI) curve was measured under continuous illumination and used to calculate the net oxygen yield, which was maximal between a PFD of 100 and 200 μmol m⁻² s⁻¹. Net oxygen yield under flashing light was duty cycle-dependent: the highest yield was observed at a duty cycle of 0.1 (i.e., time-averaged PFD of 115 μmol m⁻² s⁻¹). At lower duty cycles, maintenance respiration reduced net oxygen yield. At higher duty cycles, photon absorption rate exceeded the maximal photon utilization rate, and, as a result, surplus light energy was dissipated which led to a reduction in net oxygen yield. This behavior was identical with the observation under continuous light. Based on these data, the optimal balance between oxygen yield and production rate can be determined to maximize PBR productivity.

  15. Tailoring the Oxygen Evolution Activity and Stability Using Defect Chemistry

    National Research Council Canada - National Science Library

    Julius Scholz; Marcel Risch; Garlef Wartner; Christoph Luderer; Vladimir Roddatis; Christian Jooss

    2017-01-01

    Improving the activity of catalysts for the oxygen evolution reaction (OER) requires a detailed understanding of the surface chemistry and structure to deduce structure-function relationships (descriptors...

  16. Evolution and physiology of neural oxygen sensing

    Directory of Open Access Journals (Sweden)

    Kauê Machado Costa

    2014-08-01

    Full Text Available Major evolutionary trends in animal physiology have been heavily influenced by atmospheric O2 levels. Amongst other important factors, the increase in atmospheric O2 which occurred in the Pre-Cambrian and the development of aerobic respiration beckoned the evolution of animal organ systems that were dedicated to the absorption and transportation of O2, e.g., the respiratory and cardiovascular systems of vertebrates. Global variations of O2 levels in post-Cambrian periods have also been correlated with evolutionary changes in animal physiology, especially cardiorespiratory function. Oxygen transportation systems are, in our view, ultimately controlled by the brain related mechanisms, which senses changes in O2 availability and regulates autonomic and respiratory responses that ensure the survival of the organism in the face of hypoxic challenges. In vertebrates, the major sensorial system for oxygen sensing and responding to hypoxia is the peripheral chemoreflex neuronal pathways, which includes the oxygen chemosensitive glomus cells and several brainstem regions involved in the autonomic regulation to the cardiovascular system and respiratory control. In this review we discuss the concept that regulating O2 homeostasis was one of the primordial roles of the nervous system. We also review the physiology of the peripheral chemoreflex, focusing on the integrative repercussions of chemoreflex activation and the evolutionary importance of this system, which is essential for the survival of complex organisms such as vertebrates. The contribution of hypoxia and peripheral chemoreflex for the development of diseases associated to the cardiovascular and respiratory systems is also discussed in an evolutionary context.

  17. Evolution and physiology of neural oxygen sensing

    Science.gov (United States)

    Costa, Kauê M.; Accorsi-Mendonça, Daniela; Moraes, Davi J. A.; Machado, Benedito H.

    2014-01-01

    Major evolutionary trends in animal physiology have been heavily influenced by atmospheric O2 levels. Amongst other important factors, the increase in atmospheric O2 which occurred in the Pre-Cambrian and the development of aerobic respiration beckoned the evolution of animal organ systems that were dedicated to the absorption and transportation of O2, e.g., the respiratory and cardiovascular systems of vertebrates. Global variations of O2 levels in post-Cambrian periods have also been correlated with evolutionary changes in animal physiology, especially cardiorespiratory function. Oxygen transportation systems are, in our view, ultimately controlled by the brain related mechanisms, which senses changes in O2 availability and regulates autonomic and respiratory responses that ensure the survival of the organism in the face of hypoxic challenges. In vertebrates, the major sensorial system for oxygen sensing and responding to hypoxia is the peripheral chemoreflex neuronal pathways, which includes the oxygen chemosensitive glomus cells and several brainstem regions involved in the autonomic regulation of the cardiovascular system and respiratory control. In this review we discuss the concept that regulating O2 homeostasis was one of the primordial roles of the nervous system. We also review the physiology of the peripheral chemoreflex, focusing on the integrative repercussions of chemoreflex activation and the evolutionary importance of this system, which is essential for the survival of complex organisms such as vertebrates. The contribution of hypoxia and peripheral chemoreflex for the development of diseases associated to the cardiovascular and respiratory systems is also discussed in an evolutionary context. PMID:25161625

  18. Space Station evolution study oxygen loop closure

    Science.gov (United States)

    Wood, M. G.; Delong, D.

    1993-01-01

    In the current Space Station Freedom (SSF) Permanently Manned Configuration (PMC), physical scars for closing the oxygen loop by the addition of oxygen generation and carbon dioxide reduction hardware are not included. During station restructuring, the capability for oxygen loop closure was deferred to the B-modules. As such, the ability to close the oxygen loop in the U.S. Laboratory module (LAB A) and the Habitation A module (HAB A) is contingent on the presence of the B modules. To base oxygen loop closure of SSF on the funding of the B-modules may not be desirable. Therefore, this study was requested to evaluate the necessary hooks and scars in the A-modules to facilitate closure of the oxygen loop at or subsequent to PMC. The study defines the scars for oxygen loop closure with impacts to cost, weight and volume and assesses the effects of byproduct venting. In addition, the recommended scenarios for closure with regard to topology and packaging are presented.

  19. Oxygen and the evolution of metabolic pathways

    Science.gov (United States)

    Jahnke, L. L.

    1986-01-01

    While a considerable amount of evidence has been accumulated about the history of oxygen on this planet, little is known about the relative amounts to which primitive cells might have been exposed. One clue may be found in the metabolic pathways of extant microorganisms. While eucaryotes are principally aerobic organisms, a number are capable of anaerobic growth by fermentation. One such eucaryotic microorganism, Saccharomyces cerevisiae, will grow in the complete absence of oxygen when supplemented with unsaturated fatty acid and sterol. Oxygen-requiring enzymes are involved in the synthesis of both of these compounds. Studies have demonstrated that the oxidative desaturation of palmitic acid and the conversion of squalene to sterols occur in the range of 10-(3) to 10(-2) PAL. Thus, if the oxygen requirements of these enzymatic processes are an indication, eucaryotes might be more primitive than anticipated from the microfossil record. Results of studies on the oxygen requirements for sterol and unsaturated fatty acid synthesis in a more primitive procaryotic system are also discussed.

  20. Oxygen and animal evolution: did a rise of atmospheric oxygen "trigger" the origin of animals?

    Science.gov (United States)

    Mills, Daniel B; Canfield, Donald E

    2014-12-01

    Recent studies challenge the classical view that the origin of animal life was primarily controlled by atmospheric oxygen levels. For example, some modern sponges, representing early-branching animals, can live under 200 times less oxygen than currently present in the atmosphere - levels commonly thought to have been maintained prior to their origination. Furthermore, it is increasingly argued that the earliest animals, which likely lived in low oxygen environments, played an active role in constructing the well-oxygenated conditions typical of the modern oceans. Therefore, while oxygen is still relevant to understanding early animal evolution, the relationships between the two might be less straightforward than previously thought. © 2014 WILEY Periodicals, Inc.

  1. The evolution of reactive oxygen species metabolism.

    Science.gov (United States)

    Inupakutika, Madhuri A; Sengupta, Soham; Devireddy, Amith R; Azad, Rajeev K; Mittler, Ron

    2016-11-01

    Reactive oxygen species (ROS) play a key role in the regulation of many biological processes in plants. Nonetheless, they are considered highly reactive and toxic to cells. Owing to their toxicity, as well as their important role in signaling, the level of ROS in cells needs to be tightly regulated. The ROS gene network, encoding a highly redundant arsenal of ROS scavenging mechanisms and an array of enzymes involved in ROS production, regulates ROS metabolism and signaling in plants. In this article, we review the role of the ROS gene network in plants and examine how it evolved. We identify key components of the ROS gene network in organisms that likely originated as early as 4.1-3.5 billion years ago, prior to the great oxidation event that resulted from the rise of cyanobacteria on Earth. This estimate concurs with recent evidence for the appearance of oxygenic photosynthetic organisms on Earth, suggesting that low and/or localized levels of photosynthetically produced oxygen necessitated the emergence of ROS scavenging mechanisms to protect life. Life forms have therefore evolved in the presence of ROS on Earth for at least 3.8-3.6 billion years, highlighting the intimate relationship that exists today between many physiological and developmental processes and ROS. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  2. Evolution and physiology of neural oxygen sensing

    OpenAIRE

    Kauê Machado Costa; Daniela eAccorsi-Mendonça; Moraes, Davi J. A.; Machado, Benedito H.

    2014-01-01

    Major evolutionary trends in animal physiology have been heavily influenced by atmospheric O2 levels. Amongst other important factors, the increase in atmospheric O2 which occurred in the Pre-Cambrian and the development of aerobic respiration beckoned the evolution of animal organ systems that were dedicated to the absorption and transportation of O2, e.g., the respiratory and cardiovascular systems of vertebrates. Global variations of O2 levels in post-Cambrian periods have also been correl...

  3. Hydrogen peroxide and the evolution of oxygenic photosynthesis

    Science.gov (United States)

    McKay, C. P.; Hartman, H.

    1991-05-01

    The early atmosphere of the Earth is considered to have been reducing (H2 rich) or neutral (CO2-N2). The present atmosphere by contrast is highly oxidizing (20% O2). The source of this oxygen is generally agreed to have been oxygenic photosynthesis, whereby organisms use water as the electron donor in the production of organic matter, liberating oxygen into the atmosphere. A major question in the evolution of life is how oxygenic photosynthesis could have evolved under anoxic conditions — and also when this capability evolved. It seems unlikely that water would be employed as the electron donor in anoxic environments that were rich in reducing agents such as ferrous or sulfide ions which could play that role. The abiotic production of atmospheric oxidants could have provided a mechanism by which locally oxidizing conditions were sustained within spatially confined habitats thus removing the available reductants and forcing photosynthetic organisms to utilize water as the electron donor. We suggest that atmospheric H2O2 played the key role in inducing oxygenic photosynthesis because as peroxide increased in a local environment, organisms would not only be faced with a loss of reductant, but they would also be pressed to develop the biochemical apparatus (e.g., catalase) that would ultimately be needed to protect against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis while global conditions were still anaerobic.

  4. Net community production at Ocean Station Papa observed with nitrate and oxygen sensors on profiling floats

    Science.gov (United States)

    Plant, Joshua N.; Johnson, Kenneth S.; Sakamoto, Carole M.; Jannasch, Hans W.; Coletti, Luke J.; Riser, Stephen C.; Swift, Dana D.

    2016-06-01

    Six profiling floats equipped with nitrate and oxygen sensors were deployed at Ocean Station P in the Gulf of Alaska. The resulting six calendar years and 10 float years of nitrate and oxygen data were used to determine an average annual cycle for net community production (NCP) in the top 35 m of the water column. NCP became positive in February as soon as the mixing activity in the surface layer began to weaken, but nearly 3 months before the traditionally defined mixed layer began to shoal from its winter time maximum. NCP displayed two maxima, one toward the end of May and another in August with a summertime minimum in June corresponding to the historical peak in mesozooplankton biomass. The average annual NCP was determined to be 1.5 ± 0.6 mol C m-2 yr-1 using nitrate and 1.5 ± 0.7 mol C m-2 yr-1 using oxygen. The results from oxygen data proved to be quite sensitive to the gas exchange model used as well as the accuracy of the oxygen measurement. Gas exchange models optimized for carbon dioxide flux generally ignore transport due to gas exchange through the injection of bubbles, and these models yield NCP values that are two to three time higher than the nitrate-based estimates. If nitrate and oxygen NCP rates are assumed to be related by the Redfield model, we show that the oxygen gas exchange model can be optimized by tuning the exchange terms to reproduce the nitrate NCP annual cycle.

  5. Beyond the volcano limitations in electrocatalysis - oxygen evolution reaction

    DEFF Research Database (Denmark)

    Halck, Niels Bendtsen; Petrykin, Valery; Krtil, Petr

    2014-01-01

    Oxygen evolution catalysis is restricted by the interdependence of adsorption energies of the reaction intermediates and the surface reactivity. The interdependence reduces the number of degrees of freedom available for catalyst optimization. Here it is demonstrated that this limitation can be re...

  6. Molecular Evolution of the Oxygen-Binding Hemerythrin Domain.

    Directory of Open Access Journals (Sweden)

    Claudia Alvarez-Carreño

    Full Text Available The evolution of oxygenic photosynthesis during Precambrian times entailed the diversification of strategies minimizing reactive oxygen species-associated damage. Four families of oxygen-carrier proteins (hemoglobin, hemerythrin and the two non-homologous families of arthropodan and molluscan hemocyanins are known to have evolved independently the capacity to bind oxygen reversibly, providing cells with strategies to cope with the evolutionary pressure of oxygen accumulation. Oxygen-binding hemerythrin was first studied in marine invertebrates but further research has made it clear that it is present in the three domains of life, strongly suggesting that its origin predated the emergence of eukaryotes.Oxygen-binding hemerythrins are a monophyletic sub-group of the hemerythrin/HHE (histidine, histidine, glutamic acid cation-binding domain. Oxygen-binding hemerythrin homologs were unambiguously identified in 367/2236 bacterial, 21/150 archaeal and 4/135 eukaryotic genomes. Overall, oxygen-binding hemerythrin homologues were found in the same proportion as single-domain and as long protein sequences. The associated functions of protein domains in long hemerythrin sequences can be classified in three major groups: signal transduction, phosphorelay response regulation, and protein binding. This suggests that in many organisms the reversible oxygen-binding capacity was incorporated in signaling pathways. A maximum-likelihood tree of oxygen-binding hemerythrin homologues revealed a complex evolutionary history in which lateral gene transfer, duplications and gene losses appear to have played an important role.Hemerythrin is an ancient protein domain with a complex evolutionary history. The distinctive iron-binding coordination site of oxygen-binding hemerythrins evolved first in prokaryotes, very likely prior to the divergence of Firmicutes and Proteobacteria, and spread into many bacterial, archaeal and eukaryotic species. The later evolution of the

  7. Molecular Evolution of the Oxygen-Binding Hemerythrin Domain.

    Science.gov (United States)

    Alvarez-Carreño, Claudia; Becerra, Arturo; Lazcano, Antonio

    2016-01-01

    The evolution of oxygenic photosynthesis during Precambrian times entailed the diversification of strategies minimizing reactive oxygen species-associated damage. Four families of oxygen-carrier proteins (hemoglobin, hemerythrin and the two non-homologous families of arthropodan and molluscan hemocyanins) are known to have evolved independently the capacity to bind oxygen reversibly, providing cells with strategies to cope with the evolutionary pressure of oxygen accumulation. Oxygen-binding hemerythrin was first studied in marine invertebrates but further research has made it clear that it is present in the three domains of life, strongly suggesting that its origin predated the emergence of eukaryotes. Oxygen-binding hemerythrins are a monophyletic sub-group of the hemerythrin/HHE (histidine, histidine, glutamic acid) cation-binding domain. Oxygen-binding hemerythrin homologs were unambiguously identified in 367/2236 bacterial, 21/150 archaeal and 4/135 eukaryotic genomes. Overall, oxygen-binding hemerythrin homologues were found in the same proportion as single-domain and as long protein sequences. The associated functions of protein domains in long hemerythrin sequences can be classified in three major groups: signal transduction, phosphorelay response regulation, and protein binding. This suggests that in many organisms the reversible oxygen-binding capacity was incorporated in signaling pathways. A maximum-likelihood tree of oxygen-binding hemerythrin homologues revealed a complex evolutionary history in which lateral gene transfer, duplications and gene losses appear to have played an important role. Hemerythrin is an ancient protein domain with a complex evolutionary history. The distinctive iron-binding coordination site of oxygen-binding hemerythrins evolved first in prokaryotes, very likely prior to the divergence of Firmicutes and Proteobacteria, and spread into many bacterial, archaeal and eukaryotic species. The later evolution of the oxygen

  8. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    Science.gov (United States)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  9. Oxygen Evolution at Hematite Surfaces: The Impact of Structure and Oxygen Vacancies on Lowering the Overpotential

    NARCIS (Netherlands)

    Zhang, X.; Klaver, P.; van Santen, R.; van de Sanden, M. C. M.; Bieberle, A.

    2016-01-01

    Simulations of the oxygen evolution reaction (OER) are essential for understanding the limitations of water splitting. Most research has focused so far on the OER at flat metal oxide surfaces. The structure sensitivity of the OER has, however, recently been highlighted as a promising research

  10. A bifunctional perovskite catalyst for oxygen reduction and evolution.

    Science.gov (United States)

    Jung, Jae-Il; Jeong, Hu Young; Lee, Jang-Soo; Kim, Min Gyu; Cho, Jaephil

    2014-04-25

    La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3d is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm-scale rhombohedral LaCoO3 cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A-site cations with La3+ and local stress on Cosite sub-lattice with the cubic perovskite structure.

  11. A nickel iron diselenide-derived efficient oxygen-evolution catalyst

    OpenAIRE

    Xu, Xiang; Song, Fang; Hu, Xile

    2016-01-01

    Efficient oxygen-evolution reaction catalysts are required for the cost-effective generation of solar fuels. Metal selenides have been reported as promising oxygen-evolution catalysts; however, their active forms are yet to be elucidated. Here we show that a representative selenide catalyst, nickel selenide, is entirely converted into nickel hydroxide under oxygen-evolution conditions. This result indicates that metal selenides are unstable during oxygen evolution, and the in situ generated m...

  12. IR-doped ruthenium oxide catalyst for oxygen evolution

    Science.gov (United States)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  13. The mechanisms of oxygen reduction and evolution reactions in nonaqueous lithium-oxygen batteries.

    Science.gov (United States)

    Cao, Ruiguo; Walter, Eric D; Xu, Wu; Nasybulin, Eduard N; Bhattacharya, Priyanka; Bowden, Mark E; Engelhard, Mark H; Zhang, Ji-Guang

    2014-09-01

    A fundamental understanding of the mechanisms of both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous lithium-oxygen (Li-O2) batteries is essential for the further development of these batteries. In this work, we systematically investigate the mechanisms of the ORR/OER reactions in nonaqueous Li-O2 batteries by using electron paramagnetic resonance (EPR) spectroscopy, using 5,5-dimethyl-pyrroline N-oxide as a spin trap. The study provides direct verification of the formation of the superoxide radical anion (O2(˙-)) as an intermediate in the ORR during the discharge process, while no O2(˙-) was detected in the OER during the charge process. These findings provide insight into, and an understanding of, the fundamental reaction mechanisms involving oxygen and guide the further development of this field. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The impact of oxygen on metabolic evolution: a chemoinformatic investigation.

    Science.gov (United States)

    Jiang, Ying-Ying; Kong, De-Xin; Qin, Tao; Li, Xiao; Caetano-Anollés, Gustavo; Zhang, Hong-Yu

    2012-01-01

    The appearance of planetary oxygen likely transformed the chemical and biochemical makeup of life and probably triggered episodes of organismal diversification. Here we use chemoinformatic methods to explore the impact of the rise of oxygen on metabolic evolution. We undertake a comprehensive comparative analysis of structures, chemical properties and chemical reactions of anaerobic and aerobic metabolites. The results indicate that aerobic metabolism has expanded the structural and chemical space of metabolites considerably, including the appearance of 130 novel molecular scaffolds. The molecular functions of these metabolites are mainly associated with derived aspects of cellular life, such as signal transfer, defense against biotic factors, and protection of organisms from oxidation. Moreover, aerobic metabolites are more hydrophobic and rigid than anaerobic compounds, suggesting they are better fit to modulate membrane functions and to serve as transmembrane signaling factors. Since higher organisms depend largely on sophisticated membrane-enabled functions and intercellular signaling systems, the metabolic developments brought about by oxygen benefit the diversity of cellular makeup and the complexity of cellular organization as well. These findings enhance our understanding of the molecular link between oxygen and evolution. They also show the significance of chemoinformatics in addressing basic biological questions.

  15. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Ruiguo; Walter, Eric D.; Xu, Wu; Nasybulin, Eduard N.; Bhattacharya, Priyanka; Bowden, Mark E.; Engelhard, Mark H.; Zhang, Jiguang

    2014-09-01

    The oxygen reduction/evolution reaction (ORR/OER) mechanisms in nonaqueous Li-O2 batteries have been investigated by using electron paramagnetic resonance spectroscopy in this work. We identified the superoxide radical anion (O2•-) as an intermediate in the ORR process using 5,5-dimethyl-pyrroline N-oxide as a spin trap, while no O2•- in OER was detected during the charge process. These findings provide insightful understanding on the fundamental oxygen reaction mechanisms in rechargeable nonaqueous Li-O2 batteries.

  16. Atmospheric oxygen level and the evolution of insect body size.

    Science.gov (United States)

    Harrison, Jon F; Kaiser, Alexander; VandenBrooks, John M

    2010-07-07

    Insects are small relative to vertebrates, possibly owing to limitations or costs associated with their blind-ended tracheal respiratory system. The giant insects of the late Palaeozoic occurred when atmospheric PO(2) (aPO(2)) was hyperoxic, supporting a role for oxygen in the evolution of insect body size. The paucity of the insect fossil record and the complex interactions between atmospheric oxygen level, organisms and their communities makes it impossible to definitively accept or reject the historical oxygen-size link, and multiple alternative hypotheses exist. However, a variety of recent empirical findings support a link between oxygen and insect size, including: (i) most insects develop smaller body sizes in hypoxia, and some develop and evolve larger sizes in hyperoxia; (ii) insects developmentally and evolutionarily reduce their proportional investment in the tracheal system when living in higher aPO(2), suggesting that there are significant costs associated with tracheal system structure and function; and (iii) larger insects invest more of their body in the tracheal system, potentially leading to greater effects of aPO(2) on larger insects. Together, these provide a wealth of plausible mechanisms by which tracheal oxygen delivery may be centrally involved in setting the relatively small size of insects and for hyperoxia-enabled Palaeozoic gigantism.

  17. Electrons, life and the evolution of Earth's oxygen cycle.

    Science.gov (United States)

    Falkowski, Paul G; Godfrey, Linda V

    2008-08-27

    The biogeochemical cycles of H, C, N, O and S are coupled via biologically catalysed electron transfer (redox) reactions. The metabolic processes responsible for maintaining these cycles evolved over the first ca 2.3 Ga of Earth's history in prokaryotes and, through a sequence of events, led to the production of oxygen via the photobiologically catalysed oxidation of water. However, geochemical evidence suggests that there was a delay of several hundred million years before oxygen accumulated in Earth's atmosphere related to changes in the burial efficiency of organic matter and fundamental alterations in the nitrogen cycle. In the latter case, the presence of free molecular oxygen allowed ammonium to be oxidized to nitrate and subsequently denitrified. The interaction between the oxygen and nitrogen cycles in particular led to a negative feedback, in which increased production of oxygen led to decreased fixed inorganic nitrogen in the oceans. This feedback, which is supported by isotopic analyses of fixed nitrogen in sedimentary rocks from the Late Archaean, continues to the present. However, once sufficient oxygen accumulated in Earth's atmosphere to allow nitrification to out-compete denitrification, a new stable electron 'market' emerged in which oxygenic photosynthesis and aerobic respiration ultimately spread via endosymbiotic events and massive lateral gene transfer to eukaryotic host cells, allowing the evolution of complex (i.e. animal) life forms. The resulting network of electron transfers led a gas composition of Earth's atmosphere that is far from thermodynamic equilibrium (i.e. it is an emergent property), yet is relatively stable on geological time scales. The early coevolution of the C, N and O cycles, and the resulting non-equilibrium gaseous by-products can be used as a guide to search for the presence of life on terrestrial planets outside of our Solar System.

  18. How does oxygen rise drive evolution? Clues from oxygen-dependent biosynthesis of nuclear receptor ligands.

    Science.gov (United States)

    Jiang, Ying-Ying; Kong, De-Xin; Qin, Tao; Zhang, Hong-Yu

    2010-01-08

    It is well known that oxygen rise greatly facilitated biological evolution. However, the underlying mechanisms remain elusive. Recently, Raymond and Segrè revealed that molecular oxygen allows 1000 more metabolic reactions than can occur in anoxic conditions. From the novel metabolites produced in aerobic metabolism, we serendipitously found that some of the metabolites are signaling molecules that target nuclear receptors. Since nuclear signaling systems are indispensable to superior organisms, we speculated that aerobic metabolism may facilitate biological evolution through promoting the establishment of nuclear signaling systems. This hypothesis is validated by the observation that most (97.5%) nuclear receptor ligands are produced by aerobic metabolism, which is further explained in terms of the chemical criteria (appropriate volume and rather high hydrophobicity) of nuclear receptor ligands that aerobic metabolites are more ready than anaerobic counterparts to satisfy these criteria. Copyright 2010. Published by Elsevier Inc.

  19. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution

    Science.gov (United States)

    Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong; Hong, Wesley T.; Lee, Yueh-Lin; Giordano, Livia; Stoerzinger, Kelsey A.; Koper, Marc T. M.; Shao-Horn, Yang

    2017-05-01

    Understanding how materials that catalyse the oxygen evolution reaction (OER) function is essential for the development of efficient energy-storage technologies. The traditional understanding of the OER mechanism on metal oxides involves four concerted proton-electron transfer steps on metal-ion centres at their surface and product oxygen molecules derived from water. Here, using in situ 18O isotope labelling mass spectrometry, we provide direct experimental evidence that the O2 generated during the OER on some highly active oxides can come from lattice oxygen. The oxides capable of lattice-oxygen oxidation also exhibit pH-dependent OER activity on the reversible hydrogen electrode scale, indicating non-concerted proton-electron transfers in the OER mechanism. Based on our experimental data and density functional theory calculations, we discuss mechanisms that are fundamentally different from the conventional scheme and show that increasing the covalency of metal-oxygen bonds is critical to trigger lattice-oxygen oxidation and enable non-concerted proton-electron transfers during OER.

  20. Box models for the evolution of atmospheric oxygen: an update

    Science.gov (United States)

    Kasting, J. F.

    1991-01-01

    A simple 3-box model of the atmosphere/ocean system is used to describe the various stages in the evolution of atmospheric oxygen. In Stage I, which probably lasted until redbeds began to form about 2.0 Ga ago, the Earth's surface environment was generally devoid of free O2, except possibly in localized regions of high productivity in the surface ocean. In Stage II, which may have lasted for less than 150 Ma, the atmosphere and surface ocean were oxidizing, while the deep ocean remained anoxic. In Stage III, which commenced with the disappearance of banded iron formations around 1.85 Ga ago and has lasted until the present, all three surface reservoirs contained appreciable amounts of free O2. Recent and not-so-recent controversies regarding the abundance of oxygen in the Archean atmosphere are identified and discussed. The rate of O2 increase during the Middle and Late Proterozoic is identified as another outstanding question.

  1. Fine-tuning the activity of oxygen evolution catalysts

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares; Masini, Federico; Frydendal, Rasmus

    2016-01-01

    Water splitting is hindered by the sluggish kinetics of the oxygen evolution reaction (OER). The choice of materials for this reaction in acid is limited to the platinum group metals; high loading required of these scarce and expensive elements severely limit the scalability of such technology....... Ruthenium oxide is among the best catalysts for OER, however the reported activity and stability can vary tremendously depending on the preparation conditions and pre-treatment. Herein, we investigate the effect of oxidation treatment on mass-selected Ru nanoparticles in the size range between 2 and 10 nm....... The effect of two distinct oxidation pre-treatments on the activity and stability have been investigated: (1) thermal oxidation; and (2) oxidation with an oxygen plasma under vacuum. We report that activity and stability can be tuned by using different oxidation pre-treatments. Thermally oxidized particles...

  2. Oxygen evolution studies on perovskite films in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Hermann, V.; Comninellis, Ch. [Swiss Federal Inst. of Technology, Lausanne (Switzerland); Mueller, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Thin films of La{sub 0.6}Ca{sub 0.4}CoO{sub 3} perovskite were deposited on nickel plates by thermal decomposition of the metal nitrates. The electrochemical activity of the films for oxygen evolution in KOH solutions (0.1-1 M) was investigated. The reaction order with respect to OH{sup -} ion was found to be around 0.7. The results correlate fairly well with a mechanism in which breaking of the intermediate metal-peroxide bond at the Co ion is the rate-determining step. (author) 4 figs., 4 refs.

  3. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

    Science.gov (United States)

    McCrory, Charles C L; Jung, Suho; Peters, Jonas C; Jaramillo, Thomas F

    2013-11-13

    Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.

  4. Paleosols and the evolution of atmospheric oxygen: a critical review

    Science.gov (United States)

    Rye, R.; Holland, H. D.

    1998-01-01

    A number of investigators have used chemical profiles of paleosols to reconstruct the evolution of atmospheric oxygen levels during the course of Earth history (Holland, 1984, 1994; Kirkham and Roscoe, 1993; Ohmoto, 1996). Over the past decade Holland and his co-workers have examined reported paleosols from six localities that formed between 2.75 and 0.45 Ga. They have found that the chemical profiles of these paleosols are consistent with a dramatic change in atmospheric PO2 between 2.2 and 2.0 Ga from or = 0.03 atm (Holland, 1994). Ohmoto (1996) examined chemical data from twelve reported paleosols ranging in age from 2.9 to 1.8 Ga. He concluded that these chemical profiles indicate that atmospheric PO2 has not changed significantly during the past 3.0 Ga. We seek to resolve the conflict between these reconstructions through a broader examination of the paleosol literature, both to determine which reported paleosols can be definitively identified as such and to determine what these definite paleosols tell us about atmospheric evolution. We here review reports describing over 50 proposed paleosols, all but two are older than 1.7 Ga. Our review indicates that 15 of these reported paleosols can be definitively identified as ancient soils. The behavior of iron uring the formation of these 15 paleosols provides both qualitative and semiquantitative information about the evolution of the redox state of the atmosphere. Every definitely identified pre-2.44 Ga paleosol suffered significant Fe loss during weathering. This loss indicates that atmospheric PO2 was always less than about 5 x l0(-4) atm prior to 2.44 Ga. Analysis of the Hokkalampi paleosol (2.44-2.2 Ga) (Marmo, 1992) and the Ville Marie paleosol (2.38-2.215 Ga) (Rainbird, Nesbitt, and Donaldson, 1990) yield ambiguous results regarding atmospheric PO2. Loss of Fe during the weathering of the 2.245 to 2.203 Ga Hekpoort paleosol (Button, 1979) indicates that atmospheric PO2 was less than 8 x 10(-4) atm shortly

  5. Activating the Bifunctionality of a Perovskite Oxide toward Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Lyu, Yu-Qi; Ciucci, Francesco

    2017-10-18

    This article presents a facile and effective approach to activate the bifunctionality of calcium-manganese perovskites toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We substituted Nb into the Mn site of CaMnO3 (CMO) and treated the material with H2. The as-obtained CaMn0.75Nb0.25O3-δ (H2-CMNO) displays the same structure as that of CMO, and compared to that of CMO, H2-CMNO exhibits significantly improved OER performance, including a lower overpotential, a reduced Tafel slope, a higher mass activity, and enhanced stability. In addition, the ORR performance of H2-CMNO is also greatly enhanced, relative to CMO, with a higher ORR activity and a more efficient electron-transfer pathway. H2-CMNO shows an even higher activity-per-catalyst cost and superior stability than that of state-of-the-art materials, such as IrO2 and Pt/C. This great enhancement in ORR and OER activity of H2-CMNO is attributed to several factors, including phase stabilization, optimized eg filling, better OH- adsorption, and improved electrical conductivity.

  6. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    Science.gov (United States)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  7. Halogen substitutions leading to enhanced oxygen evolution and oxygen reduction reactions in metalloporphyrin frameworks.

    Science.gov (United States)

    Wannakao, Sippakorn; Maihom, Thana; Kongpatpanich, Kanokwan; Limtrakul, Jumras; Promarak, Vinich

    2017-11-08

    The oxygen evolution and oxygen reduction reactions (OER and ORR, respectively) are important in the field of renewable and clean energy, particularly for hydrogen production and fuel cells. These applications have so far been limited because of the high price of the catalysts and the energy loss due to overpotentials. Hence, non-precious metal catalysts with high efficiency toward the OER/ORR are desirable. In this work, we employ density functional theory (DFT) calculations to study the OER/ORR on metalloporphyrin and halogenated metalloporphyrin frameworks. The free energies of the reaction intermediates, including OH, O and OOH, were measured on 14 metal sites (Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Ir, Pt and Au) of the metalloporphyrin frameworks. Adsorption free energy relations were found and used to establish the reaction trend. The group 9 metals, namely Co, Rh and Ir, turn out to be potential candidates for both the OER and ORR because they provide intermediate free energies close to those of an ideal catalyst. The substitution of halogen atoms at the beta-positions of the metalloporphyrins of group 9 metals modifies the adsorption free energies of the intermediates so that they become closer to the ideal values and in turn reduce the OER and ORR overpotentials. After functionalization, Co-Por-F provides the lowest ORR overpotential and reduces the OER overpotential, approaching the value for an expensive Ir catalyst. Analysis of the electronic structure shows that controlling the d-band splitting by chemical manipulation of the single active site catalyst can be the key to enhancing the efficiency of these reactions.

  8. Modularity and Sparsity: Evolution of Neural Net Controllers in Physically Embodied Robots

    Directory of Open Access Journals (Sweden)

    Nicholas Livingston

    2016-12-01

    Full Text Available While modularity is thought to be central for the evolution of complexity and evolvability, it remains unclear how systems boot-strap themselves into modularity from random or fully integrated starting conditions. Clune et al. (2013 suggested that a positive correlation between sparsity and modularity is the prime cause of this transition. We sought to test the generality of this modularity-sparsity hypothesis by testing it for the first time in physically embodied robots. A population of ten Tadros — autonomous, surface-swimming robots propelled by a flapping tail — was used. Individuals varied only in the structure of their neural net control, a 2 x 6 x 2 network with recurrence in the hidden layer. Each of the 60 possible connections was coded in the genome, and could achieve one of three states: -1, 0, 1. Inputs were two light-dependent resistors and outputs were two motor control variables to the flapping tail, one for the frequency of the flapping and the other for the turning offset. Each Tadro was tested separately in a circular tank lit by a single overhead light source. Fitness was the amount of light gathered by a vertically oriented sensor that was disconnected from the controller net. Reproduction was asexual, with the top performer cloned and then all individuals entered into a roulette wheel selection process, with genomes mutated to create the offspring. The starting population of networks was randomly generated. Over ten generations, the population’s mean fitness increased two-fold. This evolution occurred in spite of an unintentional integer overflow problem in recurrent nodes in the hidden layer that caused outputs to oscillate. Our investigation of the oscillatory behavior showed that the mutual information of inputs and outputs was sufficient for the reactive behaviors observed. While we had predicted that both modularity and sparsity would follow the same trend as fitness, neither did so. Instead, selection gradients

  9. CONTINUOUS, AUTOMATED AND SIMULTANEOUS MEASUREMENT OF OXYGEN UPTAKE AND CARBON DIOXIDE EVOLUTION IN BIOLOGICAL SYSTEMS

    Science.gov (United States)

    Commercial respirometers are capable of continuously and automatically measuring oxygen uptake in bioreactors. A method for continuously and automatically measuring carbon dioxide evolution can be retrofitted to commercial respirometers. Continuous and automatic measurements of...

  10. Advanced Oxygen Evolution Catalyst for Electrolyzer Energy Storage for Lunar Surface Systems Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Future NASA lunar missions will require a high efficiency, lightweight, long life, maintenance-free water electrolyzer for energy storage. Anodic oxygen evolution...

  11. Oxygen and animal evolution: Did a rise of atmospheric oxygen trigger the origin of animals?

    DEFF Research Database (Denmark)

    Mills, Daniel Brady; Canfield, Donald Eugene

    2014-01-01

    Recent studies challenge the classical view that the origin of animal life was primarily controlled by atmospheric oxygen levels. For example, some modern sponges, representing early-branching animals, can live under 200 times less oxygen than currently present in the atmosphere - levels commonly...... thought to have been maintained prior to their origination. Furthermore, it is increasingly argued that the earliest animals, which likely lived in low oxygen environments, played an active role in constructing the well-oxygenated conditions typical of the modern oceans. Therefore, while oxygen is still...

  12. Physical model of evolution of oxygen subsystem of PLZT-ceramics at neutron irradiation and annealing

    CERN Document Server

    Kulikov, D V; Trushin, Y V; Veber, K V; Khumer, K; Bitner, R; Shternberg, A R

    2001-01-01

    The physical model of evolution of the oxygen subsystem defects of the ferroelectric PLZT-ceramics by the neutron irradiation and isochrone annealing is proposed. The model accounts for the effect the lanthanum content on the material properties. The changes in the oxygen vacancies concentration, calculated by the proposed model, agree well with the polarization experimental behavior by the irradiated material annealing

  13. Advanced Oxygen Evolution Catalysts for PEM Electrolyzers Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Future NASA missions require high efficiency, lightweight, long life, and maintenance-free water electrolyzer technologies to generate oxygen and/or hydrogen for...

  14. Interphase Evolution of a Lithium-Ion/Oxygen Battery.

    Science.gov (United States)

    Elia, Giuseppe Antonio; Bresser, Dominic; Reiter, Jakub; Oberhumer, Philipp; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

    2015-10-14

    A novel lithium-ion/oxygen battery employing Pyr14TFSI-LiTFSI as the electrolyte and nanostructured LixSn-C as the anode is reported. The remarkable energy content of the oxygen cathode, the replacement of the lithium metal anode by a nanostructured stable lithium-alloying composite, and the concomitant use of nonflammable ionic liquid-based electrolyte result in a new and intrinsically safer energy storage system. The lithium-ion/oxygen battery delivers a stable capacity of 500 mAh g(-1) at a working voltage of 2.4 V with a low charge-discharge polarization. However, further characterization of this new system by electrochemical impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy reveals the progressive decrease of the battery working voltage, because of the crossover of oxygen through the electrolyte and its direct reaction with the LixSn-C anode.

  15. Electrons, life and the evolution of Earth's oxygen cycle

    OpenAIRE

    Falkowski, Paul G; Godfrey, Linda V.

    2008-01-01

    The biogeochemical cycles of H, C, N, O and S are coupled via biologically catalysed electron transfer (redox) reactions. The metabolic processes responsible for maintaining these cycles evolved over the first ca 2.3 Ga of Earth's history in prokaryotes and, through a sequence of events, led to the production of oxygen via the photobiologically catalysed oxidation of water. However, geochemical evidence suggests that there was a delay of several hundred million years before oxygen accumulated...

  16. Modeling Variable Phanerozoic Oxygen Effects on Physiology and Evolution.

    Science.gov (United States)

    Graham, Jeffrey B; Jew, Corey J; Wegner, Nicholas C

    2016-01-01

    Geochemical approximation of Earth's atmospheric O2 level over geologic time prompts hypotheses linking hyper- and hypoxic atmospheres to transformative events in the evolutionary history of the biosphere. Such correlations, however, remain problematic due to the relative imprecision of the timing and scope of oxygen change and the looseness of its overlay on the chronology of key biotic events such as radiations, evolutionary innovation, and extinctions. There are nevertheless general attributions of atmospheric oxygen concentration to key evolutionary changes among groups having a primary dependence upon oxygen diffusion for respiration. These include the occurrence of Devonian hypoxia and the accentuation of air-breathing dependence leading to the origin of vertebrate terrestriality, the occurrence of Carboniferous-Permian hyperoxia and the major radiation of early tetrapods and the origins of insect flight and gigantism, and the Mid-Late Permian oxygen decline accompanying the Permian extinction. However, because of variability between and error within different atmospheric models, there is little basis for postulating correlations outside the Late Paleozoic. Other problems arising in the correlation of paleo-oxygen with significant biological events include tendencies to ignore the role of blood pigment affinity modulation in maintaining homeostasis, the slow rates of O2 change that would have allowed for adaptation, and significant respiratory and circulatory modifications that can and do occur without changes in atmospheric oxygen. The purpose of this paper is thus to refocus thinking about basic questions central to the biological and physiological implications of O2 change over geological time.

  17. Formation and Migration of Oxygen Vacancies in SrCoO3 and their effect on Oxygen Evolution Reactions

    KAUST Repository

    Tahini, Hassan A.

    2016-07-18

    Perovskite SrCoO3 is a potentially useful material for promoting the electrocatalytic oxygen evolution reaction, with high activities predicted theoretically and observed experimentally for closely related doped perovskite materials. However, complete stoichiometric oxidation is very difficult to realize experimentally – in almost all cases there are significant fractions of oxygen vacancies present. Here, using first principles calculations we study oxygen vacancies in perovskite SrCoO3 from thermodynamic, electronic and kinetic points of view. We find that an oxygen vacancy donates two electrons to neighboring Co sites in the form of localized charge. The formation energy of a single vacancy is very low and estimated to be 1.26 eV in the dilute limit. We find that a vacancy is quite mobile with a migration energy of ~0.5 eV. Moreover, we predict that oxygen vacancies exhibit a tendency towards clustering which is in accordance with the material’s ability to form a variety of oxygen-deficient structures. These vacancies have a profound effect on the material’s ability to facilitate OER, increasing the overpotential from ~0.3 V for the perfect material to ~0.7 for defective surfaces. A moderate compressive biaxial strain (2%) is predicted here to increase the surface oxygen vacancy formation energy by ca. 30%, thus reducing the concentration of surface vacancies and thereby preserving the OER activity of the material.

  18. The effect of oxygen on biochemical networks and the evolution of complex life.

    Science.gov (United States)

    Raymond, Jason; Segrè, Daniel

    2006-03-24

    The evolution of oxygenic photosynthesis and ensuing oxygenation of Earth's atmosphere represent a major transition in the history of life. Although many organisms retreated to anoxic environments, others evolved to use oxygen as a high-potential redox couple while concomitantly mitigating its toxicity. To understand the changes in biochemistry and enzymology that accompanied adaptation to O2, we integrated network analysis with information on enzyme evolution to infer how oxygen availability changed the architecture of metabolic networks. Our analysis revealed the existence of four discrete groups of networks of increasing complexity, with transitions between groups being contingent on the presence of key metabolites, including molecular oxygen, which was required for transition into the largest networks.

  19. The ancient oxygen exosphere of Mars - Implications for atmosphere evolution

    Science.gov (United States)

    Zhang, M. H. G.; Luhmann, J. G.; Bougher, S. W.; Nagy, A. F.

    1993-01-01

    The paper considers absorption of oxygen (atoms and ions) by the surface as a mechanism for the early Martian atmosphere escape, due to the effect of high EUV flux of the ancient sun. Hot oxygen exosphere densities in ancient atmosphere and ionosphere are calculated for different EUV fluxes and the escape fluxes associated with these exposures. Using these densities, the ion production rate above the ionopause is calculated for different epochs including photoionization, charge exchange, and solar wind electron impact. It is found that, when the inferred high solar EUV fluxes of the past are taken into account, oxygen equivalent to that in several tens of meters of water, planet-wide, should have escaped Martian atmosphere to space over the last 3 Gyr.

  20. Oxygen reduction and evolution at single-metal active sites

    DEFF Research Database (Denmark)

    Calle-Vallejo, F.; Martínez, J.I.; García Lastra, Juan Maria

    2013-01-01

    A worldwide spread of clean technologies such as low-temperature fuel cells and electrolyzers depends strictly on their technical reliability and economic affordability. Currently, both conditions are hardly fulfilled mainly due to the same reason: the oxygen electrode, which has large overpotent...

  1. The evolution of the oxygen abundance radial gradient in the Milky Way Galaxy disk

    Science.gov (United States)

    Mollá, Mercedes; Cavichia, Oscar; Costa, Roberto D. D.; Maciel, Walter J.; Gibson, Brad; Díaz, Angeles I.

    2017-10-01

    We review the state of our chemical evolution models for spiral and low mass galaxies. We analyze the consequences of using different stellar yields, infall rate laws and star formation prescriptions in the time/redshift evolution of the radial distributions of abundances, and other quantities as star formation rate or gas densities, in the Milky Way Galaxy; In particular we will study the evolution of the oxygen abundance radial gradient analyzing its relation with the ratio SFR/infall. We also compare the results with our old chemical evolution models, cosmological simulations and with the existing data, mainly with the planetary nebulae abundances.

  2. Trema and parasponia hemoglobins reveal convergent evolution of oxygen transport in plants.

    Science.gov (United States)

    Sturms, Ryan; Kakar, Smita; Trent, James; Hargrove, Mark S

    2010-05-18

    All plants contain hemoglobins that fall into distinct phylogenetic classes. The subset of plants that carry out symbiotic nitrogen fixation expresses hemoglobins that scavenge and transport oxygen to bacterial symbiotes within root nodules. These "symbiotic" oxygen transport hemoglobins are distinct in structure and function from the nonoxygen transport ("nonsymbiotic") Hbs found in all plants. Hemoglobins found in two closely related plants present a paradox concerning hemoglobin structure and function. Parasponia andersonii is a nitrogen-fixing plant that expresses a symbiotic hemoglobin (ParaHb) characteristic of oxygen transport hemoglobins in having a pentacoordinate ferrous heme iron, moderate oxygen affinity, and a relatively rapid oxygen dissociation rate constant. A close relative that does not fix nitrogen, Trema tomentosa, expresses hemoglobin (TremaHb) sharing 93% amino acid identity to ParaHb, but its phylogeny predicts a typical nonsymbiotic hemoglobin with a hexacoordinate heme iron, high oxygen affinity, and slow oxygen dissociation rate constant. Here we characterize heme coordination and oxygen binding in TremaHb and ParaHb to investigate whether or not two hemoglobins with such high sequence similarity are actually so different in functional behavior. Our results indicate that the two proteins resemble nonsymbiotic hemoglobins in the ferric oxidation state and symbiotic hemoglobins in the ferrous oxidation state. They differ from each other only in oxygen affinity and oxygen dissociation rate constants, two factors key to their different functions. These results demonstrate distinct mechanisms for convergent evolution of oxygen transport in different phylogenetic classes of plant hemoglobins.

  3. Photosynthetic oxygen evolution: Changes in magnetism of the water-oxidizing enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraja, M.; Dismukes, G.C. (Princeton Univ., NJ (USA)); Philo, J.S.; Lary, J. (Univ. of Connecticut, Storrs (USA))

    1989-04-26

    Changes in magnetic susceptibility produced by single-turnover flashes of light have been measured for the first time for four of the oxidation states, so-called S states, produced during oxygen evolution in Photosystem II (PSII) complexes of spinach. The data reveal new insights into the structure and bonding of the manganese cluster responsible for catalysis of water oxidation. In samples that have been dark adapted for 15 min or longer to favor population of the resting S{sub 1} state, a train of six flashes increases the paramagnetism on flashes 1, 3, and 5, while no or small increases are observed on flashes 2, 4, and 6. Advancement to the S{sub 1} state does not restore the dark level of S{sub 1} magnetism. This is due to two effects: formation of net paramagnetism from O{sub 2} release on the S{sub 4} {yields} S{sub 0} reaction (scavengeable by glucose oxidase) and a large increase in magnetism for the S{sub 1}(resting) {yields} S{sub 2} reaction, which is not restored without dark readaptation. Comparison of these data with models proposed for the structure of the manganese site reveals that models in which oxidation of substrate water occurs prior to S{sub 4} or oxidation of magnetically isolated Mn ions cannot account for the susceptibility changes observed. The large increase of 17 {mu}{sub B}{sup 2}/PSII observed for the S{sub 1} (resting) {yields} S{sub 2} oxidation is opposite in sign to the decrease in paramagnetism reported for oxidation of synthetic Mn dimers containing the {mu}{sub 2}-oxo-di-{mu}{sub 2}-carboxylato and di-{mu}{sub 2}-oxo-{mu}{sub 2}-carboxylato bridges undergoing the oxidation Mn{sub 2}(III,III) {yields} Mn{sub 2}(III,IV).

  4. Orientation-Dependent Oxygen Evolution on RuO2 without Lattice Exchange

    DEFF Research Database (Denmark)

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

    2017-01-01

    RuO2 catalysts exhibit record activities toward 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 poten......RuO2 catalysts exhibit record activities toward 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 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...

  5. Nickel based alloys as electrocatalysts for oxygen evolution from alkaline solutions. [Metal--air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lu, P.W.T.; Srinivasan, S.

    1977-01-01

    The slowness of the oxygen evolution reaction is one of the main reasons for significant energy losses in water electrolysis cells and secondary air--metal batteries. To date, data on the kinetics of this reaction on alloys and intermetallic compounds are sparse. In this work, mechanically polished alloys of nickel with Ir, Ru or W and Ni--Ti intermetallic compounds were studied as oxygen electrodes. Since the oxygen evolution reaction always takes place on oxide-film covered surfaces, the nature of oxide films formed on these alloys were investigated using cyclic voltametric techniques. Steady-state potentiostatic and slow potentiodynamic (at 0.1 mV/s) methods were employed to obtain the electrode kinetic parameters for the oxygen evolution reaction in 30 wt. percent KOH at 80/sup 0/C, the conditions normally used in water electrolysis cells. The peaks for the formation or reduction of oxygen-containing layers appearing on the pure metals are not always found on the alloys. The maximum decreases in oxygen overpotential at an apparent current density of 20 mA cm/sup -2/ (as compared with that on Ni) were found for the alloys of 50Ni--50Ir and 75Ni--25Ru and the intermetallic compound Ni/sub 3/Ti, these decreases being about 40, 30, and 20 mV, respectively. On the long-term polarization in the potential region of oxygen evolution, the oxygen-containing layers on Ni--Ir or Ni--Ru alloys are essentially composed of nickel oxides instead of true mixed oxide films of two components. The present work confirms that, possibly because of coverage by oxide films, there is no direct dependence of the electrocatalytic activities of the alloys on their electronic properties. 11 figures, 1 table.

  6. Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution

    Science.gov (United States)

    Han, Binghong; Stoerzinger, Kelsey A.; Tileli, Vasiliki; Gamalski, Andrew D.; Stach, Eric A.; Shao-Horn, Yang

    2017-01-01

    Understanding the interaction between water and oxides is critical for many technological applications, including energy storage, surface wetting/self-cleaning, photocatalysis and sensors. Here, we report observations of strong structural oscillations of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) in the presence of both H2O vapour and electron irradiation using environmental transmission electron microscopy. These oscillations are related to the formation and collapse of gaseous bubbles. Electron energy-loss spectroscopy provides direct evidence of O2 formation in these bubbles due to the incorporation of H2O into BSCF. SrCoO3-δ was found to exhibit small oscillations, while none were observed for La0.5Sr0.5CoO3-δ and LaCoO3. The structural oscillations of BSCF can be attributed to the fact that its oxygen 2p-band centre is close to the Fermi level, which leads to a low energy penalty for oxygen vacancy formation, high ion mobility, and high water uptake. This work provides surprising insights into the interaction between water and oxides under electron-beam irradiation.

  7. Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex

    Science.gov (United States)

    Howard, Derrick L.; Tinoco, Arthur D.; Brudvig, Gary W.; Vrettos, John S.; Allen, Bertha Connie

    2005-01-01

    Bioinorganic models of the manganese Mn4 cluster are important not only as aids in understanding the structure and function of the oxygen-evolving complex (OEC), but also in developing artificial water-oxidation catalysts. The mechanism of water oxidation by photosystem II (PSII) is thought to involve the formation of a high-valent terminal Mn-oxo…

  8. The ancient oxygen exosphere of Mars: Implications for atmosphere evolution

    Science.gov (United States)

    Zhang, M. H. G.; Luhmann, J. G.; Nagy, A. F.; Bougher, S. W.

    1992-01-01

    This study involves the calculation, by the 2-stream method of Nagy and Cravens, of 'hot' oxygen exosphere density profiles for 'ancient' atmospheres and ionospheres (e.g., different extreme ultraviolet fluxes) and the associated escaping fluxes. We computed the total production rates above different 'nominal' ionopause altitudes (not taking into account the fact that some will reenter the atmosphere). We do not consider the additional neutral escape due to the sputtering process described by Luhmann and Kozyra. The results presented here thus represent conservative estimations of the neutral escape fluxes, but generous estimates of ion loss rates (except that here we do not consider charge exchange and impact ionization ion production processes). Further work along the lines of Luhmann and Kozyra can lead to estimates of sputtering losses over time and the roles played by impact ionization and charge exchange.

  9. Stabilization of the coupled oxygen and phosphorus cycles by the evolution of bioturbation

    Science.gov (United States)

    Boyle, R. A.; Dahl, T. W.; Dale, A. W.; Shields-Zhou, G. A.; Zhu, M.; Brasier, M. D.; Canfield, D. E.; Lenton, T. M.

    2014-09-01

    Animal burrowing and sediment-mixing (bioturbation) began during the run up to the Ediacaran/Cambrian boundary, initiating a transition between the stratified Precambrian and more well-mixed Phanerozoic sedimentary records, against the backdrop of a variable global oxygen reservoir probably smaller in size than present. Phosphorus is the long-term limiting nutrient for oxygen production via burial of organic carbon, and its retention (relative to carbon) within organic matter in marine sediments is enhanced by bioturbation. Here we explore the biogeochemical implications of a bioturbation-induced organic phosphorus sink in a simple model. We show that increased bioturbation robustly triggers a net decrease in the size of the global oxygen reservoir--the magnitude of which is contingent upon the prescribed difference in carbon to phosphorus ratios between bioturbated and laminated sediments. Bioturbation also reduces steady-state marine phosphate levels, but this effect is offset by the decline in iron-adsorbed phosphate burial that results from a decrease in oxygen concentrations. The introduction of oxygen-sensitive bioturbation to dynamical model runs is sufficient to trigger a negative feedback loop: the intensity of bioturbation is limited by the oxygen decrease it initially causes. The onset of this feedback is consistent with redox variations observed during the early Cambrian rise of bioturbation, leading us to suggest that bioturbation helped to regulate early oxygen and phosphorus cycles.

  10. The effects of oxygen on the evolution of microbial membranes

    Science.gov (United States)

    Jahnke, L. L.

    1991-01-01

    One prokaryote, Methylococcus capsulatus, synthesizes both hopanoids and sterols and, thus, provides a unique opportunity to study the evolution of membrane function. When M. capsulatus was grown at different temperatures, lipid analysis of the whole cells showed that both sterol and unsaturated fatty acid levels decreased at higher growth temperatures; sterol concentrations were 0.116 micro mole/micro mole phospholipid at 30 C and 0.025 micro mole/mirco mole phospholipid at 45 C, while the saturated to unsaturated fatty acid ratio increased from 0.397 to 1.475. Hopane polyol levels were constant over this range; however, methylation of the A-ring decreased markedly in cells grown at 30 C. These results imply that sterol and hopane molecules are required for enhancement of some specific membrane function, potentially by modulating membrane fluidity.

  11. The Role of Oxygen in the Evolution of Molybdenum Nitrogenase

    Science.gov (United States)

    Peters, J.; Boyd, E. S.; Hamilton, T. L.

    2012-12-01

    Since early in Earth's history, the supply of nitrogen (N) into the biosphere has been controlled by the activity of nitrogenase, an oxygen sensitive enzyme that catalyzes the reduction of dinitrogen gas (N2) to bioavailable ammonia. The most common form of nitrogenase harbors a complex molybdenum (Mo) cofactor at its active site [Mo-nitrogenase (Nif)], although other phylogenetically related (alternative) forms of nitrogenase that differ in their active-site metal composition also likely contribute NH3 in environments that are limiting in Mo. The solubility of Mo is significantly influenced by redox and this fact has been used to argue that that the iron (Fe)-dependent nitrogenase (Anf) was predominant prior to ~ 2.5 Ga because oceans were depleted in Mo and rich in Fe. This hypothesis, however, is inconsistent with recent phylogenetic data which strongly suggest that Anf is derived from Nif. Here, we examine the evolutionary history of the Nif enzyme complex in reference to the physiological, biochemical, and morphological strategies for reducing damage by molecular oxygen. A total of 189 nif operons were characterized and quantitatively mapped on a NifHDK concatenated phylogenetic tree. An overlay of the primary mode of metabolism, as defined as either anaerobic (AN) or aerobic/facultative aerobic (AFA), on the NifHDK tree indicates that Nif originated in an anoxic environment and was first acquired in an AFA lineage within the actinobacteria. The complexity of nif operons increased during the evolutionary history of Nif, with a pronounced increase observed during the transition from AN to AFA modes of metabolism. This increase in operon complexity is accompanied by a number of gene loss (nifI1 and nifI2) and gene acquisition (nifW, nifT, nifZ, nifQ) events, with variation in the overall composition of nif operons attributable to adaptations that mediated the toxicity of O2. Collectively, these results underscore the role of O2 in shaping the evolutionary

  12. SiC-Si as a support material for oxygen evolution electrode in PEM steam electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Tomás García, Antonio Luis; Petrushina, Irina

    2011-01-01

    The need of higher energy efficiency in hydrogen production has promoted the research on improved catalysts for water electrolysis. In this work, a novel supported catalyst for oxygen evolution electrodes was prepared and characterized with different techniques. IrO2 supported on a SiC/Si composi...

  13. Action of some herbicides in photosynthesis of Scenedesmus as studied by their effects on oxygen evolution and cyclic photophosphorylation

    NARCIS (Netherlands)

    Rensen, van J.J.S.

    1971-01-01

    The mode of action of some herbicides, viz., DCMU, simetone, and diquat, was investigated by studying their effects upon oxygen evolution and cyclic photophosphorylation in the unicellular green alga, Scenedesmus spec.

    Oxygen evolution was measured with the aid of the WARBURG

  14. The role of biology in planetary evolution: cyanobacterial primary production in low‐oxygen Proterozoic oceans

    Science.gov (United States)

    Bryant, Donald A.; Macalady, Jennifer L.

    2016-01-01

    Summary Understanding the role of biology in planetary evolution remains an outstanding challenge to geobiologists. Progress towards unravelling this puzzle for Earth is hindered by the scarcity of well‐preserved rocks from the Archean (4.0 to 2.5 Gyr ago) and Proterozoic (2.5 to 0.5 Gyr ago) Eons. In addition, the microscopic life that dominated Earth's biota for most of its history left a poor fossil record, consisting primarily of lithified microbial mats, rare microbial body fossils and membrane‐derived hydrocarbon molecules that are still challenging to interpret. However, it is clear from the sulfur isotope record and other geochemical proxies that the production of oxygen or oxidizing power radically changed Earth's surface and atmosphere during the Proterozoic Eon, pushing it away from the more reducing conditions prevalent during the Archean. In addition to ancient rocks, our reconstruction of Earth's redox evolution is informed by our knowledge of biogeochemical cycles catalysed by extant biota. The emergence of oxygenic photosynthesis in ancient cyanobacteria represents one of the most impressive microbial innovations in Earth's history, and oxygenic photosynthesis is the largest source of O 2 in the atmosphere today. Thus the study of microbial metabolisms and evolution provides an important link between extant biota and the clues from the geologic record. Here, we consider the physiology of cyanobacteria (the only microorganisms capable of oxygenic photosynthesis), their co‐occurrence with anoxygenic phototrophs in a variety of environments and their persistence in low‐oxygen environments, including in water columns as well as mats, throughout much of Earth's history. We examine insights gained from both the rock record and cyanobacteria presently living in early Earth analogue ecosystems and synthesize current knowledge of these ancient microbial mediators in planetary redox evolution. Our analysis supports the hypothesis that anoxygenic

  15. Activity and Stability of RuOx Based Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares

    The focus of this Ph.D. thesis is on the electrocatalytic oxygen evolution reaction (OER) in acidic media for Proton Exchange Membrane (PEM) Electrolyser applications. This technology is an attractive alternative for storage of renewable energy, such as from solar and wind power, in small scale......, in particular under the harsh acidic and oxidizing conditions for a PEM electrolyser. Standardised protocols for assessing the stability have not been established for the oxygen evolution reaction. Hence, this thesis focuses on providing guidelines for quantifying the corrosion rate of an OER catalyst...... delocalized hydrogen refueling stations. The sluggish kinetics of OER and the high costs of the materials represent some of the biggest technological challenges for PEM electrolysers. The current technology relies on Pt group based materials and in particular ruthenium and iridium are the most active...

  16. Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

    2016-08-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

  17. Mesoporous Ruthenium/Ruthenium Oxide Thin Films: Active Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Kibsgaard, Jakob; Hellstern, Thomas R.; Choi, Shin-Jung

    2017-01-01

    We report the first synthesis of a fully contiguous large area supported thin film of highly ordered mesoporous Ru and RuO2 and investigate the electrocatalytic properties towards the oxygen evolution reaction (OER). We find that the nanoscale porous network of these catalysts provides significan...... enhancements in geometric OER activity without any loss in specific activity. This work demonstrates a strategy for engineering materials at the nanoscale that can simultaneously decrease precious metal loading and increase electrode activity....

  18. Mesoporous oxides as efficient catalysts for the electrocatalytic oxygen evolution reaction (OER)

    OpenAIRE

    Bernicke, Michael

    2016-01-01

    Hydrogen is considered an important energy carrier and feedstock for industrial applications. The generation of hydrogen can be realised by electrocatalytic water splitting. However, the efficiency of water electrolysers is limited by the slow kinetics of oxygen evolution reaction (OER). An increase in mass based OER activity is mandatory for a lower capital cost of electrolyser cells. In this thesis, synthesis routes are presented for new mesoporous metal oxide films used as catalytic lay...

  19. Evolution of oxygen-rich and carbon stars on the asymptotic giant branch

    Science.gov (United States)

    Kwok, Sun; Chan, S. Josephine; Volk, Kevine M.

    1989-01-01

    The transition from oxygen-rich (M) stars to S stars and then to C stars is examined using data on the chemical properties of the stars. The photospheric and circumstellar spectral characteristics of M and C stars are summarized. Consideration is given to the color distributions of carbon stars, visual carbon stars as transition objects, and radio observations of visual carbon stars. The chemical characteristics of S stars, the evolution of oxygen-rich stars on the AGB, and the transition between AGB stars and planetary nebulae are discussed. IRAS data are used to construct an evolutionary scenario for AGB stars, in which some mass-losing M stars remain oxygen rich, while others become carbon rich.

  20. Evolution of Oxygen Deficiency Center on Fused Silica Surface Irradiated by Ultraviolet Laser and Posttreatment

    Directory of Open Access Journals (Sweden)

    Hai-Bing Lü

    2014-01-01

    Full Text Available Evolution of oxygen deficiency centers (ODCs on a fused silica surface irradiated using a 355 nm ultraviolet (UV laser beam in both vacuum and atmospheric conditions was quantitatively studied using photoluminescence and X-ray photoelectron spectroscopy. When the fusedsilica surface was exposed to the UV laser in vacuum, the laser damage threshold was decreased whereas the concentration of the ODCs was increased. For the fuse silica operated under the high power lasers, creation of ODCs on their surface resulted from the UV laser irradiation, and this is more severe in a high vacuum. The laser fluence and/or laser intensity have significant effects on the increase of the ODCs concentration. The ODCs can be effectively repaired using postoxygen plasma treatment and UV laser irradiation in an excessive oxygen environment. Results also demonstrated that the “gain” and “loss” of oxygen at the silica surface is a reversible and dynamic process.

  1. Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

    Science.gov (United States)

    Mehandru, S. P.; Anderson, Alfred B.

    1989-01-01

    Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

  2. Photochemical cooperativity in photosystem II. Characterization of oxygen evolution discontinuities in the light-response curves.

    Science.gov (United States)

    Viruvuru, V; Fragata, M

    2008-11-28

    In two previous papers (Fragata et al., J. Phys. Chem. B, 2005, 109, 14707-14714; Fragata et al., J. Phys. Chem. B, 2007, 111, 3315-3320), it was shown that the variation of oxygen evolution with the light intensity (I) in photosystem II (PSII) in steady state conditions can be formulated according to the Langmuir adsorption isotherm for heterogeneous catalysis. This yielded the expression OEth = OEth(max) I/(L1/2 + I), where OEth is the theoretical oxygen evolution, OEth(max) the maximum oxygen evolution, and L1/2 the irradiance giving OEth(max)/2. In this approximation, the photons interaction with the chlorophylls in the PSII reaction center is assumed to be a heterogeneous reaction in which the light is represented as a stream of particles instead of an electromagnetic wave. That is, the chlorophyll molecules are the adsorption surfaces (or heterogeneous catalysts), and the incident (or exciting) photons are the substrate, or the reagent. Recently, the examination of new experimental data obtained with 2,6-dichloro-p-benzoquinone (DCBQ) and p-benzoquinone (pBQ) as exogenous electron acceptors, disclosed the presence of oxygen evolution discontinuities (or transitions) in the light-response curves. The new data were fitted with a mathematical summation of hyperbola of order n(i) > 1, OEth = Sigma(i) [OEth(max)]iIn(i)/[(L1/2)i(n(i)) + I(n(i))], where the n(i)'s are the number of sites used by the incident photons in their interaction with the photosynthetic pigments in each population i of PSII centers open for photochemistry. The mathematical simulations yielded only three distinct n(i)'s, that is, 1.8, 4.8, 8.5 and 1.8, 4.2, 8.4 for isolated PSII particles incubated with DCBQ and pBQ, respectively. Implicitly, this means the simultaneous excitation of each PSII reaction center with more than one photon, that is, the excitation of more than one pigment molecule. It is suggested that these transitions have their origin in the cooperative interaction of the

  3. The role of biology in planetary evolution: cyanobacterial primary production in low-oxygen Proterozoic oceans.

    Science.gov (United States)

    Hamilton, Trinity L; Bryant, Donald A; Macalady, Jennifer L

    2016-02-01

    Understanding the role of biology in planetary evolution remains an outstanding challenge to geobiologists. Progress towards unravelling this puzzle for Earth is hindered by the scarcity of well-preserved rocks from the Archean (4.0 to 2.5 Gyr ago) and Proterozoic (2.5 to 0.5 Gyr ago) Eons. In addition, the microscopic life that dominated Earth's biota for most of its history left a poor fossil record, consisting primarily of lithified microbial mats, rare microbial body fossils and membrane-derived hydrocarbon molecules that are still challenging to interpret. However, it is clear from the sulfur isotope record and other geochemical proxies that the production of oxygen or oxidizing power radically changed Earth's surface and atmosphere during the Proterozoic Eon, pushing it away from the more reducing conditions prevalent during the Archean. In addition to ancient rocks, our reconstruction of Earth's redox evolution is informed by our knowledge of biogeochemical cycles catalysed by extant biota. The emergence of oxygenic photosynthesis in ancient cyanobacteria represents one of the most impressive microbial innovations in Earth's history, and oxygenic photosynthesis is the largest source of O2 in the atmosphere today. Thus the study of microbial metabolisms and evolution provides an important link between extant biota and the clues from the geologic record. Here, we consider the physiology of cyanobacteria (the only microorganisms capable of oxygenic photosynthesis), their co-occurrence with anoxygenic phototrophs in a variety of environments and their persistence in low-oxygen environments, including in water columns as well as mats, throughout much of Earth's history. We examine insights gained from both the rock record and cyanobacteria presently living in early Earth analogue ecosystems and synthesize current knowledge of these ancient microbial mediators in planetary redox evolution. Our analysis supports the hypothesis that anoxygenic photosynthesis

  4. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    Science.gov (United States)

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel; Rao, Reshma R.; Frydendal, Rasmus; Qiao, Liang; Wang, Xiao Renshaw; Halck, Niels Bendtsen; Rossmeisl, Jan; Hansen, Heine A.; Vegge, Tejs; Stephens, Ifan E. L.; Koper, Marc T. M.; Shao-Horn, Yang

    2017-03-15

    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 on 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.

  6. Nanoporous BiVO4 photoanodes with dual-layer oxygen evolution catalysts for solar water splitting

    National Research Council Canada - National Science Library

    Kim, Tae Woo; Choi, Kyoung-Shin

    2014-01-01

    ...) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC...

  7. Electrodeposition of hierarchically structured three-dimensional nickel-iron electrodes for efficient oxygen evolution at high current densities

    National Research Council Canada - National Science Library

    Lu, Xunyu; Zhao, Chuan

    2015-01-01

    Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm(-2...

  8. Estimation of oxygen evolution by marine phytoplankton from measurement of the efficiency of Photosystem II electron flow.

    NARCIS (Netherlands)

    Geel, C.; Versluis, W.; Snel, J.F.H.

    1997-01-01

    The relation between photosynthetic oxygen evolution and Photosystem II electron transport was investigated for the marine algae t Phaeodactylum tricornutum, Dunaliella tertiolecta, Tetraselmis sp., t Isochrysis sp. and t Rhodomonas sp.. The rate of Photosystem II electron transport was estimated

  9. In situ TEM studies of the shape evolution of Pd nanocrystals under oxygen and hydrogen environments at atmospheric pressure.

    Science.gov (United States)

    Zhang, Xun; Meng, Jun; Zhu, Beien; Yu, Jian; Zou, Shihui; Zhang, Ze; Gao, Yi; Wang, Yong

    2017-12-12

    We demonstrate an atomic scale TEM observation of shape evolutions of Pd nanocrystals under oxygen and hydrogen environments at atmospheric pressure. Combined with multi-scale structure reconstruction model calculations, the reshaping mechanism is fully understood.

  10. Oxygen Evolution on Model Well-Characterised Mass-Selected Nanoparticles of RuOx

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares; Masini, Federico; Frydendal, Rasmus

    2014-01-01

    to the reaction: 2H2O --> O2 + 4H+ + 4e- The most active and widely used catalysts for the oxygen evolution reaction (OER) are RuOx based materials. However, RuOx corrodes under reaction conditions. Moreover, Ru is very expensive and scarce [3]. In the current investigation, we focus on the evaluation of (a......) oxygen evolution activity and (b) corrosion of well defined, mass selected Ru nanoparticles as a function of size and shape. We adapt a methodology previously used in our laboratory to study to investigate the oxygen reduction reaction [4]. The size selected electrocatalysts are prepared using an ultra......, Electrochemical Scanning Tunnelling Microscopy (EC-STM) is used to directly observe the catalyst dissolution under reaction conditions. The EC-STM images are acquired in Ar saturated 0,05 M H2SO4, while the potential is scanned at a scan rate of 2 mV/s. The metallic and pre-oxidized nanoparticles show distinct...

  11. Wine evolution and spatial distribution of oxygen during storage in high-density polyethylene tanks.

    Science.gov (United States)

    del Alamo-Sanza, María; Laurie, V Felipe; Nevares, Ignacio

    2015-04-01

    Porous plastic tanks are permeable to oxygen due to the nature of the polymers with which they are manufactured. In the wine industry, these types of tanks are used mainly for storing wine surpluses. Lately, their use in combination with oak pieces has also been proposed as an alternative to mimic traditional barrel ageing. In this study, the spatial distribution of dissolved oxygen in a wine-like model solution, and the oxygen transfer rate (OTR) of high-density polyethylene tanks (HDPE), was analysed by means of a non-invasive opto-luminescence detector. Also, the chemical and sensory evolution of red wine, treated with oak pieces, and stored in HDPE tanks was examined and compared against traditional oak barrel ageing. The average OTR calculated for these tanks was within the commonly accepted amounts reported for new barrels. With regards to wine evolution, a number of compositional and sensory differences were observed between the wines aged in oak barrels and those stored in HDPE tanks with oak barrel alternatives. The use of HDPE tanks in combination with oak wood alternatives is a viable alternative too for ageing wine. © 2014 Society of Chemical Industry.

  12. Oxygen as a driver of early arthropod micro-benthos evolution.

    Science.gov (United States)

    Williams, Mark; Vannier, Jean; Corbari, Laure; Massabuau, Jean-Charles

    2011-01-01

    We examine the physiological and lifestyle adaptations which facilitated the emergence of ostracods as the numerically dominant Phanerozoic bivalve arthropod micro-benthos. The PO(2) of modern normoxic seawater is 21 kPa (air-equilibrated water), a level that would cause cellular damage if found in the tissues of ostracods and much other marine fauna. The PO(2) of most aquatic breathers at the cellular level is much lower, between 1 and 3 kPa. Ostracods avoid oxygen toxicity by migrating to waters which are hypoxic, or by developing metabolisms which generate high consumption of O(2). Interrogation of the Cambrian record of bivalve arthropod micro-benthos suggests a strong control on ecosystem evolution exerted by changing seawater O(2) levels. The PO(2) of air-equilibrated Cambrian-seawater is predicted to have varied between 10 and 30 kPa. Three groups of marine shelf-dwelling bivalve arthropods adopted different responses to Cambrian seawater O(2). Bradoriida evolved cardiovascular systems that favoured colonization of oxygenated marine waters. Their biodiversity declined during intervals associated with black shale deposition and marine shelf anoxia and their diversity may also have been curtailed by elevated late Cambrian (Furongian) oxygen-levels that increased the PO(2) gradient between seawater and bradoriid tissues. Phosphatocopida responded to Cambrian anoxia differently, reaching their peak during widespread seabed dysoxia of the SPICE event. They lacked a cardiovascular system and appear to have been adapted to seawater hypoxia. As latest Cambrian marine shelf waters became well oxygenated, phosphatocopids went extinct. Changing seawater oxygen-levels and the demise of much of the seabed bradoriid micro-benthos favoured a third group of arthropod micro-benthos, the ostracods. These animals adopted lifestyles that made them tolerant of changes in seawater O(2). Ostracods became the numerically dominant arthropod micro-benthos of the Phanerozoic. Our work

  13. Bifunctional metal-free catalysis of mesoporous noble carbons for oxygen reduction and evolution reactions.

    Science.gov (United States)

    Sakaushi, Ken; Fellinger, Tim-Patrick; Antonietti, Markus

    2015-04-13

    Electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key reactions in lithium-oxygen batteries (LOBs) being a promising candidate to store renewable energies due to their high specific energy. However current development on LOBs is suffering from unsuitable catalysts. In particular, carbon-based catalysts were found to perform poorly in this system. Here, we show that metal-free mesoporous nitrogen-doped carbons (meso-NdCs) offer highly promising performances in both ORR and OER; they act as bifunctional catalysts, and can be synthesized by a very simple method. The efficient electrocatalytic activity of ORR and OER was used in a LOB cell during discharge and charge, respectively, and the present system showed a lower overpotential comparable to metal-based catalysts in LOB system. Thus, we demonstrate that meso-NdCs act as a new and affordable candidate for the efficient bifunctional oxygen catalysis, therefore can be applied to many energy-related applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electrochemical properties of IrO2 active anode with TNTs interlayer for oxygen evolution

    Science.gov (United States)

    Cao, Huazhen; Chen, Mengjie; Wu, Liankui; Hou, Guangya; Tang, Yiping; Zheng, Guoqu

    2018-01-01

    A novel IrO2 coating titanium anode (IrO2/TNTs/Ti) without cracks in microstructure has been prepared via a thermal decomposition method using heat-treated TiO2 nanotube arrays (TNTs) as interlayer. This electrode shows a significantly higher activity for oxygen evolution reaction (OER) and longer lifetime than the IrO2/Ti electrodes without a TNTs layer. The influence of IrO2 amount and calcination temperatures on oxygen evolution as well as morphology and phase characteristics were studied by electrochemical measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM) observations. The results show that the catalytic properties of oxide electrodes highly depended on the loading amount of IrO2 and calcination temperatures. The electrode fabricated at calcination temperature of 600 °C showed a weak electrocatalytic activity due to high degree of crystallinity, grain growth, accumulation of active component and the collapse of TNTs. On the contrary, the IrO2/TNTs/Ti electrode prepared at low calcination temperature (400 °C) possesses extremely more surface active sites and high activity for oxygen evolution in the initial stage, but its service life is very short. The IrO2/TNTs/Ti electrode was found to achieve the lowest film resistance and the charge transfer resistance at an optimal loading amount of 6 g/m2. By simply optimizing both calcination temperature and IrO2 loading amount, IrO2/TNTs/Ti electrode with high activity and long lifetime can be fabricated.

  15. Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials

    Science.gov (United States)

    Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

    2017-09-01

    It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

  16. Computational screening of doped αMnO2 catalystsfor the oxygen evolution reaction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs

    2017-01-01

    and electronic conductivity of pure and doped αMnO2 for the OER. As a model surface, we investigate the (110) and (100) facets, on which we identify three possible active sites: a coordination unsaturated, bridge and bulk site. We evaluate the performance of pure and Cr, Fe, Co, Ni, Cu, Zn, Cd, Mg, Al, Ga, In......Minimizing energy and materials costs for driving the oxygen evolution reaction (OER) is paramount for the commercialization of water electrolysis cells and rechargeable metal-air batteries. Using density functional theory calculations, we analyze the structural stability, catalytic activity...

  17. Carbon dots decorated vertical SnS2 nanosheets for efficient photocatalytic oxygen evolution

    Science.gov (United States)

    Cheng, Zhongzhou; Wang, Fengmei; Shifa, Tofik Ahmed; Liu, Kaili; Huang, Yun; Liu, Quanlin; Jiang, Chao; He, Jun

    2016-08-01

    Metal sulfides are highly desirable materials for photocatalytic water splitting because of their appropriate energy bands. However, the poor stability under light illumination in water hinders their wide applications. Here, two-dimensional SnS2 nanosheets, along with carbon dots of the size around 10 nm, are uniformly grown on fluorine doped tin oxide glasses with a layer of nickel nanoparticles. Significantly, strong light absorption and enhanced photocurrent density are achieved after integration of SnS2 nanosheets with carbon dots. Notably, the rate of oxygen evolution reached up to 1.1 mmol g-1 h-1 under simulated sunlight irradiation featuring a good stability.

  18. High-performance a -Si/c-Si heterojunction photoelectrodes for photoelectrochemical oxygen and hydrogen evolution

    KAUST Repository

    Wang, Hsin Ping

    2015-05-13

    Amorphous Si (a-Si)/crystalline Si (c-Si) heterojunction (SiHJ) can serve as highly efficient and robust photoelectrodes for solar fuel generation. Low carrier recombination in the photoelectrodes leads to high photocurrents and photovoltages. The SiHJ was designed and fabricated into both photoanode and photocathode with high oxygen and hydrogen evolution efficiency, respectively, by simply coating of a thin layer of catalytic materials. The SiHJ photoanode with sol-gel NiOx as the catalyst shows a current density of 21.48 mA/cm2 at the equilibrium water oxidation potential. The SiHJ photocathode with 2 nm sputter-coated Pt catalyst displays excellent hydrogen evolution performance with an onset potential of 0.640 V and a solar to hydrogen conversion efficiency of 13.26%, which is the highest ever reported for Si-based photocathodes. © 2015 American Chemical Society.

  19. Oxygen as a factor in eukaryote evolution - Some effects of low levels of oxygen on Saccharomyces cerevisiae

    Science.gov (United States)

    Jahnke, L.; Klein, H. P.

    1979-01-01

    A comparative study of the effects of varying levels of oxygen on some of the metabolic functions of the primitive eukaryote, Saccharomyces cerevisiae, has shown that these cells are responsive to very low levels of oxygen: the level of palmitoyl-Co A desaturase was greatly enhanced by only 0.03 vol % oxygen. Similarly, an acetyl-CoA synthetase associated predominantly with anaerobic growth was stimulated by as little as 0.1% oxygen, while an isoenzyme correlated with aerobic growth was maximally active at much higher oxygen levels (greater than 1%). Closely following this latter pattern were three mitochondrial enzymes that attained maximal activity only under atmospheric levels of oxygen.

  20. MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts

    Directory of Open Access Journals (Sweden)

    Hong Li

    2018-02-01

    Full Text Available The development of a highly efficient and stable bifunctional electrocatalyst for water splitting is still a challenging issue in obtaining clean and sustainable chemical fuels. Herein, a novel bifunctional catalyst consisting of 2D transition-metal phosphide nanosheets with abundant reactive sites templated by Co-centered metal−organic framework nanosheets, denoted as CoP-NS/C, has been developed through a facile one-step low-temperature phosphidation process. The as-prepared CoP-NS/C has large specific surface area and ultrathin nanosheets morphology providing rich catalytic active sites. It shows excellent electrocatalytic performances for hydrogen evolution reaction (HER and oxygen evolution reaction (OER in acidic and alkaline media, with the Tafel slopes of 59 and 64 mV/dec and a current density of 10 mA/cm2 at the overpotentials of 140 and 292 mV, respectively, which are remarkably superior to those of CoP/C, CoP particles, and comparable to those of commercial noble-metal catalysts. In addition, the CoP-NS/C also shows good durability after a long-term test.

  1. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems.

    Science.gov (United States)

    Zhang, Wei; Lai, Wenzhen; Cao, Rui

    2017-02-22

    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  2. Organization and evolution of the biological response to singlet oxygen stress.

    Science.gov (United States)

    Dufour, Yann S; Landick, Robert; Donohue, Timothy J

    2008-11-14

    The appearance of atmospheric oxygen from photosynthetic activity led to the evolution of aerobic respiration and responses to the resulting reactive oxygen species. In Rhodobacter sphaeroides, a photosynthetic alpha-proteobacterium, a transcriptional response to the reactive oxygen species singlet oxygen ((1)O(2)) is controlled by the group IV sigma factor sigma(E) and the anti-sigma factor ChrR. In this study, we integrated various large datasets to identify genes within the (1)O(2) stress response that contain sigma(E)-dependent promoters both within R. sphaeroides and across the bacterial phylogeny. Transcript pattern clustering and a sigma(E)-binding sequence model were used to predict candidate promoters that respond to (1)O(2) stress in R. sphaeroides. These candidate promoters were experimentally validated to nine R. sphaeroides sigma(E)-dependent promoters that control the transcription of 15 (1)O(2)-activated genes. Knowledge of the R. sphaeroides response to (1)O(2) and its regulator sigma(E)-ChrR was combined with large-scale phylogenetic and sequence analyses to predict the existence of a core set of approximately eight conserved sigma(E)-dependent genes in alpha-proteobacteria and gamma-proteobacteria. The bacteria predicted to contain this conserved response to (1)O(2) include photosynthetic species, as well as free-living and symbiotic/pathogenic nonphotosynthetic species. Our analysis also predicts that the response to (1)O(2) evolved within the time frame of the accumulation of atmospheric molecular oxygen on this planet.

  3. Discerning the effects of photoinhibition and photoprotection on the rate of oxygen evolution in Arabidopsis leaves.

    Science.gov (United States)

    Giovagnetti, Vasco; Ruban, Alexander V

    2015-11-01

    Higher plants possess a set of interconnected processes to regulate light harvesting. Non-photochemical quenching of chlorophyll a fluorescence (NPQ) is the fastest process activated to protect the photosystem (PS) II from the absorption of excess light energy. However, damage of PSII reaction centers (RCIIs) is often inevitable, a phenomenon known as photoinhibition. Both NPQ and photoinhibition undermine PSII quantum yield (ΦPSII). Recently, we devised a fluorescence-based methodology that uses the coefficient of photochemical quenching measured in the dark following illumination (qPd) to assess the intactness of RCIIs. This procedure enables to express ΦPSII as a function (ƒ) of NPQ and qPd, ΦPSII=ƒ(NPQ,qPd), thus allowing to efficiently discern between the effects of protective NPQ and photoinhibition upon the efficiency of electron transport. In this study, we addressed the relationship between qPd and ΦPSII measured by photosynthetic oxygen evolution in intact leaves of Arabidopsis. We found a linear correlation between qPd and ΦPSII of oxygen evolution (as well as Fv/Fm). This relates to the fact that qPd reflects the onset of photoinhibition. These results further demonstrate the validity of the qPd parameter and underlying theory in quantitatively assessing PSII efficiency solely by using this effective and simple fluorescence technique. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Amorphous Cobalt Vanadium Oxide as a Highly Active Electrocatalyst for Oxygen Evolution.

    Science.gov (United States)

    Liardet, Laurent; Hu, Xile

    2018-01-05

    The water-splitting reaction provides a promising mechanism to store renewable energies in the form of hydrogen fuel. The oxidation half-reaction, the oxygen evolution reaction (OER), is a complex four-electron process that constitutes an efficiency bottleneck in water splitting. Here we report a highly active OER catalyst, cobalt vanadium oxide. The catalyst is designed on the basis of a volcano plot of metal-OH bond strength and activity. The catalyst can be synthesized by a facile hydrothermal route. The most active pure-phase material ( a- CoVO x ) is X-ray amorphous and provides a 10 mA cm -2 current density at an overpotential of 347 mV in 1 M KOH electrolyte when immobilized on a flat substrate. The synthetic method can also be applied to coat a high-surface-area substrate such as nickel foam. On this three-dimensional substrate, the a- CoVO x catalyst is highly active, reaching 10 mA cm -2 at 254 mV overpotential, with a Tafel slope of only 35 mV dec -1 . This work demonstrates a- CoVO x as a promising electrocatalyst for oxygen evolution and validates M-OH bond strength as a practical descriptor in OER catalysis.

  5. Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Malkhandi, S.; Trinh, P.; Manohar, Aswin K.; Manivannan, A.; Balasubramanian, M.; Prakash, G. K. Surya; Narayanan, S. R.

    2015-04-16

    Rechargeable metal-air batteries and water electrolyzers based on aqueous alkaline electrolytes hold the potential to be sustainable solutions to address the challenge of storing large amounts of electrical energy generated from solar and wind resources. For these batteries and electrolyzers to be economically viable, it is essential to have efficient, durable, and inexpensive electrocatalysts for the oxygen evolution reaction. In this article, we describe new insights for predicting and tuning the activity of inexpensive transition metal oxides for designing efficient and inexpensive electrocatalysts. We have focused on understanding the factors determining the electrocatalytic activity for oxygen evolution in a strong alkaline medium. To this end, we have conducted a systematic investigation of nanophase calcium-doped lanthanum cobalt manganese oxide, an example of a mixed metal oxide that can be tuned for its electrocatalytic activity by varying the transition metal composition. Using X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), electrochemical polarization experiments, and analysis of mechanisms, we have identified the key determinants of electrocatalytic activity. We have found that the Tafel slopes are determined by the oxidation states and the bond energy of the surface intermediates of Mn-OH and Co-OH bonds while the catalytic activity increased with the average d-electron occupancy of the sigma* orbital of the M-OH bond. We anticipate that such understanding will be very useful in predicting the behavior of other transition metal oxide catalysts.

  6. Sea urchin-like cobalt-iron phosphide as an active catalyst for oxygen evolution reaction

    Science.gov (United States)

    Mendoza-Garcia, Adriana; Su, Dong; Sun, Shouheng

    2016-02-01

    Sea urchin-like (CoxFe1-x)2P shows Co/Fe-composition dependent catalysis for oxygen evolution reaction (OER) in 0.1 M KOH. The (Co0.54Fe0.46)2P is the most efficient OER catalyst, reaching 10 mA cm-2 at an overpotential of 0.37 V (vs. RHE). The report offers a new synergistic approach to tune and optimize the electrocatalysis of OER.Sea urchin-like (CoxFe1-x)2P shows Co/Fe-composition dependent catalysis for oxygen evolution reaction (OER) in 0.1 M KOH. The (Co0.54Fe0.46)2P is the most efficient OER catalyst, reaching 10 mA cm-2 at an overpotential of 0.37 V (vs. RHE). The report offers a new synergistic approach to tune and optimize the electrocatalysis of OER. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08763e

  7. Dependence of the flash-induced oxygen evolution pattern on the chemically and far red light-modulated redox condition in cyanobacterial photosynthetic electron transport.

    Science.gov (United States)

    Spiegel, Susanne; Bader, Klaus P

    2003-01-01

    that S2 contributes to 10-20% of the S-state distribution (in comparison to 0% in the control). Thus, far red background illumination might represent a valuable means for photosynthetic investigations where high amounts of S2 are required like e. g. EPR measurements. In such experiments the corresponding EPR signals appeared substantially enhanced following far red preillumination (Ahrling and Bader, unpublished observations). Our results clearly show that the 'controversial results' from parts of the literature suggesting the participation of different mechanisms (net oxygen evolution, inhibited uptake processes etc.) are not required to explain the flash-induced oxygen evolution in cyanobacteria: the seemingly 'incompatible' conditions and conformations can be perfectly interconverted by different modulation techniques (chemicals, far red) of the respective redox condition within the water oxidation complex of photosynthesis.

  8. Handling and Use of Oxygen by Pancrustaceans: Conserved Patterns and the Evolution of Respiratory Structures.

    Science.gov (United States)

    Harrison, Jon F

    2015-11-01

    The handling and use of oxygen are central to physiological function of all pancrustaceans. Throughout the Pancrustacea, ventilation is controlled by a central oxygen-sensitive pattern generator. The ancestral condition was likely to achieve ventilation of the gills via leg-associated or mouth-associated muscles, but in insects and some air-breathing crustaceans, new muscles were recruited for this purpose, including intersegmental muscles likely used previously for posture and locomotion. Many aspects of the sensing of oxygen and the occurrence of responses to hypoxia (increased ventilation, depressed growth and metabolic rate, developmental changes that enhance the delivery of oxygen) appear common across most pancrustaceans, but there is tremendous variation across species. Some of this can be explained by habitat (e.g., ventilation of the internal medium occurs in terrestrial species and of the external medium in aquatic species; rearing under hypoxia induces tracheal proliferation in terrestrial insects and hemocyanin production in aquatic crustaceans); some plausibly by evolutionary origin of some responses to hypoxia within the Pancrustacea (the most basal arthropods may lack a ventilatory response to hypoxia); and some by the availability of environmental oxygen (animals adapted to survive hypoxia turn on the response to hypoxia at a lower PO2). On average, crustaceans and insects have similar tolerances to prolonged anoxia, but species or life stages from habitats with a danger of being trapped in hypoxia can tolerate longer durations of anoxia. Lactate is the primary anaerobic end-product in crustaceans but some insects have evolved a more diverse array of anaerobic end-products, including ethanol, alanine, succinate, and acetate. Most clades of Pancrustacea are small and lack obvious respiratory structures. Gilled stem-pancrustaceans likely evolved in the Cambrian, and gills persist in large Ostracoda, Malacostraca, and Branchiopoda. Based on currently

  9. Electrocatalysts Derived from Metal-Organic Frameworks for Oxygen Reduction and Evolution Reactions in Aqueous Media.

    Science.gov (United States)

    Qian, Yuhong; Khan, Inayat Ali; Zhao, Dan

    2017-10-01

    Electrochemical energy conversion and storage devices such as fuel cells and metal-air batteries have been extensively studied in recent decades for their excellent conversion efficiency, high energy capacity, and low environmental impact. However, sluggish kinetics of the oxygen-related reactions at air cathodes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are still worth improving. Noble metals such as platinum (Pt), iridium (Ir), ruthenium (Ru) and their oxides are considered as the benchmark ORR and OER electrocatalysts, but they are expensive and prone to be poisoned due to the fuel crossover effect, and may suffer from agglomeration and leaching after long-term usage. To mitigate these limits, it is highly desirable to design alternative ORR/OER electrocatalysts with prominent performance. Metal-organic frameworks (MOFs) are a class of porous crystalline materials consisting metal ions/clusters coordinated by organic ligands. Their crystalline structure, tunable pore size and high surface area afford them wide opportunities as catalytic materials. This Review covers MOF-derived ORR/OER catalysts in electrochemical energy conversion, with a focus on the different strategies of material design and preparation, such as composition control and nanostructure fabrication, to improve the activity and durability of MOF-derived electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Earth’s oxygen cycle and the evolution of animal life

    Science.gov (United States)

    Reinhard, Christopher T.; Planavsky, Noah J.; Olson, Stephanie L.; Lyons, Timothy W.; Erwin, Douglas H.

    2016-01-01

    The emergence and expansion of complex eukaryotic life on Earth is linked at a basic level to the secular evolution of surface oxygen levels. However, the role that planetary redox evolution has played in controlling the timing of metazoan (animal) emergence and diversification, if any, has been intensely debated. Discussion has gravitated toward threshold levels of environmental free oxygen (O2) necessary for early evolving animals to survive under controlled conditions. However, defining such thresholds in practice is not straightforward, and environmental O2 levels can potentially constrain animal life in ways distinct from threshold O2 tolerance. Herein, we quantitatively explore one aspect of the evolutionary coupling between animal life and Earth’s oxygen cycle—the influence of spatial and temporal variability in surface ocean O2 levels on the ecology of early metazoan organisms. Through the application of a series of quantitative biogeochemical models, we find that large spatiotemporal variations in surface ocean O2 levels and pervasive benthic anoxia are expected in a world with much lower atmospheric pO2 than at present, resulting in severe ecological constraints and a challenging evolutionary landscape for early metazoan life. We argue that these effects, when considered in the light of synergistic interactions with other environmental parameters and variable O2 demand throughout an organism’s life history, would have resulted in long-term evolutionary and ecological inhibition of animal life on Earth for much of Middle Proterozoic time (∼1.8–0.8 billion years ago). PMID:27457943

  11. Plankton community respiration, net ecosystem metabolism, and oxygen dynamics on the Louisiana continental shelf: implications for hypoxia

    Science.gov (United States)

    We conducted a multi-year study of the Louisiana continental shelf (LCS) to better understand the linkages between water column metabolism and the formation of hypoxia (dissolved oxygen <2 mg L-1) in the region. Water column community respiration rates (WR) were measured on 10 cr...

  12. Simultaneous modulation of surface composition, oxygen vacancies and assembly in hierarchical Co3O4 mesoporous nanostructures for lithium storage and electrocatalytic oxygen evolution

    DEFF Research Database (Denmark)

    Sun, Hongyu; Zhao, Yanyan; Mølhave, Kristian

    2017-01-01

    in superior electrochemical properties when used as the anode materials for lithium-ion batteries and as an electrocatalyst for the oxygen evolution reaction. The excellent electrochemical performance is attributed to the synergistic effects of novel hierarchical morphology, crystal structure of the active......We developed a facile solution reductive method to simultaneously tune the surface composition, oxygen vacancies and three dimensional assembly in Co3O4 hierarchical nanostructures. The controllable surface composition, oxygen vacancies together with hierarchical micro/nanoarchitectures resulted...... materials, the improvement of intrinsic conductivity and inner surface area induced by the oxygen vacancies. The present strategy not only provides a facile method to assemble novel hierarchical architectures, but also paves a way to control surface structures (chemical composition and crystal defects...

  13. Are there ecological implications for the proposed energetic restrictions on photosynthetic oxygen evolution at high oxygen concentrations?

    Science.gov (United States)

    Raven, J A; Larkum, A W D

    2007-10-01

    It has recently been shown that, in subthylakoid particles prepared using detergent, there is inhibition of oxygen production reactions in photosynthesis by thermodynamic feedback from oxygen build-up, with 50% inhibition at 230 kPa partial pressure of oxygen. This article presents a comprehensive analysis of laboratory data on the effects of high oxygen partial pressures on photosynthesis, and on photo-lithotrophic and chemo-organotrophic growth, of oxygen-producing organisms. The article also contains an analysis of the extent to which high oxygen concentrations occur at the site of photosystem II (PSII) activity under natural conditions today and in the past. The conclusion is that the oxygen concentrations found in nature are very unlikely to reach that needed to cause 50% inhibition of the photosynthetic oxygen production reaction in subthylakoid particles, but that it is just possible that a small part of the inhibition of photosynthesis and of photo-lithotrophic growth by oxygen can be attributed to inhibition of oxygen production by PSII.

  14. Oxygen as a driver of early arthropod micro-benthos evolution.

    Directory of Open Access Journals (Sweden)

    Mark Williams

    Full Text Available BACKGROUND: We examine the physiological and lifestyle adaptations which facilitated the emergence of ostracods as the numerically dominant Phanerozoic bivalve arthropod micro-benthos. METHODOLOGY/PRINCIPAL FINDINGS: The PO(2 of modern normoxic seawater is 21 kPa (air-equilibrated water, a level that would cause cellular damage if found in the tissues of ostracods and much other marine fauna. The PO(2 of most aquatic breathers at the cellular level is much lower, between 1 and 3 kPa. Ostracods avoid oxygen toxicity by migrating to waters which are hypoxic, or by developing metabolisms which generate high consumption of O(2. Interrogation of the Cambrian record of bivalve arthropod micro-benthos suggests a strong control on ecosystem evolution exerted by changing seawater O(2 levels. The PO(2 of air-equilibrated Cambrian-seawater is predicted to have varied between 10 and 30 kPa. Three groups of marine shelf-dwelling bivalve arthropods adopted different responses to Cambrian seawater O(2. Bradoriida evolved cardiovascular systems that favoured colonization of oxygenated marine waters. Their biodiversity declined during intervals associated with black shale deposition and marine shelf anoxia and their diversity may also have been curtailed by elevated late Cambrian (Furongian oxygen-levels that increased the PO(2 gradient between seawater and bradoriid tissues. Phosphatocopida responded to Cambrian anoxia differently, reaching their peak during widespread seabed dysoxia of the SPICE event. They lacked a cardiovascular system and appear to have been adapted to seawater hypoxia. As latest Cambrian marine shelf waters became well oxygenated, phosphatocopids went extinct. Changing seawater oxygen-levels and the demise of much of the seabed bradoriid micro-benthos favoured a third group of arthropod micro-benthos, the ostracods. These animals adopted lifestyles that made them tolerant of changes in seawater O(2. Ostracods became the numerically

  15. Influence of various metallic oxides on the kinetic of the oxygen evolution reaction on platinum electrodes

    Directory of Open Access Journals (Sweden)

    Kambire Ollo

    2015-08-01

    Full Text Available Pt, 50Pt-50RuO2 and 50Pt-50IrO2 electrodes were prepared on titanium (Ti substrate by thermal decomposition techniques. The micrographs of 50Pt-50RuO2 and 50Pt-50IrO2 have revealed that their surfaces are rough with cracked structures. That of platinum was smooth, compact and homogeneous. The richer the electrode ‘surface in platinum, thinner is the crack size and also more compact is the electrode’surface. The electrodes have also been characterized electrochemically by cyclic voltammetry in acid (HClO4 and in alkaline (KOH electrolytes. These characterizations showed that the surface of the 50Pt-50RuO2 and 50Pt-50IrO2 electrodes were composed by platinum and metal dioxide active sites. The Tafel slope obtained on Pt, 50Pt-50RuO2 and 50Pt-50IrO2 for the oxygen evolution reaction (OER were respectively 120, 90 and 44 mV/dec in acid electrolyte. In the alkaline electrolyte, they were 119, 87 and 42 mV/dec respectively on Pt, 50Pt-50RuO2 and 50Pt-50IrO2 electrodes indicating that for the prepared electrodes, Tafel slopes are the same in acid and in alkaline media. Moreover, in acid and in alkaline media, the kinetic of the oxygen evolution reaction was rapid on 50Pt-50RuO2 and 50Pt-50IrO2 than Pt owing to a synergetic effect of Pt and the oxides. That additional effect of the surface component 50Pt-50RuO2 and 50Pt-50IrO2 electrodes let them possess high electrocatalytic activity towards OER than Pt in the two media. Though the kinetic of the oxygen evolution reaction is practically the same in acidic and alkaline media for all the electrodes, OER occurred at lower overpotential in alkaline electrolyte than in acidic electrolyte on the prepared electrodes.

  16. Multi-Feature Segmentation for High-Resolution Polarimetric SAR Data Based on Fractal Net Evolution Approach

    Directory of Open Access Journals (Sweden)

    Qihao Chen

    2017-06-01

    Full Text Available Segmentation techniques play an important role in understanding high-resolution polarimetric synthetic aperture radar (PolSAR images. PolSAR image segmentation is widely used as a preprocessing step for subsequent classification, scene interpretation and extraction of surface parameters. However, speckle noise and rich spatial features of heterogeneous regions lead to blurred boundaries of high-resolution PolSAR image segmentation. A novel segmentation algorithm is proposed in this study in order to address the problem and to obtain accurate and precise segmentation results. This method integrates statistical features into a fractal net evolution algorithm (FNEA framework, and incorporates polarimetric features into a simple linear iterative clustering (SLIC superpixel generation algorithm. First, spectral heterogeneity in the traditional FNEA is substituted by the G0 distribution statistical heterogeneity in order to combine the shape and statistical features of PolSAR data. The statistical heterogeneity between two adjacent image objects is measured using a log likelihood function. Second, a modified SLIC algorithm is utilized to generate compact superpixels as the initial samples for the G0 statistical model, which substitutes the polarimetric distance of the Pauli RGB composition for the CIELAB color distance. The segmentation results were obtained by weighting the G0 statistical feature and the shape features, based on the FNEA framework. The validity and applicability of the proposed method was verified with extensive experiments on simulated data and three real-world high-resolution PolSAR images from airborne multi-look ESAR, spaceborne single-look RADARSAT-2, and multi-look TerraSAR-X data sets. The experimental results indicate that the proposed method obtains more accurate and precise segmentation results than the other methods for high-resolution PolSAR images.

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

    Science.gov (United States)

    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.

  18. Operando investigation of Au-MnOx thin films with improved activity for the oxygen evolution reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Seitz, Linsey C.; Sokaras, Dimosthenis

    2017-01-01

    The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen...... evolution reaction. Manganese oxides are promising as catalysts for this reaction. Recent reports show that their activity can be drastically enhanced when modified with gold. Herein, we investigate highly active mixed Au-MnOx thin films for the oxygen evolution reaction, which exhibit more than five times...

  19. Development of Refractory Ceramics for The Oxygen Evolution Reaction (OER) Electrocatalyst Support for Water Electrolysis at elevated temperatures

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Prag, Carsten Brorson; Polonsky, J.

    2012-01-01

    Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis for their th......Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis...

  20. Evolution of oxygen and electrosynthesis of sodium perborate on Ti/SnO/sub 2/-Pt-film anodes

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, E.Yu.; Kondrikov, N.B.; Shub, D.M.

    1988-10-20

    The electrochemical properties of composite Ti/SnO/sub 2/-Pt-film anodes have been studied in the evolution of oxygen and the electrosynthesis of sodium perborate in carbonate and carbonate-borate electrolytes. It has been shown that Ti/SnO/sub 2/-Pt (30-70%) anodes give the highest oxygen evolution rates. At a Pt concentration in the coatings of more than 30% the anodes have a sufficiently high corrosion resistance and acceptable current yields of the peroxo compounds.

  1. Electrochemical Fluorographane: Hybrid Electrocatalysis of Biomarkers, Hydrogen Evolution, and Oxygen Reduction.

    Science.gov (United States)

    Gusmão, Rui; Sofer, Zdeněk; Šembera, Filip; Janoušek, Zbyněk; Pumera, Martin

    2015-11-09

    Fluorographane (C1 Hx F1-x+δ )n is a new member of the graphene family that exhibits hydrophobicity and a large band gap that is tunable based on the level of fluorination. Herein, sensing and energy applications of fluorographane are reported. The results reveal that the carbon-to-fluoride ratio of fluorographane has a great impact on the electrochemical performance of the materials. Lowered oxidation potentials for ascorbic and uric acids, in addition to a catalytic effect for hydroquinone and dopamine redox processes, are obtained with a high fluoride content. Moreover, fluorographane, together with residual copper- and nickel-based doping, acted as a hybrid electrocatalyst to promote hydrogen evolution and oxygen reduction reactions with considerably lower onset potentials than those of graphane (starting material), which makes this a promising material for a broad range of applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Silicon carbide-silicon as a support material for oxygen evolution reaction in PEM steam electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Petrushina, Irina; Christensen, Erik

    technique and the average particle diameter of silicon carbide-silicon was found to be in the range of 5-10 µm, while its specific surface area was about 5 sq.m/g. The oxygen evolution reaction was studied by the cyclic voltammetry technique in 85% phosphoric acid solution at temperatures between 22 and 150...... to the pure oxide catalyst material. This indicates a relatively higher number of active sites deduced from the charge transferred when cycling the potential between two preselected values. Based on the above results, the SiC-Si compound is a potential candidate as a support for the anode electrocatalyst...... for phosphoric acid doped membrane steam electrolysers....

  3. A Permselective CeOx Coating Improves the Stability of Oxygen Evolution Electrocatalysts

    KAUST Repository

    Obata, Keisuke

    2017-12-05

    Highly active NiFeOx electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time due to the loss of Fe species from the active sites into solution during catalysis. Here, we describe the anodic deposition of a CeOx layer that prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeOx layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH- and O2 through while preventing the diffusion of redox ions through the layer to function as a selective O2-evolving electrode. The use of such permselective protective layer provides a new strategy for improving the durability of electrocatalysts.

  4. Carbon dots decorated vertical SnS{sub 2} nanosheets for efficient photocatalytic oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Zhongzhou [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China); CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190 (China); Wang, Fengmei; Shifa, Tofik Ahmed; Liu, Kaili; Huang, Yun; Jiang, Chao; He, Jun, E-mail: hej@nanoctr.cn [CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190 (China); CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190 (China); Liu, Quanlin [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China)

    2016-08-01

    Metal sulfides are highly desirable materials for photocatalytic water splitting because of their appropriate energy bands. However, the poor stability under light illumination in water hinders their wide applications. Here, two-dimensional SnS{sub 2} nanosheets, along with carbon dots of the size around 10 nm, are uniformly grown on fluorine doped tin oxide glasses with a layer of nickel nanoparticles. Significantly, strong light absorption and enhanced photocurrent density are achieved after integration of SnS{sub 2} nanosheets with carbon dots. Notably, the rate of oxygen evolution reached up to 1.1 mmol g{sup −1} h{sup −1} under simulated sunlight irradiation featuring a good stability.

  5. Parallel electrochemical treatment system and application for identifying acid-stable oxygen evolution electrocatalysts.

    Science.gov (United States)

    Jones, Ryan J R; Shinde, Aniketa; Guevarra, Dan; Xiang, Chengxiang; Haber, Joel A; Jin, Jian; Gregoire, John M

    2015-02-09

    Many energy technologies require electrochemical stability or preactivation of functional materials. Due to the long experiment duration required for either electrochemical preactivation or evaluation of operational stability, parallel screening is required to enable high throughput experimentation. Imposing operational electrochemical conditions to a library of materials in parallel creates several opportunities for experimental artifacts. We discuss the electrochemical engineering principles and operational parameters that mitigate artifacts in the parallel electrochemical treatment system. We also demonstrate the effects of resistive losses within the planar working electrode through a combination of finite element modeling and illustrative experiments. Operation of the parallel-plate, membrane-separated electrochemical treatment system is demonstrated by exposing a composition library of mixed-metal oxides to oxygen evolution conditions in 1 M sulfuric acid for 2 h. This application is particularly important because the electrolysis and photoelectrolysis of water are promising future energy technologies inhibited by the lack of highly active, acid-stable catalysts containing only earth abundant elements.

  6. Transition metal ions regulated oxygen evolution reaction performance of Ni-based hydroxides hierarchical nanoarrays

    Science.gov (United States)

    Zhou, Tingting; Cao, Zhen; Zhang, Pan; Ma, Houyi; Gao, Zhen; Wang, Heng; Lu, Yue; He, Jia; Zhao, Yunfeng

    2017-04-01

    Nickel-based hydroxide hierarchical nanoarrays (NiyM(OH)x HNAs M = Fe or Zn) are doped with non-noble transition metals to create nanostructures and regulate their activities for the oxygen evolution reaction. Catalytic performance in these materials depends on their chemical composition and the presence of nanostructures. These novel hierarchical nanostructures contain small secondary nanosheets that are grown on the primary nanowire arrays, providing a higher surface area and more efficient mass transport for electrochemical reactions. The activities of the NiyM(OH)x HNAs for the oxygen evolution reaction (OER) followed the order of Ni2.2Fe(OH)x > Ni(OH)2 > Ni2.1Zn(OH)x, and these trends are supported by density functional theory (DFT) calculations. The Fe-doped nickel hydroxide hierarchical nanoarrays (Ni2.2Fe(OH)x HNAs), which had an appropriate elemental composition and hierarchical nanostructures, achieve the lowest onset overpotential of 234 mV and the smallest Tafel slope of 64.3 mV dec-1. The specific activity, which is normalized to the Brunauer-Emmett-Teller (BET) surface area of the catalyst, of the Ni2.2Fe(OH)x HNAs is 1.15 mA cm-2BET at an overpotential of 350 mV. This is ~4-times higher than that of Ni(OH)2. These values are also superior to those of a commercial IrOx electrocatalyst.

  7. Primary endosymbiosis and the evolution of light and oxygen sensing in photosynthetic eukaryotes

    Directory of Open Access Journals (Sweden)

    Nathan C Rockwell

    2014-10-01

    Full Text Available The origin of the photosynthetic organelle in eukaryotes, the plastid, changed forever the evolutionary trajectory of life on our planet. Plastids are highly specialized compartments derived from a putative single cyanobacterial primary endosymbiosis that occurred in the common ancestor of the supergroup Archaeplastida that comprises the Viridiplantae (green algae and plants, red algae, and glaucophyte algae. These lineages include critical primary producers of freshwater and terrestrial ecosystems, progenitors of which provided plastids through secondary endosymbiosis to other algae such as diatoms and dinoflagellates that are critical to marine ecosystems. Despite its broad importance and the success of algal and plant lineages, the phagotrophic origin of the plastid imposed an interesting challenge on the predatory eukaryotic ancestor of the Archaeplastida. By engulfing an oxygenic photosynthetic cell, the host lineage imposed an oxidative stress upon itself in the presence of light. Adaptations to meet this challenge were thus likely to have occurred early on during the transition from a predatory phagotroph to an obligate phototroph (or mixotroph. Modern algae have recently been shown to employ linear tetrapyrroles (bilins to respond to oxidative stress under high light. Here we explore the early events in plastid evolution and the possible ancient roles of bilins in responding to light and oxygen.

  8. Phosphate Ion Functionalization of Perovskite Surfaces for Enhanced Oxygen Evolution Reaction.

    Science.gov (United States)

    Yang, Chunzhen; Laberty-Robert, Christel; Batuk, Dmitry; Cibin, Giannantonio; Chadwick, Alan V; Pimenta, Vanessa; Yin, Wei; Zhang, Leiting; Tarascon, Jean-Marie; Grimaud, Alexis

    2017-08-03

    Recent findings revealed that surface oxygen can participate in the oxygen evolution reaction (OER) for the most active catalysts, which eventually triggers a new mechanism for which the deprotonation of surface intermediates limits the OER activity. We propose in this work a "dual strategy" in which tuning the electronic properties of the oxide, such as La1-xSrxCoO3-δ, can be dissociated from the use of surface functionalization with phosphate ion groups (Pi) that enhances the interfacial proton transfer. Results show that the Pi functionalized La0.5Sr0.5CoO3-δ gives rise to a significant enhancement of the OER activity when compared to La0.5Sr0.5CoO3-δ and LaCoO3. We further demonstrate that the Pi surface functionalization selectivity enhances the activity when the OER kinetics is limited by the proton transfer. Finally, this work suggests that tuning the catalytic activity by such a "dual approach" may be a new and largely unexplored avenue for the design of novel high-performance catalysts.

  9. Limited oxygen availability in utero may constrain the evolution of live birth in reptiles.

    Science.gov (United States)

    Rafferty, Anthony R; Evans, Roger G; Scheelings, T Franciscus; Reina, Richard D

    2013-02-01

    Although viviparity (live birth) has evolved from oviparity (egg laying) at least 140 times in vertebrates, nearly 120 of these independent events occurred within a single reptile taxon. Surprisingly, only squamate reptiles (lizards and snakes) are capable of facilitating embryonic development to increasingly advanced stages inside the mother during extended periods of oviducal egg retention. Viviparity has never evolved in turtle lineages, presumably because embryos enter and remain in an arrested state until after eggs are laid, regardless of the duration of egg retention. Until now, the limiting factor that initiates and maintains developmental arrest has remained elusive. Here, we show that oviducal hypoxia arrests embryonic development. We demonstrate that hypoxia can maintain developmental arrest after oviposition and that subsequent exposure of arrested embryos to normoxia triggers resumption of their development. We discovered remarkably low oxygen partial pressure in the oviducts of gravid turtles and found that secretions produced by the oviduct retard oxygen diffusion. Our results suggest that an extremely hypoxic environment in the oviduct arrests embryonic development and may constrain the evolution of viviparity in turtles, with the reduced diffusive capacity of oviducal secretions possibly creating or contributing to this hypoxia. We anticipate that these findings will allow us to better understand the mechanisms underlying the evolutionary transition between reproductive modes.

  10. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitly...... molecules binding to bridging oxygens. The third chain interacts weakly and predominantly with the H2O molecules of the second layer, resembling bulk water. We find that the stability of the water layer close to the oxide surface is almost the same as the one found on flat metal surfaces, such as the Pt(111...... adsorbed H2O molecules, which are found to form two-dimensional water chains (layers) on all investigated oxide surfaces. The first chain formed by the most strongly bound H2O molecules is adsorbed on the 5-fold coordinated surface metal atoms. The second chain is composed of less strongly bound H2O...

  11. Scalable Self-Supported Graphene Foam for High-Performance Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Zhu, Yun-Pei; Ran, Jingrun; Qiao, Shi-Zhang

    2017-12-06

    Developing efficient electrocatalysts consisting of earth-abundant elements for oxygen evolution reaction (OER) is crucial for energy devices and technologies. Herein, we report self-supported highly porous nitrogen-doped graphene foam synthesized through the electrochemical expansion of carbon-fiber paper and subsequent nitrogen plasma treatment. A thorough characterization, such as electron microscopy and synchrotron-based near-edge X-ray absorption fine structure, indicates the well-developed porous structures featuring homogeneously doped nitrogen heteroatoms. These merits ensure enriched active sites, an enlarged active surface area, and improved mass/electron transport within the continuous graphene framework, thus leading to an outstanding capability toward electrocatalyzing OER in alkaline media, even competitive with the state-of-the-art noble-/transition-metal and nonmetal electrocatalysts reported to date, from the perspectives of the sharp onset potential, a small Tafel slope, and remarkable durability. Furthermore, a rechargeable Zn-air battery with this self-supported electrocatalyst directly used as the air cathode renders a low charge/discharge overpotential and considerable life span. The finding herein suggests that a rational methodology to synthesize graphene-based materials can significantly enhance the oxygen electrocatalysis, thereby promoting the overall performance of the energy-related system.

  12. Metallic Transition Metal Selenide Holey Nanosheets for Efficient Oxygen Evolution Electrocatalysis.

    Science.gov (United States)

    Fang, Zhiwei; Peng, Lele; Lv, Haifeng; Zhu, Yue; Yan, Chunshuang; Wang, Shengqi; Kalyani, Pranav; Wu, Xiaojun; Yu, Guihua

    2017-09-26

    Catalysts for oxygen evolution reaction (OER) are pivotal to the scalable storage of sustainable energy by means of converting water to oxygen and hydrogen fuel. Designing efficient electrocatalysis combining the features of excellent electrical conductivity, abundant active surface, and structural stability remains a critical challenge. Here, we report the rational design and controlled synthesis of metallic transition metal selenide NiCo2Se4-based holey nanosheets as a highly efficient and robust OER electrocatalyst. Benefiting from synergistic effects of metallic nature, heteroatom doping, and holey nanoarchitecture, NiCo2Se4 holey nanosheets exhibit greatly enhanced kinetics and improved cycling stability for OER. When further employed as an alkaline electrolyzer, the NiCo2Se4 holey nanosheet electrocatalyst enables a high-performing overall water splitting with a low applied external potential of 1.68 V at 10 mA cm-2. This work not only represents a promising strategy to design the efficient and robust OER catalysts but also provides fundamental insights into the structure-property-performance relationship of transition metal selenide-based electrocatalytic materials.

  13. Understanding the reaction of nuclear graphite with molecular oxygen: Kinetics, transport, and structural evolution

    Science.gov (United States)

    Kane, Joshua J.; Contescu, Cristian I.; Smith, Rebecca E.; Strydom, Gerhard; Windes, William E.

    2017-09-01

    For the next generation of nuclear reactors, HTGRs specifically, an unlikely air ingress warrants inclusion in the license applications of many international regulators. Much research on oxidation rates of various graphite grades under a number of conditions has been undertaken to address such an event. However, consequences to the reactor result from the microstructural changes to the graphite rather than directly from oxidation. The microstructure is inherent to a graphite's properties and ultimately degradation to the graphite's performance must be determined to establish the safety of reactor design. To understand the oxidation induced microstructural change and its corresponding impact on performance, a thorough understanding of the reaction system is needed. This article provides a thorough review of the graphite-molecular oxygen reaction in terms of kinetics, mass and energy transport, and structural evolution: all three play a significant role in the observed rate of graphite oxidation. These provide the foundations of a microstructurally informed model for the graphite-molecular oxygen reaction system, a model kinetically independent of graphite grade, and capable of describing both the observed and local oxidation rates under a wide range of conditions applicable to air-ingress.

  14. Fish Ecology and Evolution in the World's Oxygen Minimum Zones and Implications of Ocean Deoxygenation.

    Science.gov (United States)

    Gallo, N D; Levin, L A

    Oxygen minimum zones (OMZs) and oxygen limited zones (OLZs) are important oceanographic features in the Pacific, Atlantic, and Indian Ocean, and are characterized by hypoxic conditions that are physiologically challenging for demersal fish. Thickness, depth of the upper boundary, minimum oxygen levels, local temperatures, and diurnal, seasonal, and interannual oxycline variability differ regionally, with the thickest and shallowest OMZs occurring in the subtropics and tropics. Although most fish are not hypoxia-tolerant, at least 77 demersal fish species from 16 orders have evolved physiological, behavioural, and morphological adaptations that allow them to live under the severely hypoxic, hypercapnic, and at times sulphidic conditions found in OMZs. Tolerance to OMZ conditions has evolved multiple times in multiple groups with no single fish family or genus exploiting all OMZs globally. Severely hypoxic conditions in OMZs lead to decreased demersal fish diversity, but fish density trends are variable and dependent on region-specific thresholds. Some OMZ-adapted fish species are more hypoxia-tolerant than most megafaunal invertebrates and are present even when most invertebrates are excluded. Expansions and contractions of OMZs in the past have affected fish evolution and diversity. Current patterns of ocean warming are leading to ocean deoxygenation, causing the expansion and shoaling of OMZs, which is expected to decrease demersal fish diversity and alter trophic pathways on affected margins. Habitat compression is expected for hypoxia-intolerant species, causing increased susceptibility to overfishing for fisheries species. Demersal fisheries are likely to be negatively impacted overall by the expansion of OMZs in a warming world. © 2016 Elsevier Ltd. All rights reserved.

  15. Hydroxyl-dependent Evolution of Oxygen Vacancies Enables the Regeneration of BiOCl photocatalyst

    KAUST Repository

    Wu, Sujuan

    2017-05-02

    Photoinduced oxygen vacancies (OVs) are widely investigated as a vital point defect in wide-band-gap semiconductors. Still, the formation mechanism of OVs remains unclear in various materials. To elucidate the formation mechanism of photoinduced OVs in bismuth oxychloride (BiOCl), we synthesized two surface hydroxyl discrete samples in light of the discovery of the significant variance of hydroxyl groups before and after UV light exposure. It is noted that OVs can be obtained easily after UV light irradiation in the sample with surface hydroxyl groups, while variable changes were observed in samples without surface hydroxyls. Density functional theory (DFT) calculations reveal that the binding energy of Bi-O is drastically influenced by surficial hydroxyl groups, which is intensely correlated to the formation of photoinduced OVs. Moreover, DFT calculations reveal that the adsorbed water molecules are energetically favored to dissociate into separate hydroxyl groups at the OV sites via proton transfer to a neighboring bridging oxygen atom, forming two bridging hydroxyl groups per initial oxygen vacancy. This result is consistent with the experimental observation that the disappearance of photoinduced OVs and the recovery of hydroxyl groups on the surface of BiOCl after exposed to a H2O(g)-rich atmosphere, and finally enables the regeneration of BiOCl photocatalyst. Here, we introduce new insights that the evolution of photoinduced OVs is dependent on surface hydroxyl groups, which will lead to the regeneration of active sites in semiconductors. This work is useful for controllable designs of defective semiconductors for applications in photocatalysis and photovoltaics.

  16. Plants, Weathering, and the Evolution of Atmospheric Carbon Dioxide and Oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Berner, Robert A

    2008-02-05

    Over the past six years we have published 24 papers that can be divided into three sections: (1) Study of plants and weathering, (2) modeling the evolution of atmospheric CO2 over Phanerozoic time (past 550 million years). (3) Modeling of atmospheric O2 over Phanerozoic time. References to papers published acknowledging this grant can be found at the end of this report and almost all are supplied in pdf form. (1) In the temperate forests of the Cascade Mountains, USA, calcium and magnesium meet vastly different fates beneath angiosperms vs gymnosperms. Calcium is leached beneath both groves of trees, but leached 20-40% more beneath the angiosperms. Magnesium is retained in the forest system beneath the angiosperms and leached from beneath the gymnosperms. (2) We have shown that climate and CO2, based on both carbon cycle modeling and hundreds of independent proxies for paleo-CO2, correlate very well over the past 550 million year. In a recent paper we use this correlation to deduce the sensitivity of global mean temperature to a doubling of atmospheric CO2, and results are in excellent agreement with the results of climatologists based on the historical record and on theoretical climate models (GCM’s).(3) We have shown that concentrations of atmospheric oxygen, calculated by a combined carbon-sulfur cycle model, over the past 550 million years have varied with and influenced biological evolution.

  17. Fluid evolution in CM carbonaceous chondrites tracked through the oxygen isotopic compositions of carbonates

    Science.gov (United States)

    Lindgren, P.; Lee, M. R.; Starkey, N. A.; Franchi, I. A.

    2017-05-01

    The oxygen isotopic compositions of calcite grains in four CM carbonaceous chondrites have been determined by NanoSIMS, and results reveal that aqueous solutions evolved in a similar manner between parent body regions with different intensities of aqueous alteration. Two types of calcite were identified in Murchison, Mighei, Cold Bokkeveld and LaPaz Icefield 031166 by differences in their petrographic properties and oxygen isotope values. Type 1 calcite occurs as small equant grains that formed by filling of pore spaces in meteorite matrices during the earliest stages of alteration. On average, the type 1 grains have a δ18O of ∼32-36‰ (VSMOW), and Δ17O of between ∼2‰ and -1‰. Most grains of type 2 calcite precipitated after type 1. They contain micropores and inclusions, and have replaced ferromagnesian silicate minerals. Type 2 calcite has an average δ18O of ∼21-24‰ (VSMOW) and a Δ17O of between ∼-1‰ and -3‰. Such consistent isotopic differences between the two calcite types show that they formed in discrete episodes and from solutions whose δ18O and δ17O values had changed by reaction with parent body silicates, as predicted by the closed-system model for aqueous alteration. Temperatures are likely to have increased over the timespan of calcite precipitation, possibly owing to exothermic serpentinisation. The most highly altered CM chondrites commonly contain dolomite in addition to calcite. Dolomite grains in two previously studied CM chondrites have a narrow range in δ18O (∼25-29‰ VSMOW), with Δ17O ∼-1‰ to -3‰. These grains are likely to have precipitated between types 1 and 2 calcite, and in response to a transient heating event and/or a brief increase in fluid magnesium/calcium ratios. In spite of this evidence for localised excursions in temperature and/or solution chemistry, the carbonate oxygen isotope record shows that fluid evolution was comparable between many parent body regions. The CM carbonaceous chondrites

  18. Palaeoproterozoic ice houses and the evolution of oxygen-mediating enzymes: the case for a late origin of photosystem II.

    Science.gov (United States)

    Kirschvink, Joseph L; Kopp, Robert E

    2008-08-27

    Two major geological problems regarding the origin of oxygenic photosynthesis are (i) identifying a source of oxygen pre-dating the biological oxygen production and capable of driving the evolution of oxygen tolerance, and (ii) determining when oxygenic photosynthesis evolved. One solution to the first problem is the accumulation of photochemically produced H(2)O(2) at the surface of the glaciers and its subsequent incorporation into ice. Melting at the glacier base would release H(2)O(2), which interacts with seawater to produce O(2) in an environment shielded from the lethal levels of ultraviolet radiation needed to produce H(2)O(2). Answers to the second problem are controversial and range from 3.8 to 2.2 Gyr ago. A sceptical view, based on the metals that have the redox potentials close to oxygen, argues for the late end of the range. The preponderance of geological evidence suggests little or no oxygen in the Late Archaean atmosphere (less than 1 ppm). The main piece of evidence for an earlier evolution of oxygenic photosynthesis comes from lipid biomarkers. Recent work, however, has shown that 2-methylhopanes, once thought to be unique biomarkers for cyanobacteria, are also produced anaerobically in significant quantities by at least two strains of anoxygenic phototrophs. Sterane biomarkers provide the strongest evidence for a date 2.7 Gyr ago or above, and could also be explained by the common evolutionary pattern of replacing anaerobic enzymes with oxygen-dependent ones. Although no anaerobic sterol synthesis pathway has been identified in the modern biosphere, enzymes that perform the necessary chemistry do exist. This analysis suggests that oxygenic photosynthesis could have evolved close in geological time to the Makganyene Snowball Earth Event and argues for a causal link between the two.

  19. The oxygen evolution on La0.5Ba0.5CoO3 : Passivation processes

    NARCIS (Netherlands)

    Kobussen, A.G.C.; Willems, H.; Broers, G.H.J.

    1982-01-01

    Earlier publications on the oxygen evolution of La0.5Ba0.5CoO3 have left a number of observations involving passivation effects of the electrode unexplained. Therefore, the electrode surface used was studied by means of X-ray powder diffraction and electron microscopy (with diffraction and elemental

  20. Tailoring the Activity for Oxygen Evolution Electrocatalysis on Rutile TiO2(110) by Transition-Metal Substitution

    DEFF Research Database (Denmark)

    Garcia-Mota, Monica; Vojvodic, Aleksandra; Metiu, Horia

    2011-01-01

    The oxygen evolution reaction (OER) on the rutile M-TiO2(110) (M = V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Ir, Ni) surfaces was investigated by using density functional theory calculations. The stability of different doped TiO2 systems was analyzed. The scaling relationship between the binding energies...

  1. Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti-Stabilized MnO2

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Paoli, Elisa Antares; Chorkendorff, Ib

    2015-01-01

    Catalysts are required for the oxygen evolution reaction, which are abundant, active, and stable in acid. MnO2 is a promising candidate material for this purpose. However, it dissolves at high overpotentials. Using first-principles calculations, a strategy to mitigate this problem by decorating...

  2. A TiO2/FeMnP Core/Shell Nanorod Array Photoanode for Efficient Photoelectrochemical Oxygen Evolution.

    Science.gov (United States)

    Schipper, Desmond E; Zhao, Zhenhuan; Leitner, Andrew P; Xie, Lixin; Qin, Fan; Alam, Md Kamrul; Chen, Shuo; Wang, Dezhi; Ren, Zhifeng; Wang, Zhiming; Bao, Jiming; Whitmire, Kenton H

    2017-04-25

    A variety of catalysts have recently been developed for electrocatalytic oxygen evolution, but very few of them can be readily integrated with semiconducting light absorbers for photoelectrochemical or photocatalytic water splitting. Here, we demonstrate an efficient core/shell photoanode with a highly active oxygen evolution electrocatalyst shell (FeMnP) and semiconductor core (rutile TiO2) for photoelectrochemical oxygen evolution reaction. Metal-organic chemical vapor deposition from a single-source precursor was used to ensure good contact between the FeMnP and the TiO2. The TiO2/FeMnP core/shell photoanode reaches the theoretical photocurrent density for rutile TiO2 of 1.8 mA cm(-2) at 1.23 V vs reversible hydrogen electrode under simulated 100 mW cm(-2) (1 sun) irradiation. The dramatic enhancement is a result of the synergistic effects of the high oxygen evolution reaction activity of FeMnP (delivering an overpotential of 300 mV with a Tafel slope of 65 mV dec(-1) in 1 M KOH) and the conductive interlayer between the surface active sites and semiconductor core which boosts the interfacial charge transfer and photocarrier collection. The facile fabrication of the TiO2/FeMnP core/shell nanorod array photoanode offers a compelling strategy for preparing highly efficient photoelectrochemical solar energy conversion devices.

  3. On the influence of hydronium and hydroxide ion diffusion on the hydrogen and oxygen evolution reactions in aqueous media

    DEFF Research Database (Denmark)

    Wiberg, Gustav Karl Henrik; Arenz, Matthias

    2015-01-01

    We present a study concerning the influence of the diffusion of H+ and OH- ions on the hydrogen and oxygen evolution reactions (HER and OER) in aqueous electrolyte solutions. Using a rotating disk electrode (RDE), it is shown that at certain conditions the observed current, i.e., the reaction rate...

  4. Molecular evolution of the reactive oxygen-generating NADPH oxidase (Nox/Duox family of enzymes

    Directory of Open Access Journals (Sweden)

    Lambeth J David

    2007-07-01

    Full Text Available Abstract Background NADPH-oxidases (Nox and the related Dual oxidases (Duox play varied biological and pathological roles via regulated generation of reactive oxygen species (ROS. Members of the Nox/Duox family have been identified in a wide variety of organisms, including mammals, nematodes, fruit fly, green plants, fungi, and slime molds; however, little is known about the molecular evolutionary history of these enzymes. Results We assembled and analyzed the deduced amino acid sequences of 101 Nox/Duox orthologs from 25 species, including vertebrates, urochordates, echinoderms, insects, nematodes, fungi, slime mold amoeba, alga and plants. In contrast to ROS defense enzymes, such as superoxide dismutase and catalase that are present in prokaryotes, ROS-generating Nox/Duox orthologs only appeared later in evolution. Molecular taxonomy revealed seven distinct subfamilies of Noxes and Duoxes. The calcium-regulated orthologs representing 4 subfamilies diverged early and are the most widely distributed in biology. Subunit-regulated Noxes represent a second major subdivision, and appeared first in fungi and amoeba. Nox5 was lost in rodents, and Nox3, which functions in the inner ear in gravity perception, emerged the most recently, corresponding to full-time adaptation of vertebrates to land. The sea urchin Strongylocentrotus purpuratus possesses the earliest Nox2 co-ortholog of vertebrate Nox1, 2, and 3, while Nox4 first appeared somewhat later in urochordates. Comparison of evolutionary substitution rates demonstrates that Nox2, the regulatory subunits p47phox and p67phox, and Duox are more stringently conserved in vertebrates than other Noxes and Nox regulatory subunits. Amino acid sequence comparisons identified key catalytic or regulatory regions, as 68 residues were highly conserved among all Nox/Duox orthologs, and 14 of these were identical with those mutated in Nox2 in variants of X-linked chronic granulomatous disease. In addition to

  5. Molecular evolution of the reactive oxygen-generating NADPH oxidase (Nox/Duox) family of enzymes

    Science.gov (United States)

    Kawahara, Tsukasa; Quinn, Mark T; Lambeth, J David

    2007-01-01

    Background NADPH-oxidases (Nox) and the related Dual oxidases (Duox) play varied biological and pathological roles via regulated generation of reactive oxygen species (ROS). Members of the Nox/Duox family have been identified in a wide variety of organisms, including mammals, nematodes, fruit fly, green plants, fungi, and slime molds; however, little is known about the molecular evolutionary history of these enzymes. Results We assembled and analyzed the deduced amino acid sequences of 101 Nox/Duox orthologs from 25 species, including vertebrates, urochordates, echinoderms, insects, nematodes, fungi, slime mold amoeba, alga and plants. In contrast to ROS defense enzymes, such as superoxide dismutase and catalase that are present in prokaryotes, ROS-generating Nox/Duox orthologs only appeared later in evolution. Molecular taxonomy revealed seven distinct subfamilies of Noxes and Duoxes. The calcium-regulated orthologs representing 4 subfamilies diverged early and are the most widely distributed in biology. Subunit-regulated Noxes represent a second major subdivision, and appeared first in fungi and amoeba. Nox5 was lost in rodents, and Nox3, which functions in the inner ear in gravity perception, emerged the most recently, corresponding to full-time adaptation of vertebrates to land. The sea urchin Strongylocentrotus purpuratus possesses the earliest Nox2 co-ortholog of vertebrate Nox1, 2, and 3, while Nox4 first appeared somewhat later in urochordates. Comparison of evolutionary substitution rates demonstrates that Nox2, the regulatory subunits p47phox and p67phox, and Duox are more stringently conserved in vertebrates than other Noxes and Nox regulatory subunits. Amino acid sequence comparisons identified key catalytic or regulatory regions, as 68 residues were highly conserved among all Nox/Duox orthologs, and 14 of these were identical with those mutated in Nox2 in variants of X-linked chronic granulomatous disease. In addition to canonical motifs, the B

  6. Bimetallic electrocatalysts on titanium dioxide-based supports for methanol oxidation and oxygen evolution

    Science.gov (United States)

    Fuentes, Roderick Eliel

    Electrocatalysts are essential for the development of active and durable fuel cells and hydrogen production technologies. Generally, electrochemical processes of energy conversion and hydrogen generation in a Proton Exchange Membrane (PEM) utilize precious metals, such as platinum, iridium and ruthenium, as electrocatalysts. For the methanol oxidation and oxygen evolution reaction, a bimetallic structure can be used to enhance kinetics and increase stability. It is desired to support electrocatalysts to disperse nanoparticles on the surface and promote better catalyst utilization. Traditionally, carbon has been used as an electrochemical support because it has a high surface area and high electrical conductivity. The problem with carbon is that it is not a very stable material and can corrode at voltages more than 0.9 V, affecting performance of the electrochemical reaction. Therefore, it would be useful to support electrocatalysts in a stable material with suitable conductivity. Using titanium dioxide as a support can be advantageous due to its corrosion-resistant capability. TiO2 exhibit different crystalline structures, such as anatase and rutile, which can have an effect on catalytic activity. Unfortunately, it is not conductive; hence, it is not used in electrochemical applications. However, it can be doped with niobium to increase electronic conductivity; but, it usually come at the expense of surface area. In this work, TiO 2 and Nb-TiO2 were studied as platinum/ruthenium and iridium/ruthenium nanoparticles supports for the electrochemical oxidation of methanol and oxygen evolution, respectively. Even though the conductivity of our supports was very low, adding a considerable loading of nanoparticles increased conductivity of the composite material (support + catalyst) to acceptable levels. Using cyclic voltammetry (CV) and direct methanol fuel cell tests creating a membrane electrode assembly (MEA), Pt-Ru supported on Nb-TiO2 and TiO 2 showed superior

  7. The Paleoproterozoic Snowball as the Trigger for Atmospheric Oxygen and the Evolution of Eukaryotes

    Science.gov (United States)

    Kirschvink, J. L.

    2001-05-01

    Paleoproterozoic Snowball itself marks the major boundary between the anaerobic Archean and the oxidizing Proterozoic and younger surface environments. H. Hartman (personal communication) suggests that the ecological stress of the Snowball may have promoted the horizontal gene transfer events which led to the formation of photosystem II. The chemistry of hydrothermal vent waters released from the present mid-ocean spreading centers is remarkably similar to the nutrient media typically used for growing cyanobacteria in pure culture (Kirschvink et al., 2000). During a long snowball event, the entire volume of the world oceans is expected to go through these vent systems many times; hence, the bulk chemistry of the world oceans should approach the hydrothermal vent composition. Upon melting, cyanobacteria ought to turn the entire surface of the oceans green with photosynthetic activity. The post-Paleoproterozoic Snowball oxygen burst could then foster the evolution of the eukaryotic cell which appears shortly thereafter in the stratigraphic record. Similar oxygen bursts after the Neoproterozoic glacial episodes would incrementally allow the evolution of larger animal forms.

  8. Molecular Mixed-Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts.

    Science.gov (United States)

    Suseno, Sandy; McCrory, Charles C L; Tran, Rosalie; Gul, Sheraz; Yano, Junko; Agapie, Theodor

    2015-09-14

    Well-defined mixed-metal [CoMn3 O4 ] and [NiMn3 O4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3 O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3 O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Oxidatively Electrodeposited Thin-Film Transition Metal (Oxy)hydroxides as Oxygen Evolution Catalysts.

    Science.gov (United States)

    Morales-Guio, Carlos G; Liardet, Laurent; Hu, Xile

    2016-07-20

    The electrolysis of water to produce hydrogen and oxygen is a simple and attractive approach to store renewable energies in the form of chemical fuels. The oxygen evolution reaction (OER) is a complex four-electron process that constitutes the most energy-inefficient step in water electrolysis. Here we describe a novel electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as OER catalysts. The thin films have nanodomains of crystallinity with lattice spacing similar to those of double-layered hydroxides. The loadings of these thin-film catalysts were accurately determined with a resolution of below 1 μg cm(-2) using an electrochemical quartz microcrystal balance. The loading-activity relations for various catalysts were established using voltammetry and impedance spectroscopy. The thin-film catalysts have up to four types of loading-activity dependence due to film nucleation and growth as well as the resistance of the films. A zone of intrinsic activity has been identified for all of the catalysts where the mass-averaged activity remains constant while the loading is increased. According to their intrinsic activities, the metal oxides can be classified into three categories: NiOx, MnOx, and FeOx belong to category I, which is the least active; CoOx and CoNiOx belong to category II, which has medium activity; and FeNiOx, CoFeOx, and CoFeNiOx belong to category III, which is the most active. The high turnover frequencies of CoFeOx and CoFeNiOx at low overpotentials and the simple deposition method allow the fabrication of high-performance anode electrodes coated with these catalysts. In 1 M KOH and with the most active electrode, overpotentials as low as 240 and 270 mV are required to reach 10 and 100 mA cm(-2), respectively.

  10. Cobalt hydroxide nanoflakes and their application as supercapacitors and oxygen evolution catalysts

    Science.gov (United States)

    Rovetta, A. A. S.; Browne, M. P.; Harvey, A.; Godwin, I. J.; Coleman, J. N.; Lyons, M. E. G.

    2017-09-01

    Finding alternative routes to access and store energy has become a major issue recently. Transition metal oxides have shown promising behaviour as catalysts and supercapacitors. Recently, liquid exfoliation of bulk metal oxides appears to be an effective route which provides access to two-dimensional (2D) nano-flakes, the size of which can be easily selected. These 2D materials exhibit excellent electrochemical charge storage and catalytic activity for the oxygen evolution reaction. In this study, various sized selected cobalt hydroxide nano-flake materials are fabricated by this time efficient and highly reproducible process. Subsquently, the electrochemical properties of the standard size Co(OH)2 nanoflakes were investigated. The oxide modified electrodes were prepared by spraying the metal oxide flake suspension onto a porous conductive support electrode foam, either glassy carbon or nickel. The cobalt hydroxide/nickel foam system was found to have an overpotential value at 10 mA cm-2 in 1 M NaOH as low as 280 mV and an associated redox capacitance exhibiting numerical values up to 1500 F g-1, thereby making it a viable dual use electrode.

  11. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    KAUST Repository

    Shinagawa, Tatsuya

    2017-03-27

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 °C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeOx electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cmgeo(-2) .

  12. Ultrafast and large scale preparation of superior catalyst for oxygen evolution reaction

    Science.gov (United States)

    Tian, Xianqing; Liu, Yunhua; Xiao, Dan; Sun, Jie

    2017-10-01

    The development of efficient and earth abundant catalyst for the oxygen evolution reaction (OER) is a key challenge for the renewable energy research community. Here, we report a facile and ultrafast route to immobilize nickel-iron layered double hydroxide (NiFe-LDH) nanoparticles on nickel foam (NF) via soaking the direct electroless deposited prussian blue analogue (PBA) on NF in 1 M KOH. This NiFe-LDH/NF electrode can be prepared in a few seconds without further treatments. It has three-dimensional interpenetrating network originated from its PBA precursor which facilitate the diffusion and ad/desorption of the reactants and producing for OER. And further characterization of the Faradaic efficiency and forced convection tests show direct evidence to demonstrate the formation of free intermediate(s) in the OER process. This electrode (typically NiFe-LDH-20s/NF) exhibits outstanding electrocatalytic activity with low overpotential of ∼0.240 V at 10 mA cm-2, low Tafel slope of 38 mV dec-1, and great stability. This feasible strategy affords a new strategy for the large scale manufacture of low-cost, effective and robust OER electrodes.

  13. Boosting the performance of the nickel anode in the oxygen evolution reaction by simple electrochemical activation

    Energy Technology Data Exchange (ETDEWEB)

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro [King Abdullah Univ. of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Div. PSE, Thuwal (Saudi Arabia)

    2017-04-24

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeO{sub x} electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cm{sub geo}{sup -2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Uniquely confining Cu2S nanoparticles in graphitized carbon fibers for enhanced oxygen evolution reaction

    Science.gov (United States)

    Zhao, Xiaoqian; Liu, Li; Zhang, Yan; Zhang, Huijuan; Wang, Yu

    2017-08-01

    Up to now, the literature on Cu2S with specific morphology applied to oxygen evolution reaction (OER) in the electrocatalytic field has been limited. In this work, unique peapod-like Cu2S/C exhibiting superb electrocatalytic performance toward OER is successfully synthesized, by employing Cu(OH)2 nanorods as the template and nontoxic glucose as the carbon source and then annealing with sublimed sulfur. It can be seen that this work explores a new application area for Cu2S. More precisely, the novel morphology contributes to increasing the electrochemical active surface area effectively and promoting contact between the Cu2S nanoparticles and the electrolyte. During electrochemical measurements, the peapod-like Cu2S/C shows enhanced electrocatalytic activity with a low overpotential of 401 mV at the current density of 10 mA cm-2 and a Tafel slope of 52 mV dec-1. More importantly, our material is able to maintain stability for at least 8 h at constant potential and the current loss is negligible after 2000 cycles. Obviously, these striking properties fully demonstrate that the peapod-like Cu2S/C as an efficient catalyst shows great promise for OER.

  15. Composition- and Structure-Tunable Gold-Cobalt Nanoparticles and Electrocatalytic Synergy for Oxygen Evolution Reaction.

    Science.gov (United States)

    Lu, Aolin; Peng, Dong-Liang; Chang, Fangfang; Skeete, Zakiya; Shan, Shiyao; Sharma, Anju; Luo, Jin; Zhong, Chuan-Jian

    2016-08-10

    The increasing energy crisis constitutes an inspiring drive seeking alternative energies such as hydrogen from water splitting which is clean and abundant, but a key challenge for water splitting is the need of highly efficient catalysts for oxygen evolution reaction (OER). This report describes findings of an investigation of the synthesis of gold-cobalt (AuCo) nanoparticles by a facile one-pot and injection method and their use as highly efficient catalysts for OER. While particle size depends on the synthesis method, the composition of the nanoparticles is controlled by feeding ratio of Au and Co precursors in the synthesis. Depending on Co content, the nanoparticles exhibit largely phase-segregated domains with a core (Au)-shell (Co) type of structure at a high level of Co. Upon the thermochemical treatment of carbon-supported AuCo nanoparticles, the redox activity of Co species in the nanoparticles with cycle number is shown to decrease which changes the surface oxidation state of Co species without changing the composition significantly. The electrocatalytic activity for OER in alkaline electrolytes is shown to depend on the bimetallic composition, displaying a maximum activity for an Au:Co ratio of ∼2:3. This dependence is also shown to correlate with the surface oxidation state and redox activities, providing an insight into the electrocatalytic activity. Mechanistic aspects of the electrocataltytic properties are discussed in terms of the bifunctional synergy of Co and Au in the nanoparticle catalysts.

  16. A fascinating combination of Co, Ni and Al nanomaterial for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Sher Bahadar, E-mail: sbkhan@kau.edu.sa [Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah, 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, King Abdulaziz University, P. O. Box 80203, Jeddah, 21589 (Saudi Arabia); Khan, Shahid Ali; Asiri, Abdullah M. [Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah, 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, King Abdulaziz University, P. O. Box 80203, Jeddah, 21589 (Saudi Arabia)

    2016-05-01

    Graphical abstract: - Highlights: • Cobalt based nanomaterials. • Water splitting. • Low overpotential. • Plausible self-repair electrocatalyst. - Abstract: Interesting combination of Co, Ni and Al have been assessed for oxygen evolution reaction (OER). Layered double hydroxide (LDH) nanosheets of NiCoAl, Co-Al oxide nanoparticles and Co-Ni oxide nanoparticles were prepared and studied for the first time as OER catalyst. Among all the subjected catalysts, the binary LDH comprise of NiCoAl showed comparatively high catalytic activity than Co-Al oxide nanoparticles and Co-Ni oxide nanoparticles. The Co-Al and Co-Ni oxide nanoparticles showed current densities of 34.6 and 24.5 mA cm{sup −2}, respectively at 1 V in 0.3 M KOH solution. However at the same conditions, NiCoAl-LDH showed comparatively low overpotential, high current density (40.8 mA cm{sup −2}) and lower Tafel slope. The low overpotential and high catalytic activity of NiCoAl-LDH stipulate the possibility to reduce the demand of precious, rare earth and expensive transition metal catalyst in electrochemical water splitting for OER.

  17. A fascinating combination of Co, Ni and Al nanomaterial for oxygen evolution reaction

    Science.gov (United States)

    Khan, Sher Bahadar; Khan, Shahid Ali; Asiri, Abdullah M.

    2016-05-01

    Interesting combination of Co, Ni and Al have been assessed for oxygen evolution reaction (OER). Layered double hydroxide (LDH) nanosheets of NiCoAl, Co-Al oxide nanoparticles and Co-Ni oxide nanoparticles were prepared and studied for the first time as OER catalyst. Among all the subjected catalysts, the binary LDH comprise of NiCoAl showed comparatively high catalytic activity than Co-Al oxide nanoparticles and Co-Ni oxide nanoparticles. The Co-Al and Co-Ni oxide nanoparticles showed current densities of 34.6 and 24.5 mA cm-2, respectively at 1 V in 0.3 M KOH solution. However at the same conditions, NiCoAl-LDH showed comparatively low overpotential, high current density (40.8 mA cm-2) and lower Tafel slope. The low overpotential and high catalytic activity of NiCoAl-LDH stipulate the possibility to reduce the demand of precious, rare earth and expensive transition metal catalyst in electrochemical water splitting for OER.

  18. Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Seo Hyoung; Danilovic, Nemanja; Chang, Kee-Chul; Subbaraman, Ram; Paulikas, Arvydas P.; Fong, Dillon D.; Highland, Matthew J.; Baldo, Peter M.; Stamenkovic, Vojislav R.; Freeland, John W.; Eastman, Jeffrey A.; Markovic, Nenad M.

    2014-06-18

    In developing cost-effective complex oxide materials for the oxygen evolution reaction, it is critical to establish the missing links between structure and function at the atomic level. The fundamental and practical implications of the relationship on any oxide surface are prerequisite to the design of new stable and active materials. Here we report an intimate relationship between the stability and reactivity of oxide catalysts in exploring the reaction on strontium ruthenate single-crystal thin films in alkaline environments. We determine that for strontium ruthenate films with the same conductance, the degree of stability, decreasing in the order (001)4(110)4(111), is inversely proportional to the activity. Both stability and reactivity are governed by the potential-induced transformation of stable Ru4þ to unstable Run44þ. This ordered(Ru4þ)-to-disordered(Run44þ) transition and the development of active sites for the reaction are determined by a synergy between electronic and morphological effects.

  19. Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

    Directory of Open Access Journals (Sweden)

    Joel Sanchez

    2017-05-01

    Full Text Available Zirconium phosphate (ZrP, an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER. Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II, Fe(III, Co(II, and Ni(II cations. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the composite materials and confirm the incorporation of the metal cations either between the layers or on the surface of ZrP. Both types of metal-modified systems were examined for their catalytic activity for the OER in 0.1 M KOH solution. All metal-modified ZrP systems were active for the OER. Trends in activity are discussed as a function of the molar ratio in relation to the two types of catalyst systems, resulting in overpotentials for metal-adsorbed ZrP catalysts that were less than, or equal to, their metal-intercalated counterparts.

  20. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

  1. Surface evolution of a Pt-Pd-Au electrocatalyst for stable oxygen reduction

    Science.gov (United States)

    Li, Jian; Yin, Hui-Ming; Li, Xi-Bo; Okunishi, Eiji; Shen, Yong-Li; He, Jia; Tang, Zhen-Kun; Wang, Wen-Xin; Yücelen, Emrah; Li, Chao; Gong, Yue; Gu, Lin; Miao, Shu; Liu, Li-Min; Luo, Jun; Ding, Yi

    2017-08-01

    Core-shell nanocatalysts have demonstrated potential as highly active low-Pt fuel cell cathodes for the oxygen reduction reaction (ORR); however, challenges remain in optimizing their surface and interfacial structures, which often exhibit undesirable structural degradation and poor durability. Here, we construct an unsupported nanoporous catalyst with a Pt-Pd shell of sub-nanometre thickness on Au, which demonstrates an initial ORR activity of 1.140 A mgPt-1 at 0.9 V. The activity increases to 1.471 A mgPt-1 after 30,000 potential cycles and is stable over a further 70,000 cycles. Using aberration-corrected scanning transmission electron microscopy and atomically resolved elemental mapping, the origin of the activity change is revealed to be an atomic-scale evolution of the shell from an initial Pt-Pd alloy into a bilayer structure with a Pt-rich trimetallic surface, and finally into a uniform and stable Pt-Pd-Au alloy. This Pt-Pd-Au alloy possesses a suitable configuration for ORR, giving a relatively low free energy change for the final water formation from adsorbed OH intermediate during the reaction.

  2. Modular and Stepwise Synthesis of a Hybrid Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Shen, Jian-Qiang; Liao, Pei-Qin; Zhou, Dong-Dong; He, Chun-Ting; Wu, Jun-Xi; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2017-02-08

    The paddle-wheel type cluster Co2(RCOO)4(LT)2 (R = substituent group, LT = terminal ligand), possessing unusual metal coordination geometry compared with other cobalt compounds, may display high catalytic activity but is highly unstable especially in water. Here, we show that with judicious considerations of the host/guest geometries and modular synthetic strategies, the labile dicobalt clusters can be immobilized and stabilized in a metal-organic framework (MOF) as coordinative guests. The Fe(na)4(LT) fragment in the MOF [{Fe3(μ3-O)(bdc)3}4{Fe(na)4(LT)}3] (H2bdc = 1,4-benzenedicaboxylic acid, Hna = nicotinic acid) can be removed to give [{Fe3(μ3-O)(bdc)3}4] with a unique framework connectivity possessing suitable distribution of open metal sites for binding the dicobalt cluster in the form of Co2(na)4(LT)2. After two-step, single-crystal to single-crystal, postsynthetic modifications, a thermal-, water-, and alkaline-stable MOF [{Fe3(μ3-O)(bdc)3}4{Co2(na)4(LT)2}3] containing the desired dicobalt cluster was obtained, giving extraordinarily high electrocatalytic oxygen evolution activity in water at pH = 13 with overpotential as low as 225 mV at 10.0 mA cm-2.

  3. Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Alia, Shaun M. [Chemistry; Shulda, Sarah [Department; Ngo, Chilan [Department; Pylypenko, Svitlana [Department; Pivovar, Bryan S. [Chemistry

    2018-01-30

    Iridium-nickel (Ir-Ni) and iridium-cobalt (Ir-Co) nanowires have been synthesized by galvanic displacement and studied for their potential to increase the performance and durability of electrolysis systems. Performances of Ir-Ni and Ir-Co nanowires for the oxygen evolution reaction (OER) have been measured in rotating disk electrode half-cells and single-cell electrolyzers and compared with commercial baselines and literature references. The nanowire catalysts showed improved mass activity, by more than an order of magnitude compared with commercial Ir nanoparticles in half-cell tests. The nanowire catalysts also showed greatly improved durability, when acid-leached to remove excess Ni and Co. Both Ni and Co templates were found to have similarly positive impacts, although specific differences between the two systems are revealed. In single-cell electrolysis testing, nanowires exceeded the performance of Ir nanoparticles by 4-5 times, suggesting that significant reductions in catalyst loading are possible without compromising performance.

  4. High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

    2017-08-17

    Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

  5. Ancient atmospheres and the evolution of oxygen sensing via the hypoxia-inducible factor in metazoans.

    Science.gov (United States)

    Taylor, Cormac T; McElwain, Jennifer C

    2010-10-01

    Metazoan diversification occurred during a time when atmospheric oxygen levels fluctuated between 15 and 30%. The hypoxia-inducible factor (HIF) is a primary regulator of the adaptive transcriptional response to hypoxia. Although the HIF pathway is highly conserved, its complexity increased during periods when atmospheric oxygen concentrations were increasing. Thus atmospheric oxygen levels may have provided a selection force on the development of cellular oxygen-sensing pathways.

  6. Enhanced kinetics of hole transfer and electrocatalysis during photocatalytic oxygen evolution by cocatalyst tuning

    KAUST Repository

    Nurlaela, Ela

    2016-05-23

    Understanding photophysical and electrocatalytic processes during photocatalysis in a powder suspension system is crucial for developing efficient solar energy conversion systems. We report a substantial enhancement by a factor of 3 in photocatalytic effi-ciency for the oxygen evolution reaction (OER) by adding trace amounts (~0.05 wt%) of noble metals (Rh or Ru) to a 2 wt% cobalt oxide-modified Ta3N5 photocatalyst particulate. The optimized system exhibited high quantum efficiencies (QEs) of up to 28 and 8.4% at 500 and 600 nm in 0.1 M Na2S2O8 at pH 14. By isolating the electrochemical components to generate doped cobalt oxide electrodes, the electrocatalytic activity of cobalt oxide when doped with Ru or Rh was improved compared with cobalt oxide, as evidenced by the onset shift for electrochemical OER. Density functional theory (DFT) calculation shows that the ef-fects of a second metal addition perturbs the electronic structure and redox properties in such a way that both hole transfer kinetics and electrocatalytic rates improve. Time resolved terahertz spectroscopy (TRTS) measurement provides evidence of long-lived electron populations (>1 ns; with mobilities μe ~0.1-3 cm2 V-1 s-1), which are not perturbed by the addition of CoOx-related phases. Furthermore, we find that Ta3N5 phases alone suffer ultrafast hole trapping (within 10 ps); the CoOx and M-CoOx decorations most likely induce a kinetic competition between hole transfer toward the CoOx-related phases and trapping in the Ta3N5 phase, which is consistent with the improved OER rates. The present work not only provides a novel way to improve electrocatalytic and photocatalytic performance but also gives additional tools and insight to understand the characteristics of photocatalysts that can be used in a suspension system.

  7. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela

    2016-01-25

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

  8. Chasing Neoproterozoic Atmospheric Oxygen Ghosts

    Science.gov (United States)

    Bjerrum, C. J.; Canfield, D. E.; Dahl, T. W.

    2016-12-01

    Increasing atmospheric oxygen has been considered a necessary condition for the evolution of animal life for over half a century. While direct proxies for atmospheric oxygen are difficult to obtain, a number of indirect proxies have been giving us a ghost image of rising atmospheric oxygen at the close of the Precambrian. In this context, redox sensitive elements and isotopes represent the hallmark for a significant reduction in anoxic areas of the world ocean, implicating a significant rise of atmospheric oxygen during the Neoproterozoic. Here, we test to what degree redox sensitive elements in ancient marine sediments are proxies of atmospheric oxygen. We model the redox-chemical evolution of the shelf seas and ocean using a combination of 3D high resolution shelf sea models and a simpler global ocean biogeochemical model including climate weathering feedbacks, a free sea level and parameterized icecaps. We find that ecosystem evolution would have resulted in reorganization of the nutrient and redox balance of the shelf-ocean system causing a significant increase in oxygenated areas that permitted a boosting of trace metal concentrations in the remaining anoxic areas. While this reorganization takes place there is limited net change in the modelled atmospheric oxygen, warning us against interpreting changing trace metal concentrations and isotopes as reflecting a rise in atmospheric oxygen.

  9. Oxygen and hydrogen peroxide in the early evolution of life on earth: in silico comparative analysis of biochemical pathways.

    Science.gov (United States)

    Slesak, Ireneusz; Slesak, Halina; Kruk, Jerzy

    2012-08-01

    In the Universe, oxygen is the third most widespread element, while on Earth it is the most abundant one. Moreover, oxygen is a major constituent of all biopolymers fundamental to living organisms. Besides O(2), reactive oxygen species (ROS), among them hydrogen peroxide (H(2)O(2)), are also important reactants in the present aerobic metabolism. According to a widely accepted hypothesis, aerobic metabolism and many other reactions/pathways involving O(2) appeared after the evolution of oxygenic photosynthesis. In this study, the hypothesis was formulated that the Last Universal Common Ancestor (LUCA) was at least able to tolerate O(2) and detoxify ROS in a primordial environment. A comparative analysis was carried out of a number of the O(2)-and H(2)O(2)-involving metabolic reactions that occur in strict anaerobes, facultative anaerobes, and aerobes. The results indicate that the most likely LUCA possessed O(2)-and H(2)O(2)-involving pathways, mainly reactions to remove ROS, and had, at least in part, the components of aerobic respiration. Based on this, the presence of a low, but significant, quantity of H(2)O(2) and O(2) should be taken into account in theoretical models of the early Archean atmosphere and oceans and the evolution of life. It is suggested that the early metabolism involving O(2)/H(2)O(2) was a key adaptation of LUCA to already existing weakly oxic zones in Earth's primordial environment.

  10. Evolution of Eighteen Degree Water and deep mixed layer oxygen and properties from profiling floats during CLIMODE

    Science.gov (United States)

    Navarro, B.; Talley, L.

    2008-12-01

    As part of the CLIMODE observations of Eighteen Degree Water (EDW) formation and destruction, 9 profiling floats equipped with optical oxygen sensors as well as CTDs profiled temperature, salinity and oxygen every 5 days to 500 m and every 10 days to 1800 m during 2006 and 2007 in the Gulf Stream region. Thick (200- 450 m) late winter mixed layers with EDW properties were observed close to the Gulf Stream at about 52W, and in a separate cluster up to several hundred kilometers south of the Gulf Stream at about 62W, within the westward recirculation. Relatively thick winter mixed layers at 14C were observed north of the Gulf Stream, and also adjacent to the North Atlantic Current much farther to the east. Mixed layer oxygen saturation is a robust indicator of deep mixing: it is depressed in the thick winter mixed layers and increases abruptly upon cessation of deep mixing. EDW layers for these floats, defined by low potential density gradient, were thickest during and just after late- winter outcropping. EDW thickness declined by about 100 m when mixing ceased, with the EDW layer center also shifting physically downward. Oxygen saturation decreased in the EDW by about 10 percent from late winter to late summer, indicating annual aging of the water mass followed by renewal again in the winter. The oxygen-equipped floats provide an excellent opportunity to study the seasonal evolution of oxygen in the upper ocean in the Sargasso Sea. A well-developed oxygen minimum, centered at about 27.2 sigma theta and originating in the tropical Atlantic, underlies the EDW at about 800 m (south of the Gulf Stream). Above the EDW were the seasonally-evolving mixed layer with a thin underlying oxygen maximum layer in spring/summer and a thin oxygen minimum layer in fall/early winter, associated with photosynthesis/respiration. Although the EDW's absolute oxygen content decreased throughout the year following late winter formation, the EDW was marked by a slight vertical oxygen

  11. Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts

    KAUST Repository

    Yang, Xiulin

    2016-04-21

    Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments.

  12. Light dependence of quantum yields for PSII charge separation and oxygen evolution in eucaryotic algae

    NARCIS (Netherlands)

    Flameling, I.A.; Kromkamp, J.C.

    1998-01-01

    Quantum yields of photosystem II (PSII) charge separation (Phi(P)) and oxygen production (Phi(O2)) were determined by simultaneous measurements of oxygen production and variable fluorescence in four different aquatic microalgae representing three different taxonomic groups: the freshwater alga

  13. Stabilization of the coupled oxygen and phosphorus cycles by the evolution of bioturbation

    DEFF Research Database (Denmark)

    Boyle, Richard; Dahl, Tais Wittchen; Dale, A. W.

    2014-01-01

    between bioturbated and laminated sediments. Bioturbation also reduces steady-state marine phosphate levels, but this effect is offset by the decline in iron-adsorbed phosphate burial that results from a decrease in oxygen concentrations. The introduction of oxygen-sensitive bioturbation to dynamical...

  14. Metal-organic-frameworks derived cobalt embedded in various carbon structures as bifunctional electrocatalysts for oxygen reduction and evolution reactions.

    Science.gov (United States)

    Chen, Binling; Ma, Guiping; Zhu, Yanqiu; Xia, Yongde

    2017-07-13

    A series of nanocomposites of cobalt embedded in N-doped nanoporous carbons, carbon nanotubes or hollow carbon onions have been synthesized by a one-step carbonization of metal-organic-framework ZIF-67. The effect of the carbonization temperature on the structural evolution of the resulting nanocomposites has been investigated in detail. Among the as-synthesized materials, the cobalt/nanoporous N-doped carbon composites have demonstrated excellent electrocatalytic activities and durability towards oxygen reduction reaction in alkaline medium. Compared to the benchmark Pt/C catalyst, the optimized Co@C-800 (carbonized at 800 °C) exhibited high oxygen reduction reaction activity with an onset potential of 0.92 V, and a half-wave potential of 0.82 V. Moreover, the optimized Co@C-800 also showed enhanced electrocatalytic activity towards oxygen evolution reaction from water splitting, with a low onset potential of 1.43 V and a potential of 1.61 V at 10 mA cm-2 current density. This work offered a simple solution to develop metal-organic-framework-derived materials for highly efficient electrochemical applications.

  15. Self-Assembly of Spinel Nanocrystals into Mesoporous Spheres as Bifunctionally Active Oxygen Reduction and Evolution Electrocatalysts.

    Science.gov (United States)

    Lee, Dong Un; Li, Jingde; Park, Moon Gyu; Seo, Min Ho; Ahn, Wook; Stadelmann, Ian; Ricardez-Sandoval, Luis; Chen, Zhongwei

    2017-05-22

    The present work introduces spinel oxide nanocrystals self-assembled into mesoporous spheres that are bifunctionally active towards catalyzing both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The electrochemical evaluation reveals that (Ni,Co) 3 O 4 demonstrates a significantly positive-shifted ORR onset and half-wave potentials [-0.127 and -0.292 V vs. saturated calomel electrode (SCE), respectively], whereas Co 3 O 4 results in a negative-shifted OER potential (0.65 V vs. SCE) measured at 10 mA cm -2 . Based on the DFT analysis, the potential at which all oxygen intermediate reactions proceed spontaneously is the highest for (Ni,Co) 3 O 4 (U=0.66 eV) during ORR, whereas it is the lowest for Co 3 O 4 (U=2.09 eV) during OER. The high ORR activity of (Ni,Co) 3 O 4 is attributed to the enhanced electrical conductivity of the spinel lattice, and the high OER activity of Co 3 O 4 is attributed to relatively weak adsorption energy promoting rapid release of evolved oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Towards identifying the active sites on RuO2(110) in catalyzing oxygen evolution  

    DEFF Research Database (Denmark)

    Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen

    2017-01-01

    on the coordinatively unsaturated Ru sites (CUS) and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential...... to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H2O...

  17. Oxygen evolution on well-characterized mass-selected Ru and RuO2 nanoparticles

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares; Masini, Federico; Frydendal, Rasmus

    2015-01-01

    Oxygen evolution was investigated on model, mass-selected RuO2 nanoparticles in acid, prepared by magnetron sputtering. Our investigations include electrochemical measurements, electron microscopy, scanning tunneling microscopy and X-ray photoelectron spectroscopy. We show that the stability and ...... and activity of nanoparticulate RuO2 is highly sensitive to its surface pretreatment. At 0.25 V overpotential, the catalysts show a mass activity of up to 0.6 A mg(-1) and a turnover frequency of 0.65 s-1, one order of magnitude higher than the current state-of-the-art....

  18. Oxygen evolution from tomato (C3) plants with and without mycorrhiza: Open photoacoustic cell measurement and statistical analysis

    Science.gov (United States)

    Sanchez-Rocha, S.; Vargas-Luna, M.; Gutiérrez-Juárez, G.; Huerta Franco, R.; Madueño, L.; Olalde-Portugal, V.

    2005-06-01

    Mycorrhiza, a common association between root plants and mycorrhizic fungus provides some benefits to the plant, improving its nutrient uptake and increasing the drought resistance as well as the photosynthetic rate. Open photoacoustic (OPC) cell technique was used here to study oxygen evolution from C3 plants (tomato) with and with mycorrhizic fungus (Glomus Fasciculatum) under the lighting conditions similar to those characteristic for the mid-day sunlight. The OPC was found capable of discriminating between the two contributions to photoacoustic signal. The experimental evidence was collected for statistically significant differences between photobaric signals from plants with and without mycorrhiza.

  19. Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

    Science.gov (United States)

    Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

    2018-01-01

    Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Reduced and reversed temperature dependence of blood oxygenation in an ectothermic scombrid fish: implications for the evolution of regional heterothermy?

    Science.gov (United States)

    Clark, Timothy Darren; Rummer, J L; Sepulveda, C A; Farrell, A P; Brauner, C J

    2010-01-01

    Tunas (family Scombridae) are exceptional among most teleost fishes in that they possess vascular heat exchangers which allow heat retention in specific regions of the body (termed 'regional heterothermy'). Seemingly exclusive to heterothermic fishes is a markedly reduced temperature dependence of blood-oxygen (blood-O(2)) binding, or even a reversed temperature dependence where increasing temperature increases blood-O(2) affinity. These unusual binding properties have been documented in whole blood and in haemoglobin (Hb) solutions, and they are hypothesised to prevent oxygen loss from arteries to veins within the vascular heat exchangers and/or to prevent excessive oxygen unloading to the warm tissues and ensure an adequate supply of oxygen to tissues positioned efferent to the heat exchangers. The temperature sensitivity of blood-O(2) binding has not been characterised in an ectothermic scombrid (mackerels and bonitos), but the existence of the unusual binding properties in these fishes would have clear implications for their proposed association with regional heterothermy. Accordingly, the present study examined oxygenation of whole blood of the chub mackerel (Scomber japonicus) at 10, 20 and 30 degrees C and at 0.5, 1 and 2% CO(2). Oxygen affinity was generally highest at 20 degrees C for all levels of CO(2). Temperature-independent binding was observed at low (0.5%) CO(2), where the PO(2) at 50% blood-O(2) saturation (P (50)) was not statistically different at 10 and 30 degrees C (2.58 vs. 2.78 kPa, respectively) with an apparent heat of oxygenation (H degrees ) close to zero (-6 kJ mol(-1)). The most significant temperature-mediated difference occurred at high (2%) CO(2), where the P (50) at 10 degrees C was twofold higher than that at 20 degrees C with a corresponding H degrees of +43 kJ mol(-1). These results provide clear evidence of independent and reversed open-system temperature effects on blood oxygenation in S. japonicus, and it is therefore

  1. Evolution of structure and magnetic properties of stoichiometry and oxygen rich LaMnO3 nanoparticles

    Science.gov (United States)

    Tiwari, Priyanka; Rath, Chandana

    2017-11-01

    In this report, the evolution of structure and magnetic properties in stoichiometry and oxygen rich LaMnO3 samples synthesized by a simple, cost effective, conventional co-precipitation technique are systematically studied. While X-ray powder diffraction reveals a monoclinic, I2/a structure in both samples, Reitveld refinement demonstrates higher John-Teller (J-T) distortion in the former one. Higher J-T distortion is accompanied with a large deviation in Mnsbnd O bond length. FESEM (Field Emission Scanning Electron Microscopy) analysis combined with crystallite size calculated from XRD peak profile suggest that the particles are of 50-60 nm and are polycrystalline in nature. The antiferromagnetism observed in bulk LaMnO3 with TN = 140 K evolves towards a ferromagnetic order in both stoichiometry and oxygen rich samples. However, Curie temperature, TC, is found to be higher in oxygen rich sample due to higher Mnsbnd Osbnd Mn bond angle. The large effective magnetic moment calculated from Curie-Weiss plot is found to be higher in stoichiometry sample. Higher moment is ascribed to high oxygen vacancies evidenced from XPS analysis. Dispersion behavior observed in frequency dependent ac susceptibility (χ) indicates the spin-glass, cluster-glass and interacting superparamagnetic behavior. Fitting the susceptibility data with phenomenological models such as Neel-Arrhenius, Vogel-Fulcher and Power law, while canonical spin-glass, cluster-glass and interacting superparamagnetism is ruled out, the spin-glass behavior with a higher relaxation time in oxygen rich sample is confirmed.

  2. Alternating terminal electron-acceptors at the basis of symbiogenesis: How oxygen ignited eukaryotic evolution.

    Science.gov (United States)

    Speijer, Dave

    2017-02-01

    What kind of symbiosis between archaeon and bacterium gave rise to their eventual merger at the origin of the eukaryotes? I hypothesize that conditions favouring bacterial uptake were based on exchange of intermediate carbohydrate metabolites required by recurring changes in availability and use of the two different terminal electron chain acceptors, the bacterial one being oxygen. Oxygen won, and definitive loss of the archaeal membrane potential allowed permanent establishment of the bacterial partner as the proto-mitochondrion, further metabolic integration and highly efficient ATP production. This represents initial symbiogenesis, when crucial eukaryotic traits arose in response to the archaeon-bacterium merger. The attendant generation of internal reactive oxygen species (ROS) gave rise to a myriad of further eukaryotic adaptations, such as extreme mitochondrial genome reduction, nuclei, peroxisomes and meiotic sex. Eukaryotic origins could have started with shuffling intermediate metabolites as is still essential today. © 2017 The Authors. BioEssays Published by WILEY Periodicals, Inc.

  3. Evolution of air breathing: oxygen homeostasis and the transitions from water to land and sky.

    Science.gov (United States)

    Hsia, Connie C W; Schmitz, Anke; Lambertz, Markus; Perry, Steven F; Maina, John N

    2013-04-01

    Life originated in anoxia, but many organisms came to depend upon oxygen for survival, independently evolving diverse respiratory systems for acquiring oxygen from the environment. Ambient oxygen tension (PO2) fluctuated through the ages in correlation with biodiversity and body size, enabling organisms to migrate from water to land and air and sometimes in the opposite direction. Habitat expansion compels the use of different gas exchangers, for example, skin, gills, tracheae, lungs, and their intermediate stages, that may coexist within the same species; coexistence may be temporally disjunct (e.g., larval gills vs. adult lungs) or simultaneous (e.g., skin, gills, and lungs in some salamanders). Disparate systems exhibit similar directions of adaptation: toward larger diffusion interfaces, thinner barriers, finer dynamic regulation, and reduced cost of breathing. Efficient respiratory gas exchange, coupled to downstream convective and diffusive resistances, comprise the "oxygen cascade"-step-down of PO2 that balances supply against toxicity. Here, we review the origin of oxygen homeostasis, a primal selection factor for all respiratory systems, which in turn function as gatekeepers of the cascade. Within an organism's lifespan, the respiratory apparatus adapts in various ways to upregulate oxygen uptake in hypoxia and restrict uptake in hyperoxia. In an evolutionary context, certain species also become adapted to environmental conditions or habitual organismic demands. We, therefore, survey the comparative anatomy and physiology of respiratory systems from invertebrates to vertebrates, water to air breathers, and terrestrial to aerial inhabitants. Through the evolutionary directions and variety of gas exchangers, their shared features and individual compromises may be appreciated.

  4. Evolution of Air Breathing: Oxygen Homeostasis and the Transitions from Water to Land and Sky

    Science.gov (United States)

    Hsia, Connie C. W.; Schmitz, Anke; Lambertz, Markus; Perry, Steven F.; Maina, John N.

    2014-01-01

    Life originated in anoxia, but many organisms came to depend upon oxygen for survival, independently evolving diverse respiratory systems for acquiring oxygen from the environment. Ambient oxygen tension (PO2) fluctuated through the ages in correlation with biodiversity and body size, enabling organisms to migrate from water to land and air and sometimes in the opposite direction. Habitat expansion compels the use of different gas exchangers, for example, skin, gills, tracheae, lungs, and their intermediate stages, that may coexist within the same species; coexistence may be temporally disjunct (e.g., larval gills vs. adult lungs) or simultaneous (e.g., skin, gills, and lungs in some salamanders). Disparate systems exhibit similar directions of adaptation: toward larger diffusion interfaces, thinner barriers, finer dynamic regulation, and reduced cost of breathing. Efficient respiratory gas exchange, coupled to downstream convective and diffusive resistances, comprise the “oxygen cascade”—step-down of PO2 that balances supply against toxicity. Here, we review the origin of oxygen homeostasis, a primal selection factor for all respiratory systems, which in turn function as gatekeepers of the cascade. Within an organism's lifespan, the respiratory apparatus adapts in various ways to upregulate oxygen uptake in hypoxia and restrict uptake in hyperoxia. In an evolutionary context, certain species also become adapted to environmental conditions or habitual organismic demands. We, therefore, survey the comparative anatomy and physiology of respiratory systems from invertebrates to vertebrates, water to air breathers, and terrestrial to aerial inhabitants. Through the evolutionary directions and variety of gas exchangers, their shared features and individual compromises may be appreciated. PMID:23720333

  5. Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

    Science.gov (United States)

    Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

    2017-02-01

    The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

  6. Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae; Lee, A-Yeong; Lim, Jinkyu; Lee, Hyunjoo; Back, Seoin; Jung, Yousung; Danilovic, Nemanja; Stamenkovic, Vojislav; Erlebacher, Jonah; Snyder, Joshua; Markovic, Nenad M.

    2017-11-13

    The selection of oxide materials for catalyzing the Oxygen Evolution Reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity – a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir25Os75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the Activity-Stability FactorASF. Based on this metric, the nanoporous Ir/IrO2 morphology of dealloyed Ir25Os75 shows a factor of ~30 improvement ASFrelative to conventional Ir-based oxide materials and a ~8 times improvement over dealloyed Ir25Os75 nanoparticles due to optimized stability and conductivity, respectively. We propose that the Activity-Stability FactorASF is the key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

  7. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    Science.gov (United States)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

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

    Science.gov (United States)

    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.

  9. Effect of annealing ambience on the formation of surface/bulk oxygen vacancies in TiO2 for photocatalytic hydrogen evolution

    Science.gov (United States)

    Hou, Lili; Zhang, Min; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

    2018-01-01

    The surface and bulk oxygen vacancy have a prominent effect on the photocatalytic performance of TiO2. In this study, TiO2 possessing different types and concentration of oxygen vacancies were prepared by annealing nanotube titanic acid (NTA) at various temperatures in air or vacuum atmosphere. TiO2 with the unitary bulk single-electron-trapped oxygen vacancies (SETOVs) formed when NTA were calcined in air. Whereas, TiO2 with both bulk and surface oxygen vacancies were obtained when NTA were annealed in vacuum. The series of TiO2 with different oxygen vacancies were systematically characterized by TEM, XRD, PL, XPS, ESR, and TGA. The PL and ESR analysis verified that surface oxygen vacancies and more bulk oxygen vacancies could form in vacuum atmosphere. Surface oxygen vacancies can trap electron and hinder the recombination of photo-generated charges, while bulk SETOVs act as the recombination center. The surface or bulk oxygen vacancies attributed different roles on the photo-absorbance and activity, leading that the sample of NTA-A400 displayed higher hydrogen evolution rate under UV light, whereas NTA-V400 displayed higher hydrogen evolution rate under visible light because bulk SETOVs can improve visible light absorption because sub-band formed by bulk SETOVs prompted the secondary transition of electron excited.

  10. Photocatalytic oxygen evolution from low-bandgap conjugated microporous polymer nanosheets: a combined first-principles calculation and experimental study.

    Science.gov (United States)

    Wang, Lei; Wan, Yangyang; Ding, Yanjun; Niu, Yuchen; Xiong, Yujie; Wu, Xiaojun; Xu, Hangxun

    2017-03-23

    Nanostructured semiconducting polymers have emerged as a very promising class of metal-free photocatalytic materials for solar water splitting. However, they generally exhibit low efficiency and lack the ability to utilize long-wavelength photons in a photocatalytic oxygen evolution reaction (OER). Here, based on first-principles calculations, we reveal that the two-dimensional (2D) aza-fused conjugated microporous polymer (aza-CMP) with a honeycomb network is a semiconductor with novel layer-dependent electronic properties. The bandgap of the as-synthesized aza-CMP nanosheets is measured to be 1.22 eV, suggesting that they can effectively boost light absorption in the visible and near infrared (NIR) region. More importantly, aza-CMP also possesses a valence band margin suitable for a photocatalytic OER. Taking advantage of the 2D layered nanostructure, we further show that the exfoliated ultrathin aza-CMP nanosheets can exhibit a three-fold enhancement in the photocatalytic OER. After deposition of a Co(OH) 2 cocatalyst, the hybrid Co(OH) 2 /aza-CMP photocatalyst exhibits a markedly improved performance for photocatalytic O 2 evolution. Furthermore, first-principles calculations reveal that the photocatalytic O 2 evolution reaction is energetically feasible for aza-CMP nanosheets under visible light irradiation. Our findings reveal that nanostructured polymers hold great potential for photocatalytic applications with efficient solar energy utilization.

  11. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    KAUST Repository

    Joya, Khurram

    2015-07-15

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  12. Directed evolution to produce sludge communities with improved oxygen uptake abilities.

    Science.gov (United States)

    Kunkel, Stephanie A; Pagilla, Krishna R; Stark, Benjamin C

    2015-12-01

    Two activated sludge cultures, seeded with activated sludge from the same source, were cultivated for 370 days in synthetic wastewater. Both cultures were transferred weekly to fresh medium; one culture was operated at high dissolved oxygen (DO) (near saturation) and the other at low DO (0.25 mg O2/L). There were significant changes in the abundances of bacterial species and phyla present in each culture throughout the 370-day operational period. In the low DO culture, over time, there was a continuously increasing proportion of cells of species known to encode truncated hemoglobins (Hbs). These are the types of Hbs which may enhance delivery of oxygen to the respiratory chain, to enhance ATP production, especially under low aeration conditions. The levels of heme b, the heme found in Vitreoscilla hemoglobin, increased in parallel to the increase in Hb-encoding species, to much higher levels in the low DO culture than in the high DO culture. Specific oxygen uptake rates increased by 3 % for the high DO culture near the end of the 370-day period, while those for the low DO culture increased steadily to a level 28 % higher than that of the starting culture. Thus, imposition of low DO conditions may, due to selection for Hb-expressing species, be useful in developing bacterial communities with enhanced ability to function efficiently in aerobic wastewater treatment, especially under low aeration conditions.

  13. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

    Science.gov (United States)

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-01-01

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH− oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion. PMID:27199009

  14. Evolutions of Molecular Oxygen Formation and Sodium Migration in Xe Ion Irradiated Borosilicate Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liang; Zhang, Duofei F.; Lv, Peng; Zhang, Jiandong; Du, Xing; Yuan, Wei; Nan, Shuai; Zhu, Zihua; Wang, Tieshan

    2016-07-23

    The modifications of a commercial borosilicate glass induced by Xe ion irradiation have been studied by Raman spectroscopy and ToF-SIMS depth profiling. A decrease in the average Si–O–Si angle, an increase in the population of three-membered rings and an increase of the glass polymerization are evidenced. The molecular oxygen appears in the irradiated glasses after the irradiation fluence reaches approximately 1015 ions/cm2. The O2 concentration decreaseswith the depth of irradiated glass at the ion fluence of 2 × 1016 ions/cm2. A sodiumdepleted layer at the surface and a depleted zone at around the penetration depth of 5 MeV Xe ions are observed. The thickness of the sodium depleted layer increases with the irradiation fluence. Moreover, comparing with previous results after electron and Ar ion irradiation, it can be concluded that the nuclear energy deposition can partially inhibit the formation of molecular oxygen and increase the threshold value of electron energy deposition for the molecular oxygen formation.

  15. The urchin-like sphere arrays Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction

    Science.gov (United States)

    Li, Ruchun; Zhou, Dan; Luo, Jiaxian; Xu, Weiming; Li, Jingwei; Li, Shuoshuo; Cheng, Pengpeng; Yuan, Dingsheng

    2017-02-01

    Electrochemical water splitting has attracted great interest because of the growing demand for sustainable energy and increasing concerns for the environment. We present a facile strategy to design the three-dimensional (3D) urchin-like sphere arrays Co3O4 as an effective bifunctional catalyst for electrochemical water splitting. The 3D urchin-like Co3O4 was directly grown on Ni foam by a hydrothermal reaction and annealing treatment at a low temperature. This process offers several advantages including facile synthesis, binder-free, and low cost. The 3D urchin-like Co3O4 as a catalyst for hydrogen evolution reaction exhibits a low onset potential (-130 mV vs. RHE) and good cycling stability in an alkaline electrolyte. When urchin-like Co3O4 is used as a catalyst for oxygen evolution reaction, the onset potential is at 1.46 V (vs. RHE) with a low overpotential of only 230 mV. The good catalytic activity can be attributed to the unique urchin-like nanostructure, abundant mesopores, and low charge-transfer resistance (compared with Co3O4 NPs). In addition, H2 and O2 generation was performed using Co3O4 as both cathode and anode catalysts with a potential of 1.64 V to reach a current density of 10 mA cm-2.

  16. Carbon combustion supernovae - Numerical studies of the final evolution of degenerate carbon-oxygen cores

    Science.gov (United States)

    Mueller, E.; Arnett, W. D.

    1986-01-01

    The evolution of polytropic 1.46-solar-mass 3-Gg/cu cm (4 x 10 to the 8th)-K pure C cores is investigated theoretically by means of model computations starting from the runaway stage. The temperature in central zones is raised to the runaway temperature, and the evolution is followed in a spherical coordinate system. In models of burning without detonation, it is found that the initially spherical burning front is Rayleigh-Taylor unstable, without bipolar jets or equatorial rings; that some C is not burned to Ni; and that the Ni in the 0.8-1.0 solar mass of burned fuel produced can account for observed properties of type I supernovae.

  17. In Operando Self-Healing of Perovskite Electrocatalysts: A Case Study of SrCoO3 for the Oxygen Evolution Reaction

    KAUST Repository

    Tahini, Hassan A.

    2017-01-24

    Perovskites are promising catalysts for oxygen evolution reactions (OER); among them, SrCoO3 is one of the best for these reactions. We study the O* intermediates and the role of surface oxygen vacancies of SrCoO3 during OER. A self-healing mechanism is proposed in which O* are incorporated into the surface to recover the redox capabilities of the material.

  18. Oxygen isotopes in the Martian atmosphere - Implications for the evolution of volatiles

    Science.gov (United States)

    Mcelroy, M. B.; Yung, Y. L.

    1976-01-01

    Nonthermal escape of oxygen by recombination of exospheric O2(+) combined with diffusive separation of gases at lower altitude provides a mechanism through which the Martian atmosphere may be enriched in O-18 relative to O-16. Measurement of the abundance of O-18 relative to O-16 together with a determination of the turbopause may be used to develop important constraints on the history of Martian volatiles. Models for the interpretation of these data are developed and discussed in light of present information.

  19. Evolution of membrane oxygenator technology for utilization during pediatric cardiopulmonary bypass

    Directory of Open Access Journals (Sweden)

    Melchior RW

    2016-06-01

    Full Text Available Richard W Melchior,1 Steven W Sutton,2 William Harris,3 Heidi J Dalton4,5 1Department of Perfusion Services, The Children's Hospital of Philadelphia, Philadelphia, PA, 2Cardiovascular Support Services, Inc., Dallas, TX, 3Department of Perfusion Services, Ochsner Clinic Foundation, New Orleans, LA, 4Alaskan Native Tribal Health Consortium, Anchorage, AK, 5Department of Child Health, University of Arizona-College of Medicine, Phoenix, AZ, USAAbstract: The development of the membrane oxygenator for pediatric cardiopulmonary bypass has been an incorporation of ideology and technological advancements with contributions by many investigators throughout the past two centuries. With the pursuit of this technological achievement, the ability to care for mankind in the areas of cardiac surgery has been made possible. Heart disease can affect anyone within the general population, but one such segment that it can affect from inception includes children. Currently, congenital heart defects are the most common birth defects nationally and worldwide. A large meta-analysis study from 1930 to 2010 was conducted in review of published medical literature totaling 114 papers with a study population of 24,091,867 live births, and divulged a staggering incidence of congenital heart disease involving 164,396 subjects with diverse cardiac illnesses. The prevalence of these diseases increased from 0.6 per 1,000 live births from 1930–1934 to 9.1 per 1,000 live births after 1995. These data reveal an emphasis on a growing public health issue regarding congenital heart disease. This discovery displays a need for heightened awareness in the scientific and medical industrial community to accelerate investigative research on emerging cardiovascular devices in an effort to confront congenital anomalies. One such device that has evolved over the past several decades is the pediatric membrane oxygenator. The pediatric membrane oxygenator, in conjunction with the heart lung

  20. Net Locality

    DEFF Research Database (Denmark)

    de Souza e Silva, Adriana Araujo; Gordon, Eric

    Provides an introduction to the new theory of Net Locality and the profound effect on individuals and societies when everything is located or locatable. Describes net locality as an emerging form of location awareness central to all aspects of digital media, from mobile phones, to Google Maps...... of emerging technologies, from GeoCities to GPS, Wi-Fi, Wiki Me, and Google Android....

  1. Net Neutrality

    DEFF Research Database (Denmark)

    Savin, Andrej

    2017-01-01

    Repealing “net neutrality” in the US will have no bearing on Internet freedom or security there or anywhere else.......Repealing “net neutrality” in the US will have no bearing on Internet freedom or security there or anywhere else....

  2. Manufacturing of a LaNiO3 composite electrode for oxygen evolution in commercial alkaline water electrolysis

    DEFF Research Database (Denmark)

    Egelund, Sune; Caspersen, Michael; Nikiforov, Aleksey Valerievich

    2016-01-01

    The LaNiO3 perovskite was chosen for incorporation into a nickel matrix in order to obtain a metallic composite electrode suitable for improving the oxygen evolution reaction (OER) in commercial water electrolysis at elevated temperature. The manufactured LaNiO3 + Ni composite coatings were...... deposited in a Watts type nickel electrolyte in a specially designed beaker with continuous particle circulation. Activity of the composite coatings was evaluated using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and anodic potentiodynamic polarization measurements. The obtained...... results were compared to a non-catalysed Watts nickel reference sample and the electrochemical measurements confirmed that the coating decreased the OER overpotential by 70 mV. XRD furthermore revealed that a LaNiO3 + Ni composite structure was obtained. Conventional alkaline water electrolysis...

  3. A Porous Cobalt (II Metal–Organic Framework with Highly Efficient Electrocatalytic Activity for the Oxygen Evolution Reaction

    Directory of Open Access Journals (Sweden)

    Qingguo Meng

    2017-12-01

    Full Text Available A 3D porous framework ([Co1.5(tib(dcpna]·6H2O (1 with a Wei topology has been synthesized by solvothermal reaction of 1,3,5-tris(1-imidazolyl-benzene (tib, 5-(3′,5′-dicarboxylphenylnicotinic acid (H3dcpna and cobalt nitrate. The electrocatalytic activity for water oxidation of 1 has been investigated in alkaline solution. Compound 1 exhibits good oxygen evolution reaction (OER activities in alkaline solution, exhibiting 10 mA·cm−2 at η = 360 mV with a Tafel slope of 89 mV·dec−1. The high OER activity can be ascribe to 1D open channels along b axis of 1, which expose more activity sites and facilitate the electrolyte penetration.

  4. Architecting a Mesoporous N-Doped Graphitic Carbon Framework Encapsulating CoTe2 as an Efficient Oxygen Evolution Electrocatalyst.

    Science.gov (United States)

    Liu, Ming; Lu, Xiaoqing; Guo, Chen; Wang, Zhaojie; Li, Yanpeng; Lin, Yan; Zhou, Yan; Wang, Shutao; Zhang, Jun

    2017-10-18

    To improve the efficiency of cobalt-based catalysts for water electrolysis, tremendous efforts have been dedicated to tuning the composition, morphology, size, and structure of the materials. We report here a facile preparation of orthorhombic CoTe2 nanocrystals embedded in an N-doped graphitic carbon matrix to form a 3D architecture with a size of ∼500 nm and abundant mesopores of ∼4 nm for the oxygen evolution reaction (OER). The hybrid electrocatalyst delivers a small overpotential of 300 mV at 10 mA cm-2, which is much lower than that for pristine CoTe2 powder. After cycling for 2000 cycles or driving continual OER for 20 h, only a slight loss is observed. The mesoporous 3D architecture and the strong interaction between N-doped graphitic carbon and CoTe2 are responsible for the enhancement of the electrocatalytic performance.

  5. Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Yi Cheng

    2015-12-01

    Full Text Available The water electrolysis for hydrogen production is constrained by the thermodynamically unfavorable oxygen evolution reaction (OER, which requires input of a large amount of energy to drive the reaction. One of the key challenges to increase the efficiency of the water electrolysis system is to develop highly effective and robust electrocatalysts for the OER. In the past 20–30 years, significant progresses have been made in the development of efficient electrocatalysts, including metal oxides, metal oxide-carbon nanotubes (CNTs hybrid and metal-free CNTs based materials for the OER. In this critical review, the overall progress of metal oxides catalysts and the role of CNTs in the development of OER catalyst are summarized, and the latest development of new metal free CNTs-based OER catalyst is discussed.

  6. Influence of the oxygen partial pressure on the phase evolution during Bi-2212 wire melt processing

    CERN Document Server

    Scheuerlein, C.; Rikel, M.O.; Kadar, J.; Doerrer, C.; Di Michiel, M.; Ballarino, A.; Bottura, L.; Jiang, J.; Kametani, F.; Hellstrom, E.E.; Larbalestier, D.C.

    2016-01-01

    We have studied the influence of the oxygen partial pressure pO2 up to 5.5 bar on the phase changes that occur during melt processing of a state-of-the-art Bi-2212 multifilamentary wire. Phase changes have been monitored in situ by high energy synchrotron X-ray diffraction (XRD). We found that the stability of Bi-2212 phase is reduced with increasing pO2. For pO2>1 bar a significant amount of Bi-2212 phase decomposes upon heating in the range 400 to 650 °C. The extent of decomposition strongly increases with increasing pO2, and at pO2=5.5 bar Bi-2212 decomposes completely in the solid state. Textured Bi-2212 can be formed during solidification when pO2 is reduced to 0.45 bar when the precursor is molten. Since the formation of current limiting second phases is very sensitive to pO2 when it exceeds 1 bar, we recommend to reduce the oxygen partial pressure below the commonly used pO2=1 bar, in order to increase the pO2 margins and to make the overpressure process more robust.

  7. Long-term evolution of an activated sludge system under low dissolved oxygen conditions.

    Science.gov (United States)

    Guo, Jinsong; Xu, Yufeng; Chen, Youpeng; Fan, Leilei; Fang, Fang

    2013-04-01

    This study aims to evaluate the impacts of low dissolved oxygen (DO) levels on activated sludge performance. Two sequencing batch reactors (SBR), each with a working volume of 10 l, were investigated with different DO levels. Compared with high DO conditions (above 2 mg l(-1) on average), low DO conditions in the SBR did not result in poor sludge bulking, lower chemical oxygen demand, and ammonium removal efficiency. Moreover, simultaneous nitrification and denitrification (SND) via nitrite and shortcut nitrification-denitrification were carried out under low DO levels. The average efficiencies of SND and nitrite accumulation ratios (NAR) in reactors A and B were 10.6 and 60.4%, respectively, under high DO levels and 4.1 and 76%, respectively, under low DO levels. Scanning electron microscopy revealed that the main types of bacteria in reactor A were spherical and short rod-shaped bacteria, whereas those in reactor B were long rod-shaped bacteria and filamentous bacteria. Thus, the appropriate DO concentration created excellent microbial community structures, which helped the biological systems to perform well under low DO level operating conditions.

  8. Calibration of simultaneous measurements of photosynthetic carbon dioxide uptake and oxygen evolution in leaves.

    Science.gov (United States)

    Oja, Vello; Eichelmann, Hillar; Laisk, Agu

    2007-01-01

    The stoichiometric ratio of O2 evolution to CO2 uptake during photosynthesis reveals information about reductive metabolism, including the reduction of alternative electron acceptors, such as nitrite and oxaloacetate. Recently we reported that in simultaneous measurements of CO2 uptake and O2 evolution in a sunflower leaf, O2 evolution changed by 7% more than CO2 uptake when light intensity was varied. Since the O2/CO2 exchange ratio is approximately 1, small differences are important. Thus, these gas exchange measurements need precise calibration. In this work, we describe a new calibration procedure for such simultaneous measurements, based on the changes of O2 concentration caused by the addition of pure CO2 or O2 into a flow of dry air (20.95% O2) through one and the same capillary. The relative decrease in O2 concentration during the addition of CO2 and the relative increase in O2 concentration during the addition of O2 allowed us to calibrate the CO2 and O2 scales of the measurement system with an error (relative standard deviation, RSD) of O2/CO2 ratio between 1.0 and 1.03 under different CO2 concentrations and light intensities, in the presence of an ambient O2 concentration of 20-50 micromol mol(-1). This shows that the percentage use of reductive power from photochemistry in synthesis of inorganic or organic matter other than CO2 assimilation in the C3 cycle is very low in mature leaves and, correspondingly, the reduction of alternative acceptors is a weak source of coupled ATP synthesis.

  9. Tailored Combination of Low Dimensional Catalysts for Efficient Oxygen Reduction and Evolution in Li-O2 Batteries.

    Science.gov (United States)

    Yoon, Ki Ro; Kim, Dae Sik; Ryu, Won-Hee; Song, Sung Ho; Youn, Doo-Young; Jung, Ji-Won; Jeon, Seokwoo; Park, Yong Joon; Kim, Il-Doo

    2016-08-23

    The development of efficient bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key issue pertaining high performance Li-O2 batteries. Here, we propose a heterogeneous electrocatalyst consisting of LaMnO3 nanofibers (NFs) functionalized with RuO2 nanoparticles (NPs) and non-oxidized graphene nanoflakes (GNFs). The Li-O2 cell employing the tailored catalysts delivers an excellent electrochemical performance, affording significantly reduced discharge/charge voltage gaps (1.0 V at 400 mA g(-1) ), and superior cyclability for over 320 cycles. The outstanding performance arises from (1) the networked LaMnO3 NFs providing ORR/OER sites without severe aggregation, (2) the synergistic coupling of RuO2 NPs for further improving the OER activity and the electrical conductivity on the surface of the LaMnO3 NFs, and (3) the use of GNFs providing a fast electronic pathway as well as improved ORR kinetics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Evolution of the concept of oxygen transport in the critically ill, with a focus on children after cardiopulmonary bypass.

    Science.gov (United States)

    Li, Jia

    2017-10-11

    The concept of oxygen transport, defined as the relation between oxygen consumption (VO2) and delivery (DO2), is of fundamental importance in critically ill patients. The past 200 years have witnessed a stepwise progressive improvement in the understanding of pathophysiological disturbances in the balance of DO2 and VO2 in critically ill patients including those after cardiopulmonary bypass surgery. Intermittent spectacular technological achievements have accelerated the rate of progress. Therapeutic advances have been particularly impressive during the recent decades. Examination of the relation between DO2 and VO2 provides a useful framework around which the care of the critically ill may be developed. Until now, only a few groups have used this framework to examine children after cardiopulmonary bypass. The key topics that will be covered in this review article are the evolution of the concept from its early development to its present, increasingly sophisticated, role in the management of critically ill patients, with a focus on children after cardiopulmonary bypass surgery.

  11. Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

    Science.gov (United States)

    Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

    2018-01-01

    A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

  12. Evolution of oxygenated cadmium sulfide (CdS:O) during high-temperature CdTe solar cell fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Meysing, Daniel M.; Reese, Matthew O.; Warren, Charles W.; Abbas, Ali; Burst, James M.; Mahabaduge, Hasitha P.; Metzger, Wyatt K.; Walls, John M.; Lonergan, Mark C.; Barnes, Teresa M.; Wolden, Colin A.

    2016-12-01

    Oxygenated cadmium sulfide (CdS:O) produced by reactive sputtering has emerged as a promising alternative to conventional CdS for use as the n-type window layer in CdTe solar cells. Here, complementary techniques are used to expose the window layer (CdS or CdS:O) in completed superstrate devices and combined with a suite of materials characterization to elucidate its evolution during high temperature device processing. During device fabrication amorphous CdS:O undergoes significant interdiffusion with CdTe and recrystallization, forming CdS1-yTey nanocrystals whose Te fraction approaches solubility limits. Significant oxygen remains after processing, concentrated in sulfate clusters dispersed among the CdS1-yTey alloy phase, accounting for ~30% of the post-processed window layer based on cross-sectional microscopy. Interdiffusion and recrystallization are observed in devices with un-oxygenated CdS, but to a much lesser extent. Etching experiments suggest that the CdS thickness is minimally changed during processing, but the CdS:O window layer is reduced from 100 nm to 60-80 nm, which is confirmed by microscopy. Alloying reduces the band gap of the CdS:O window layer to 2.15 eV, but reductions in thickness and areal density improve its transmission spectrum, which is well matched to device quantum efficiency. The changes to the window layer in the reactive environments of device fabrication are profoundly different than what occurs by thermal annealing in an inert environment, which produced films with a band gap of 2.4 eV for both CdS and CdS:O. These results illustrate for the first time the significant changes that occur to the window layer during processing that are critical to the performance of CdTe solar cells.

  13. On the origin and evolution of isotopes of carbon, nitrogen, and oxygen

    Science.gov (United States)

    Dearborn, D.; Schramm, D. N.; Tinsley, B. M.

    1978-01-01

    Calculations of CNO processing in stellar envelopes, based on theoretical nucleosynthesis rather than empirical abundances in evolving stars, are presented and used in two models for the chemical evolution of the solar neighborhood. Seven stable isotopes are considered: C-12, C-13, N-14, N-15, O-16, O-17, and O-18. The two models ('infall' and 'initial-burst') represent extremes of types consistent with general constraints and include theoretical estimates of other nucleosynthesis sites and yields for CNO isotopes. The results obtained are found to predict that all CNO isotopes are produced mainly by stars with lifetimes much less than the age of the Galaxy (even at the present time when low-mass stars have the greatest death rate), so that isotopic ratios evolve very slowly after the first few billion years. Consequences of these slow changes are that the isotopic ratios cannot be employed to test between alternative hypotheses and that galactic evolution does not seem to be able to account for the apparent difference between the C-13/C-12 ratio in the solar system and in molecular clouds. The predicted envelope processing is shown to lead to approximately the solar-system values for the C-13/C-12 and O-17/O-16 abundance ratios but to a N-14/C-12 ratio that is too small by at least a factor of 2.

  14. Leptin integrates vertebrate evolution: from oxygen to the blood-gas barrier.

    Science.gov (United States)

    Torday, J S; Powell, F L; Farmer, C G; Orgeig, S; Nielsen, H C; Hall, A J

    2010-08-31

    The following are the proceedings of a symposium held at the Second International Congress for Respiratory Science in Bad Honnef, Germany. The goals of the symposium were to delineate the blood-gas barrier phenotype across vertebrate species; to delineate the interrelationship between the evolution of the blood-gas barrier, locomotion and metabolism; to introduce the selection pressures for the evolution of the surfactant system as a key to understanding the physiology of the blood-gas barrier; to introduce the lung lipofibroblast and its product, leptin, which coordinately regulates pulmonary surfactant, type IV collagen in the basement membrane and host defense, as the cell-molecular site of selection pressure for the blood-gas barrier; to drill down to the gene regulatory network(s) involved in leptin signaling and the blood-gas barrier phenotype; to extend the relationship between leptin and the blood-gas barrier to diving mammals. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  15. Reactive oxygen species drive evolution of pro-biofilm variants in pathogens by modulating cyclic-di-GMP levels.

    Science.gov (United States)

    Chua, Song Lin; Ding, Yichen; Liu, Yang; Cai, Zhao; Zhou, Jianuan; Swarup, Sanjay; Drautz-Moses, Daniela I; Schuster, Stephan Christoph; Kjelleberg, Staffan; Givskov, Michael; Yang, Liang

    2016-11-01

    The host immune system offers a hostile environment with antimicrobials and reactive oxygen species (ROS) that are detrimental to bacterial pathogens, forcing them to adapt and evolve for survival. However, the contribution of oxidative stress to pathogen evolution remains elusive. Using an experimental evolution strategy, we show that exposure of the opportunistic pathogen Pseudomonas aeruginosa to sub-lethal hydrogen peroxide (H2O2) levels over 120 generations led to the emergence of pro-biofilm rough small colony variants (RSCVs), which could be abrogated by l-glutathione antioxidants. Comparative genomic analysis of the RSCVs revealed that mutations in the wspF gene, which encodes for a repressor of WspR diguanylate cyclase (DGC), were responsible for increased intracellular cyclic-di-GMP content and production of Psl exopolysaccharide. Psl provides the first line of defence against ROS and macrophages, ensuring the survival fitness of RSCVs over wild-type P. aeruginosa Our study demonstrated that ROS is an essential driving force for the selection of pro-biofilm forming pathogenic variants. Understanding the fundamental mechanism of these genotypic and phenotypic adaptations will improve treatment strategies for combating chronic infections. © 2016 The Authors.

  16. Evolution of magnetic oxygen states in Sr-doped LaCoO3.

    Science.gov (United States)

    Medling, S; Lee, Y; Zheng, H; Mitchell, J F; Freeland, J W; Harmon, B N; Bridges, F

    2012-10-12

    Magnetism in La(1-x)Sr(x)CoO(3) as a function of doping is investigated with x-ray absorption spectroscopy and x-ray magnetic circular dicrhoism at the O K edge, and corresponding first principles electronic structure calculations. For small x, the spectra are consistent with the formation of ferromagnetic clusters occurring within a nonmagnetic insulating matrix. Sr-induced, magnetic O-hole states form just above E(F) and grow with increasing Sr doping. Density functional calculations for x=0 yield a nonmagnetic ground state with the observed rhombohedral distortion and indicates that doping introduces holes at the Fermi level in magnetic states with significant O 2p and Co t(2g) character for the undistorted pseudocubic structure. Supercell calculations show stronger magnetism on oxygen atoms having more Sr neighbors.

  17. Evolution of Magnetic Oxygen States in Sr-Doped LaCoO3

    Energy Technology Data Exchange (ETDEWEB)

    Medling, S.; Lee, Yuen; Zheng, H.; Mitchell, J.F.; Freeland, J.W.; Harmon, Bruce N.; Bridges, F.

    2012-10-12

    Magnetism in La1-xSrxCoO3 as a function of doping is investigated with x-ray absorption spectroscopy and x-ray magnetic circular dicrhoism at the O K edge, and corresponding first principles electronic structure calculations. For small x, the spectra are consistent with the formation of ferromagnetic clusters occurring within a nonmagnetic insulating matrix. Sr-induced, magnetic O-hole states form just above EF and grow with increasing Sr doping. Density functional calculations for x=0 yield a nonmagnetic ground state with the observed rhombohedral distortion and indicates that doping introduces holes at the Fermi level in magnetic states with significant O 2p and Co t2g character for the undistorted pseudocubic structure. Supercell calculations show stronger magnetism on oxygen atoms having more Sr neighbors.

  18. Chironomid oxygen isotope record of mid- to late Holocene climate evolution from southern Spitsbergen

    Science.gov (United States)

    Arppe, Laura; Kurki, Eija; Wooller, Matthew; Luoto, Tomi; Zajączkowski, Marek; Ojala, Antti

    2017-04-01

    The oxygen isotope composition of head capsule chitin of chironomid larvae picked from a sediment core covering the past 5500 years from lake Svartvatnet in southern Spitsbergen was used to reconstruct the isotopic composition of oxygen in lake water (δ18Olw) and local precipitation. Consistent with the gradual cooling of climate over the Neoglacial period, the δ18Olw record displays a gentle decreasing trend over the study period. The Svartvatnet δ18Olwrecord shows a maximum at ca. 1900-1800 cal BP, consistent with the timing of the Roman Warm Period, and three negative excursions increasing in intensity towards the present-day at 3400-3200, 1250-1100 and 350-50 cal BP, which are tentatively linked to multidecadal periods of low solar activity amplified by oceanic and atmospheric feedbacks. The time period of the Little Ice Age shows a two-step decrease in δ18Olwvalues, with a remarkable, 8-9‰ drop at 350-50 cal BP construed to predominantly represent significantly decreased winter temperatures during a period of increased seasonal differences and extended sea ice cover inducing changes in moisture source regions. Similarity of the trends between the δ18Olwrecord and a July-T reconstruction based on chironomid assemblages (Luoto et al., in review) from the same core suggests that air temperature exerts a significant control over the δ18Olwvalues, but the record is most likely influenced by changes in sea ice extent and possibly the seasonal distribution of precipitation. Reference: Luoto TP, Ojala A, Brooks S et al. Synchronized proxy-based temperature reconstructions reveal mid-to late Holocene climate oscillations in High Arctic Svalbard. Journal of Quaternary Science, submitted.

  19. Behaviors of trace elements in Neoarchean and Paleoproterozoic paleosols: Implications for atmospheric oxygen evolution and continental oxidative weathering

    Science.gov (United States)

    Murakami, Takashi; Matsuura, Kei; Kanzaki, Yoshiki

    2016-11-01

    The behaviors of redox-sensitive and/or bio-essential trace elements in Neoarchean and Paleoproterozoic paleosols (ancient weathering profiles) were investigated to better understand atmospheric oxygen evolution. The loss or retention of individual trace elements in the paleosols can show how continental oxidative weathering, and thus atmospheric oxygen evolution, took place against age mainly due to their various redox potentials. The V, Cr, Ni, Cu, Zn and Mo concentrations of two Paleoproterozoic paleosols were measured by inductively coupled plasma optical emission spectrometry and mass spectrometry, and those, as well as Co, W and U concentrations, of nine Neoarchean and Paleoproterozoic paleosols were obtained from the literature. The trace element behaviors were constrained by their degrees of loss or retention in the paleosols. We applied two methods to the estimation: (i) retention fraction of element M (a mass ratio of element M of paleosol to parent rock using immobile elements such as Ti) and (ii) element-element (in particular, Si-element) correlations at different profile depths of a paleosol. There are two distinct groups in trace element behavior in the Neoarchean and Paleoproterozoic paleosols: Co, Ni, Zn and W were lost from weathering profiles until the early Paleoproterozoic but retained in the middle and late Paleoproterozoic, while V, Cr, Cu, Mo and U were retained in the profiles until the early Paleoproterozoic or slightly later but lost from the profiles in the middle and late Paleoproterozoic. More precisely, the timings of such loss and retention were different between trace elements during the Paleoproterozoic. The characteristics of these changes from retention to loss or from loss to retention indicate that the changes occurred and lasted throughout the Paleoproterozoic. The trace element behaviors, accordingly, suggest that continental weathering became oxidative progressively with age during almost the whole Paleoproterozoic, and thus

  20. Reassessment of roles of oxygen and ultraviolet light in Precambrian evolution

    Science.gov (United States)

    Margulis, L.; Rambler, M.; Walker, J. C. G.

    1976-01-01

    It is argued that the transition to an oxidizing atmosphere preceded the origin of eukaryotic cells, which in turn must have preceded the origin of metazoa. Moreover, the number of methods by which organisms can protect themselves from harmful UV radiation is sufficiently large to suggest that solar UV, even when the atmosphere was anaerobic, was not such as to control the distribution and diversification of life. An alternative explanation for the late and sudden appearance of metazoa in lower Cambrian sediments is proposed, which is related to the mechanisms by which fully mature eukaryotic cells probably originated. There was probably a protracted evolution of modern genetic systems based on mitosis in cells which acquired organelles (e.g., plastids and mitochondria) by hereditary endosymbiosis. The origin of hard parts underlies the Cambrian explosion of metazoans.

  1. Carbon and oxygen in H II regions of the Magellanic Clouds: abundance discrepancy and chemical evolution

    Science.gov (United States)

    Toribio San Cipriano, L.; Domínguez-Guzmán, G.; Esteban, C.; García-Rojas, J.; Mesa-Delgado, A.; Bresolin, F.; Rodríguez, M.; Simón-Díaz, S.

    2017-05-01

    We present C and O abundances in the Magellanic Clouds derived from deep spectra of H II regions. The data have been taken with the Ultraviolet-Visual Echelle Spectrograph at the 8.2-m Very Large Telescope. The sample comprises five H II regions in the Large Magellanic Cloud (LMC) and four in the Small Magellanic Cloud (SMC). We measure pure recombination lines (RLs) of C ii and O ii in all the objects, permitting to derive the abundance discrepancy factors (ADFs) for O2+, as well as their O/H, C/H and C/O ratios. We compare the ADFs with those of other H II regions in different galaxies. The results suggest a possible metallicity dependence of the ADF for the low-metallicity objects; but more uncertain for high-metallicity objects. We compare nebular and B-type stellar abundances and we find that the stellar abundances agree better with the nebular ones derived from collisionally excited lines (CELs). Comparing these results with other galaxies we observe that stellar abundances seem to agree better with the nebular ones derived from CELs in low-metallicity environments and from RLs in high-metallicity environments. The C/H, O/H and C/O ratios show almost flat radial gradients, in contrast with the spiral galaxies where such gradients are negative. We explore the chemical evolution analysing C/O versus O/H and comparing with the results of H II regions in other galaxies. The LMC seems to show a similar chemical evolution to the external zones of small spiral galaxies and the SMC behaves as a typical star-forming dwarf galaxy.

  2. Changes in photosynthetic properties measured by oxygen evolution and variable chlorophyll fluorescence in a simulated entrainment experiment with the cyanobacterium Planktothrix rubescens

    NARCIS (Netherlands)

    Kromkamp, J.C.; Domin, A.; Dubinsky, Z.; Lehmann, C.; Schanz, F.

    2001-01-01

    The metalimnion of lake Zurich is dominated by the red coloured cyanobacterium Planktotrix rubescens, where it lives in an extremely low light environment. Photosynthesis of the organism was studied using oxygen evolution and variable fluorescence. After transfer to 2 in depth in the epilimnion.

  3. Metal-organic framework derived carbon-confined Ni2P nanocrystals supported on graphene for an efficient oxygen evolution reaction.

    Science.gov (United States)

    Wang, Manman; Lin, Mengting; Li, Jiantao; Huang, Lei; Zhuang, Zechao; Lin, Chao; Zhou, Liang; Mai, Liqiang

    2017-07-20

    Metal-organic framework derived carbon-confined Ni2P nanocrystals supported on graphene with high effective surface area, more exposed active sites, and enhanced charge transport were successfully designed. The resulting material shows excellent oxygen evolution reaction performance with a remarkably low overpotential of 285 mV at 10 mA cm-2 and outstanding durability.

  4. Single and multigenerational responses of body mass to atmospheric oxygen concentrations in Drosophila melanogaster : evidence for roles of plasticity and evolution.

    Science.gov (United States)

    Klok, C J; Hubb, A J; Harrison, J F

    2009-12-01

    Greater oxygen availability has been hypothesized to be important in allowing the evolution of larger invertebrates during the Earth's history, and across aquatic environments. We tested for evolutionary and developmental responses of adult body size of Drosophila melanogaster to hypoxia and hyperoxia. Individually reared flies were smaller in hypoxia, but hyperoxia had no effect. In each of three oxygen treatments (hypoxia, normoxia or hyperoxia) we reared three replicate lines of flies for seven generations, followed by four generations in normoxia. In hypoxia, responses were due primarily to developmental plasticity, as average body size fell in one generation and returned to control values after one to two generations of normoxia. In hyperoxia, flies evolved larger body sizes. Maximal fly mass was reached during the first generation of return from hyperoxia to normoxia. Our results suggest that higher oxygen levels could cause invertebrate species to evolve larger average sizes, rather than simply permitting evolution of giant species.

  5. Convergent Evolution of Pathogen Effectors toward Reactive Oxygen Species Signaling Networks in Plants

    Directory of Open Access Journals (Sweden)

    Nam-Soo Jwa

    2017-09-01

    Full Text Available Microbial pathogens have evolved protein effectors to promote virulence and cause disease in host plants. Pathogen effectors delivered into plant cells suppress plant immune responses and modulate host metabolism to support the infection processes of pathogens. Reactive oxygen species (ROS act as cellular signaling molecules to trigger plant immune responses, such as pathogen-associated molecular pattern (PAMP-triggered immunity (PTI and effector-triggered immunity. In this review, we discuss recent insights into the molecular functions of pathogen effectors that target multiple steps in the ROS signaling pathway in plants. The perception of PAMPs by pattern recognition receptors leads to the rapid and strong production of ROS through activation of NADPH oxidase Respiratory Burst Oxidase Homologs (RBOHs as well as peroxidases. Specific pathogen effectors directly or indirectly interact with plant nucleotide-binding leucine-rich repeat receptors to induce ROS production and the hypersensitive response in plant cells. By contrast, virulent pathogens possess effectors capable of suppressing plant ROS bursts in different ways during infection. PAMP-triggered ROS bursts are suppressed by pathogen effectors that target mitogen-activated protein kinase cascades. Moreover, pathogen effectors target vesicle trafficking or metabolic priming, leading to the suppression of ROS production. Secreted pathogen effectors block the metabolic coenzyme NADP-malic enzyme, inhibiting the transfer of electrons to the NADPH oxidases (RBOHs responsible for ROS generation. Collectively, pathogen effectors may have evolved to converge on a common host protein network to suppress the common plant immune system, including the ROS burst and cell death response in plants.

  6. Convergent Evolution of Pathogen Effectors toward Reactive Oxygen Species Signaling Networks in Plants.

    Science.gov (United States)

    Jwa, Nam-Soo; Hwang, Byung Kook

    2017-01-01

    Microbial pathogens have evolved protein effectors to promote virulence and cause disease in host plants. Pathogen effectors delivered into plant cells suppress plant immune responses and modulate host metabolism to support the infection processes of pathogens. Reactive oxygen species (ROS) act as cellular signaling molecules to trigger plant immune responses, such as pathogen-associated molecular pattern (PAMP)-triggered immunity (PTI) and effector-triggered immunity. In this review, we discuss recent insights into the molecular functions of pathogen effectors that target multiple steps in the ROS signaling pathway in plants. The perception of PAMPs by pattern recognition receptors leads to the rapid and strong production of ROS through activation of NADPH oxidase Respiratory Burst Oxidase Homologs (RBOHs) as well as peroxidases. Specific pathogen effectors directly or indirectly interact with plant nucleotide-binding leucine-rich repeat receptors to induce ROS production and the hypersensitive response in plant cells. By contrast, virulent pathogens possess effectors capable of suppressing plant ROS bursts in different ways during infection. PAMP-triggered ROS bursts are suppressed by pathogen effectors that target mitogen-activated protein kinase cascades. Moreover, pathogen effectors target vesicle trafficking or metabolic priming, leading to the suppression of ROS production. Secreted pathogen effectors block the metabolic coenzyme NADP-malic enzyme, inhibiting the transfer of electrons to the NADPH oxidases (RBOHs) responsible for ROS generation. Collectively, pathogen effectors may have evolved to converge on a common host protein network to suppress the common plant immune system, including the ROS burst and cell death response in plants.

  7. Establishing efficient cobalt based catalytic sites for oxygen evolution on a Ta3N5 photocatalyst

    KAUST Repository

    Nurlaela, Ela

    2015-08-05

    In a photocatalytic suspension system with a powder semiconductor, the interface between the photocatalyst semiconductor and catalyst should be constructed to minimize resistance for charge transfer of excited carriers. This study demonstrates an in-depth understanding of pretreatment effects on the photocatalytic O2 evolution reaction (OER) activity of visible-light-responsive Ta3N5 decorated with CoOx nanoparticles. The CoOx/Ta3N5 sample was synthesized by impregnation followed by sequential heat treat-ments under NH3 flow and air flow at various temperatures. Various characterization techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and X-ray photoelectron spec-troscopy (XPS), were used to clarify the state and role of cobalt. No improvement in photocatalytic activity for OER over the bare Ta3N5 was observed for the as-impregnated CoOx/Ta3N5, likely because of insufficient contact between CoOx and Ta3N5. When the sample was treated in NH3 at high temperature, a substantial improvement in the photocatalytic activity was observed. After NH3 treatment at 700 °C, the Co0-CoOx core-shell agglomerated cobalt structure was identified by XAS and STEM. No metallic cobalt species was evident after the photocatalytic OER, indicating that the metallic cobalt itself is not essential for the reaction. Accordingly, mild oxidation (200 °C) of the NH3-treated CoOx/Ta3N5 sample enhanced photocatalytic OER activity. Oxidation at higher temperatures drastically eliminated the photocatalytic activity, most likely because of unfavorable Ta3N5 oxidation. These results suggest that the intimate contact between cobalt species and Ta3N5 facilitated at high temperature is beneficial to enhancing hole transport and that the cobalt oxide provides electrocatalytic sites for OER.

  8. ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua; He, Xiao-Bo; Lv, Peng-Liang; Ye, Cai-Yun; Liu, Di-Jia

    2017-05-01

    Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

  9. Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

    Science.gov (United States)

    Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

    2017-08-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier.

    Science.gov (United States)

    Wang, Baowen; Gao, Chuchang; Wang, Weishu; Zhao, Haibo; Zheng, Chuguang

    2014-05-01

    Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier (OC) was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi (LZ) bituminous coal, was performed in a thermogravimetric analyzer (TGA)-Fourier transform infrared (FT-IR) spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFe2O4 OC was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn3O4 or Fe2O3, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe3O4 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  11. Evolution of the metabolic and regulatory networks associated with oxygen availability in two phytopathogenic enterobacteria.

    Science.gov (United States)

    Babujee, Lavanya; Apodaca, Jennifer; Balakrishnan, Venkatesh; Liss, Paul; Kiley, Patricia J; Charkowski, Amy O; Glasner, Jeremy D; Perna, Nicole T

    2012-03-22

    Dickeya dadantii and Pectobacterium atrosepticum are phytopathogenic enterobacteria capable of facultative anaerobic growth in a wide range of O2 concentrations found in plant and natural environments. The transcriptional response to O2 remains under-explored for these and other phytopathogenic enterobacteria although it has been well characterized for animal-associated genera including Escherichia coli and Salmonella enterica. Knowledge of the extent of conservation of the transcriptional response across orthologous genes in more distantly related species is useful to identify rates and patterns of regulon evolution. Evolutionary events such as loss and acquisition of genes by lateral transfer events along each evolutionary branch results in lineage-specific genes, some of which may have been subsequently incorporated into the O2-responsive stimulon. Here we present a comparison of transcriptional profiles measured using densely tiled oligonucleotide arrays for two phytopathogens, Dickeya dadantii 3937 and Pectobacterium atrosepticum SCRI1043, grown to mid-log phase in MOPS minimal medium (0.1% glucose) with and without O2. More than 7% of the genes of each phytopathogen are differentially expressed with greater than 3-fold changes under anaerobic conditions. In addition to anaerobic metabolism genes, the O2 responsive stimulon includes a variety of virulence and pathogenicity-genes. Few of these genes overlap with orthologous genes in the anaerobic stimulon of E. coli. We define these as the conserved core, in which the transcriptional pattern as well as genetic architecture are well preserved. This conserved core includes previously described anaerobic metabolic pathways such as fermentation. Other components of the anaerobic stimulon show variation in genetic content, genome architecture and regulation. Notably formate metabolism, nitrate/nitrite metabolism, and fermentative butanediol production, differ between E. coli and the phytopathogens. Surprisingly, the

  12. Evolution of the metabolic and regulatory networks associated with oxygen availability in two phytopathogenic enterobacteria

    Science.gov (United States)

    2012-01-01

    Background Dickeya dadantii and Pectobacterium atrosepticum are phytopathogenic enterobacteria capable of facultative anaerobic growth in a wide range of O2 concentrations found in plant and natural environments. The transcriptional response to O2 remains under-explored for these and other phytopathogenic enterobacteria although it has been well characterized for animal-associated genera including Escherichia coli and Salmonella enterica. Knowledge of the extent of conservation of the transcriptional response across orthologous genes in more distantly related species is useful to identify rates and patterns of regulon evolution. Evolutionary events such as loss and acquisition of genes by lateral transfer events along each evolutionary branch results in lineage-specific genes, some of which may have been subsequently incorporated into the O2-responsive stimulon. Here we present a comparison of transcriptional profiles measured using densely tiled oligonucleotide arrays for two phytopathogens, Dickeya dadantii 3937 and Pectobacterium atrosepticum SCRI1043, grown to mid-log phase in MOPS minimal medium (0.1% glucose) with and without O2. Results More than 7% of the genes of each phytopathogen are differentially expressed with greater than 3-fold changes under anaerobic conditions. In addition to anaerobic metabolism genes, the O2 responsive stimulon includes a variety of virulence and pathogenicity-genes. Few of these genes overlap with orthologous genes in the anaerobic stimulon of E. coli. We define these as the conserved core, in which the transcriptional pattern as well as genetic architecture are well preserved. This conserved core includes previously described anaerobic metabolic pathways such as fermentation. Other components of the anaerobic stimulon show variation in genetic content, genome architecture and regulation. Notably formate metabolism, nitrate/nitrite metabolism, and fermentative butanediol production, differ between E. coli and the phytopathogens

  13. Evolution of the metabolic and regulatory networks associated with oxygen availability in two phytopathogenic enterobacteria

    Directory of Open Access Journals (Sweden)

    Babujee Lavanya

    2012-03-01

    Full Text Available Abstract Background Dickeya dadantii and Pectobacterium atrosepticum are phytopathogenic enterobacteria capable of facultative anaerobic growth in a wide range of O2 concentrations found in plant and natural environments. The transcriptional response to O2 remains under-explored for these and other phytopathogenic enterobacteria although it has been well characterized for animal-associated genera including Escherichia coli and Salmonella enterica. Knowledge of the extent of conservation of the transcriptional response across orthologous genes in more distantly related species is useful to identify rates and patterns of regulon evolution. Evolutionary events such as loss and acquisition of genes by lateral transfer events along each evolutionary branch results in lineage-specific genes, some of which may have been subsequently incorporated into the O2-responsive stimulon. Here we present a comparison of transcriptional profiles measured using densely tiled oligonucleotide arrays for two phytopathogens, Dickeya dadantii 3937 and Pectobacterium atrosepticum SCRI1043, grown to mid-log phase in MOPS minimal medium (0.1% glucose with and without O2. Results More than 7% of the genes of each phytopathogen are differentially expressed with greater than 3-fold changes under anaerobic conditions. In addition to anaerobic metabolism genes, the O2 responsive stimulon includes a variety of virulence and pathogenicity-genes. Few of these genes overlap with orthologous genes in the anaerobic stimulon of E. coli. We define these as the conserved core, in which the transcriptional pattern as well as genetic architecture are well preserved. This conserved core includes previously described anaerobic metabolic pathways such as fermentation. Other components of the anaerobic stimulon show variation in genetic content, genome architecture and regulation. Notably formate metabolism, nitrate/nitrite metabolism, and fermentative butanediol production, differ between E

  14. RESTful NET

    CERN Document Server

    Flanders, Jon

    2008-01-01

    RESTful .NET is the first book that teaches Windows developers to build RESTful web services using the latest Microsoft tools. Written by Windows Communication Foundation (WFC) expert Jon Flanders, this hands-on tutorial demonstrates how you can use WCF and other components of the .NET 3.5 Framework to build, deploy and use REST-based web services in a variety of application scenarios. RESTful architecture offers a simpler approach to building web services than SOAP, SOA, and the cumbersome WS- stack. And WCF has proven to be a flexible technology for building distributed systems not necessa

  15. Effective Construction of High-quality Iron Oxy-hydroxides and Co-doped Iron Oxy-hydroxides Nanostructures: Towards the Promising Oxygen Evolution Reaction Application

    Science.gov (United States)

    Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping

    2017-01-01

    Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co0.54Fe0.46OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co0.54Fe0.46OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal−air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application. PMID:28272443

  16. Effective Construction of High-quality Iron Oxy-hydroxides and Co-doped Iron Oxy-hydroxides Nanostructures: Towards the Promising Oxygen Evolution Reaction Application

    Science.gov (United States)

    Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping

    2017-03-01

    Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co0.54Fe0.46OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co0.54Fe0.46OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application.

  17. The role of nano-sized manganese oxides in the oxygen-evolution reactions by manganese complexes: towards a complete picture.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Hołyńska, Małgorzata; Shamkhali, Amir Nasser; Kazemi, Sayed Habib; Hillier, Warwick; Amini, Emad; Ghaemmaghami, M; Jafarian Sedigh, Davood; Nemati Moghaddam, Atefeh; Mohamadi, Rahim; Zaynalpoor, Sasan; Beckmann, Katrin

    2014-09-14

    Eighteen Mn complexes with N-donor and carboxylate ligands have been synthesized and characterized. Three Mn complexes among them are new and are reported for the first time. The reactions of oxygen evolution in the presence of oxone (2KHSO5·KHSO4·K2SO4) and cerium(iv) ammonium nitrate catalyzed by these complexes are studied and characterized by UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy, membrane-inlet mass spectrometry and electrochemistry. Some of these complexes evolve oxygen in the presence of oxone as a primary oxidant. CO2 and MnO4(-) are other products of these reactions. Based on spectroscopic studies, the true catalysts for oxygen evolution in these reactions are different. We proposed that for the oxygen evolution reactions in the presence of oxone, the true catalysts are both high valent Mn complexes and Mn oxides, but for the reactions in the presence of cerium(iv) ammonium nitrate, the active catalyst is most probably a Mn oxide.

  18. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template.

    Science.gov (United States)

    Ziani, Ahmed; Shinagawa, Tatsuya; Stegenburga, Liga; Takanabe, Kazuhiro

    2016-11-30

    The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

  19. Self-Template Synthesis of Porous Perovskite Titanate Solid and Hollow Submicrospheres for Photocatalytic Oxygen Evolution and Mesoscopic Solar Cells.

    Science.gov (United States)

    Pan, Jia Hong; Shen, Chao; Ivanova, Irina; Zhou, Na; Wang, Xingzhu; Tan, Wee Chong; Xu, Qing-Hua; Bahnemann, Detlef W; Wang, Qing

    2015-07-15

    We describe a general synthesis strategy, which combines sol-gel and hydrothermal processes, for the large-scale synthesis of porous perovskite titanates spheres with tunable particle size and inner structures. Amorphous hydrous TiO2 solid spheres (AHTSS) are first synthesized by a sol-gel method and are then used as precursor and template for the subsequent hydrothermal reaction with alkaline earth metal ions in an alkaline medium. This strategy can be generalized to synthesize porous spheres of various perovskite titanates (i.e., SrTiO3, BaTiO3, and CaTiO3) consisting of single-crystalline nanocubes. By controlling the textural properties (i.e., size, porosity, and structure) of AHTSS, perovskite titanates with tunable size and inner structures are selectively synthesized. The underlying formation mechanism is manifested by XRD and TEM to involve in situ crystallization or Ostwald ripening during the hydrothermal process. The obtained porous SrTiO3 spheres present superior performance in photocatalytic oxygen evolution and CdSe-sensitized mesoscopic solar cells.

  20. Microstructural Evolution of a Nanostructured Complex Copper Alloy Processed by Accumulative Roll-Bonding of Oxygen Free Copper and DLP.

    Science.gov (United States)

    Lee, Seong-Hee; Lee, Seong Ro; Ahn, In-Sook; Lim, Cha-Yong

    2016-02-01

    The accumulative roll-bonding (ARB) process using different copper alloys of oxygen free copper (OFC) and dioxide low-phosphorous copper (DLPC) was performed up to six cycles at ambient temperature without lubrication. A complex copper alloy sheet'in which OFC and DLPC alloys are stacked alternately each other was successfully fabricated by the ARB process. The microstructural evolution and texture development of the complex copper alloy with proceeding of the ARB were investigated by electron back scatter diffraction (EBSD) measurement. The specimen after 1 cycle showed significantly inhomogeneous microstructure in thickness direction, however, the inhomogeneity decreased gradually with increasing the number of ARB cycles. In addition, the grains became finer with the proceeding of the ARB. Resultantly, after 6 cycles, the specimen exhibited an ultrafine grained structure in which the grains above 65% were surrounded by the high angle grain boundaries above 15 degrees. On the other hand, there was no difference in texture development between OFC and DLPC in almost all specimens. In addition, the texture development did not depend on positions in thickness direction; the rolling texture such as {112} and {011} components developed strongly at all regions.

  1. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

    2017-09-01

    Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhanced reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and poor durability. Here, we report OER catalysts of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells derived from bimetallic metal–organic frameworks (MOFs) precursors. The optimal OER catalyst shows excellent activity (360 mV overpotential at 10 mA cm–2GEO) and durability (no obvious degradation after 20 000 cycles). The electron-donation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by chemical state of precursors. Severe metal particle growth probably caused by oxidation of carbon shells and encapsulated nanoparticles is believed to the main mechanism for activity degradation in these catalysts.

  2. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

    2017-09-01

    Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and durability. Herein, we report a highly active (360 mV overpotential at 10 mA cm–2GEO) and durable (no degradation after 20000 cycles) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron-donation/deviation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.

  3. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed

    2016-11-04

    The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

  4. Surface analysis of topmost layer of epitaxial layered oxide thin film: Application to delafossite oxide for oxygen evolution reaction

    Science.gov (United States)

    Toyoda, Kenji; Adachi, Hideaki; Miyata, Nobuhiro; Hinogami, Reiko; Orikasa, Yuki; Uchimoto, Yoshiharu

    2018-02-01

    Delafossite oxides (ABO2) have a layered structure with alternating layers of A and B elements, the topmost layer of which appears to determine their performance, such as the oxygen evolution reaction (OER) activity. In this study, we investigated the topmost layer of single-domain (0 0 1)-oriented AgCoO2 epitaxial thin film for potential use as an OER catalyst. The thin film was confirmed to possess OER activity at a level comparable to the catalyst in powder form. Atomic scattering spectroscopy revealed the topmost layer to be composed of CoO6 octahedra. In situ X-ray absorption spectroscopy showed that the oxidation of Co at the surface did not change under different potentials, which suggests that there is no valence fluctuation of Co in the stable CoO6 octahedral structure. However, the oxidation number of Co at the surface was lower than that in the bulk. Our density functional theoretical calculations also showed the Co atoms at the surface to have a slightly higher electron occupancy than those in the bulk, and suggests that the unoccupied t2g states of Co at the surface have an influence on OER activity.

  5. Fe3O4@NiFexOyNanoparticles with Enhanced Electrocatalytic Properties for Oxygen Evolution in Carbonate Electrolyte.

    Science.gov (United States)

    Luo, Zhishan; Martí-Sànchez, Sara; Nafria, Raquel; Joshua, Gihan; de la Mata, Maria; Guardia, Pablo; Flox, Cristina; Martínez-Boubeta, Carlos; Simeonidis, Konstantinos; Llorca, Jordi; Morante, Joan Ramon; Arbiol, Jordi; Ibáñez, Maria; Cabot, Andreu

    2016-11-02

    The design and engineering of earth-abundant catalysts that are both cost-effective and highly active for water splitting are crucial challenges in a number of energy conversion and storage technologies. In this direction, herein we report the synthesis of Fe 3 O 4 @NiFe x O y core-shell nanoheterostructures and the characterization of their electrocatalytic performance toward the oxygen evolution reaction (OER). Such nanoparticles (NPs) were produced by a two-step synthesis procedure involving the colloidal synthesis of Fe 3 O 4 nanocubes with a defective shell and the posterior diffusion of nickel cations within this defective shell. Fe 3 O 4 @NiFe x O y NPs were subsequently spin-coated over ITO-covered glass and their electrocatalytic activity toward water oxidation in carbonate electrolyte was characterized. Fe 3 O 4 @NiFe x O y catalysts reached current densities above 1 mA/cm 2 with a 410 mV overpotential and Tafel slopes of 48 mV/dec, which is among the best electrocatalytic performances reported in carbonate electrolyte.

  6. Porphyrinic Metal-Organic Framework-Templated Fe-Ni-P/Reduced Graphene Oxide for Efficient Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Fang, Xinzuo; Jiao, Long; Zhang, Rui; Jiang, Hai-Long

    2017-07-19

    The sluggish kinetics of oxygen evolution reaction (OER) hampers the H2 production by H2O electrolysis, and it is very important for the development of highly efficient and low-priced OER catalysts. Herein, a representative metalloporphyrinic MOF, PCN-600-Ni, integrated with graphene oxide (GO), serves as an ideal precursor and template to afford bimetallic iron-nickel phosphide/reduced graphene oxide composite (denoted as Fe-Ni-P/rGO-T; T represents pyrolysis temperature) via pyrolysis and subsequent phosphidation process. Thanks to the highly porous structure, the synergetic effect of Fe and Ni elements in bimetallic phosphide, and the good conductivity endowed by rGO, the optimized Fe-Ni-P/rGO-400 exhibits remarkable OER activity in 1 M KOH solution, affording an extremely low overpotential of 240 mV at 10 mA/cm2, which is far superior to the commercial IrO2 and among the best in all non-noble metal-based electrocatalysts.

  7. Petri Nets

    Indian Academy of Sciences (India)

    Associate Professor of. Computer Science and. Automation at the Indian. Institute of Science,. Bangalore. His research interests are broadly in the areas of stochastic modeling and scheduling methodologies for future factories; and object oriented modeling. GENERAL I ARTICLE. Petri Nets. 1. Overview and Foundations.

  8. Petri Nets

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 4; Issue 8. Petri Nets - Overview and Foundations. Y Narahari. General Article Volume 4 Issue 8 August 1999 pp ... Author Affiliations. Y Narahari1. Department ot Computer Science and Automation, Indian Institute of Science, Bangalore 560 012, India.

  9. Seasonal evolution of net and regenerated silica production around a natural Fe-fertilized area in the Southern Ocean estimated with Si isotopic approaches

    Science.gov (United States)

    Closset, I.; Lasbleiz, M.; Leblanc, K.; Quéguiner, B.; Cavagna, A.-J.; Elskens, M.; Navez, J.; Cardinal, D.

    2014-10-01

    A massive diatom bloom is observed each year in the surface waters of the naturally Fe-fertilized Kerguelen Plateau (Southern Ocean). We measured biogenic silica production and dissolution fluxes (ρSi and ρDiss, respectively) in the mixed layer in the vicinity of the Kerguelen Plateau during austral spring 2011 (KEOPS-2 cruise). We compare results from a high-nutrient low-chlorophyll reference station and stations with different degrees of iron enrichment and bloom conditions. Above the plateau biogenic ρSi are among the highest reported so far in the Southern Ocean (up to 47.9 mmol m-2 d-1). Although significant (10.2 mmol m-2 d-1 on average), ρDiss were generally much lower than production rates. Uptake ratios (ρSi : ρC and ρSi : ρN) confirm that diatoms strongly dominate primary production in this area. At the bloom onset, decreasing dissolution-to-production ratios (D : P) indicate that the remineralization of silica could sustain most of the low silicon uptake and that the system progressively shifts toward a silica production regime which must be mainly supported by new source of silicic acid. Moreover, by comparing results from the two KEOPS expeditions (spring 2011 and summer 2005), we suggest that there is a seasonal evolution of the processes decoupling Si and N cycles in the area. Indeed, the consumption of H4SiO4 standing stocks occurs only during the growing stage of the bloom when strong net silica production is observed, contributing to higher H4SiO4 depletion relative to NO3-. Then, the decoupling of H4SiO4 and NO3- is mainly controlled by the more efficient nitrogen recycling relative to Si. Gross Si : N uptake ratios were higher in the Fe-rich regions compared to the high-nutrient low-chlorophyll (HNLC) area, likely due to different diatom communities. This suggests that the diatom responses to natural Fe fertilization are more complex than previously thought, and that natural iron fertilization over long timescales does not necessarily

  10. Seasonal evolution of net and regenerated silica production around a natural Fe-fertilized area in the Southern Ocean estimated from Si isotopic approaches

    Science.gov (United States)

    Closset, I.; Lasbleiz, M.; Leblanc, K.; Quéguiner, B.; Cavagna, A.-J.; Elskens, M.; Navez, J.; Cardinal, D.

    2014-05-01

    A massive diatom-bloom is observed each year in the surface waters of the naturally Fe fertilized Kerguelen Plateau (Southern Ocean). We measured biogenic silica production and dissolution fluxes in the mixed layer in the vicinity of the Kerguelen Plateau during austral spring 2011 (KEOPS-2 cruise). We compare results from a High-Nutrient Low-Chlorophyll reference station and stations with different degrees of iron enrichment and bloom conditions. Above the Plateau biogenic silica production fluxes are among the highest reported so far in the Southern Ocean (up to 47.9 mmol m-2 d-1). Although significant (10.2 mmol m-2 d-1 in average), silica dissolution rates were generally much lower than production rates. Uptake ratios (Si:C and Si:N) confirm that diatoms strongly dominate the primary production in this area. At the bloom onset, decreasing dissolution to production ratios (D:P) indicate that the remineralization of silica could sustained most of the low silicon uptake and that the system progressively shifts toward a silica production regime which must be mainly supported by new source of silicic acid. Moreover, by comparing results from the two KEOPS-expeditions (spring 2011 and summer 2005), we suggest that there is a seasonal evolution on the processes decoupling Si and N cycles in the area. Indeed, the consumption of H4SiO4 standing stocks occurs only during the growing stage of the bloom when strong net silica production is observed, contributing to a higher H4SiO4 depletion relative to NO3-. Then, the decoupling between H4SiO4 and NO3- is mainly controlled by the more efficient nitrogen recycling relative to Si. Gross-Si:N uptake ratios were higher in the Fe-rich regions compared to the HNLC area, likely due to different diatoms communities. This suggests that the diatom responses to natural Fe fertilization are more complex than previously thought, and that natural iron fertilization over long time scales does not necessarily decrease Si:N uptake ratios

  11. Physical and photoelectrochemical characterizations of hematite {alpha}-Fe{sub 2}O{sub 3}: Application to photocatalytic oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Boumaza, S.; Boudjemaa, A. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Laboratory of Chemistry of Natural Gas, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria); Omeiri, S. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria); Bouarab, R. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Bouguelia, A.; Trari, M. [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria)

    2010-04-15

    The physical properties and photoelectrochemical characterization of {alpha}-Fe{sub 2}O{sub 3}, synthesized by co-precipitation, have been investigated in regard to solar energy conversion. The optical gap is found to be 1.94 eV and the transition is indirectly allowed. The chemical analysis reveals an oxygen deficiency and the oxide exhibits n-type conductivity, confirmed by a negative thermopower. The plot log {sigma} vs 1/T shows linearity in the range (400-670 K) with the donor levels at 0.14 eV below the conduction band and a break at {proportional_to}590 K, attributed to the ionization of the donors. The conduction occurs by small polaron hopping through mixed valences Fe{sup 2+/3+} with an electron mobility {mu}{sub 400} {sub K} of 10{sup -3} V cm{sup 2} s{sup -1}. {alpha}-Fe{sub 2}O{sub 3} exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as bias-free O{sub 2}-photoanode. The flat band potential V{sub fb} (-0.45V{sub SCE}) and the electron density N{sub D} (1.63 x 10{sup 18} cm{sup -3}) were determined, respectively, by extrapolating the linear part to C{sup -2} = 0 and the slope of the Mott Schottky plot. At pH 6.5, the valence band (+1.35V{sub SCE}) is suitably positioned with respect to the O{sub 2}/H{sub 2}O level (+0.62 V) and {alpha}-Fe{sub 2}O{sub 3} has been evaluated for the chemical energy storage through the photocatalytic reaction: (2SO{sub 3}{sup 2-}+2 H{sup +}{yields} S{sub 2} O{sub 3}{sup 2-}+ O{sub 2}+ H{sub 2} O, {delta}G = 213.36 kJ mol{sup -1}). The best photoactivity occurs in SO{sub 3}{sup 2-} solution (0.025 M, pH 8) with an oxygen rate evolution of 7.8 cm{sup 3} (g catalyst){sup -1} h{sup -1}. (author)

  12. Hollow Fluffy Co3O4 Cages as Efficient Electroactive Materials for Supercapacitors and Oxygen Evolution Reaction.

    Science.gov (United States)

    Zhou, Xuemei; Shen, Xuetao; Xia, Zhaoming; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-09-16

    Nano-/micrometer multiscale hierarchical structures not only provide large surface areas for surface redox reactions but also ensure efficient charge conductivity, which is of benefit for utilization in areas of electrochemical energy conversion and storage. Herein, hollow fluffy cages (HFC) of Co3O4, constructed of ultrathin nanosheets, were synthesized by the formation of Co(OH)2 hollow cages and subsequent calcination at 250 °C. The large surface area (245.5 m2 g(-1)) of HFC Co3O4 annealed at 250 °C ensures the efficient interaction between electrolytes and electroactive components and provides more active sites for the surface redox reactions. The hierarchical structures minimize amount of the grain boundaries and facilitate the charge transfer process. Thin thickness of nanosheets (2-3 nm) ensures the highly active sites for the surface redox reactions. As a consequence, HFC Co3O4 as the supercapacitor electrode exhibits a superior rate capability, shows an excellent cycliability of 10,000 cycles at 10 A g(-1), and delivers large specific capacitances of 948.9 and 536.8 F g(-1) at 1 and 40 A g(-1), respectively. Catalytic studies of HFC Co3O4 for oxygen evolution reaction display a much higher turnover frequency of 1.67×10(-2) s(-1) in pH 14.0 KOH electrolyte at 400 mV overpotential and a lower Tafel slope of 70 mV dec(-1). HFC Co3O4 with the efficient electrochemical activity and good stability can remain a promising candidate for the electrochemical energy conversion and storage.

  13. First-Principles Design of Graphene-Based Active Catalysts for Oxygen Reduction and Evolution Reactions in the Aprotic Li-O2 Battery.

    Science.gov (United States)

    Kang, Joonhee; Yu, Jong-Sung; Han, Byungchan

    2016-07-21

    Using first-principles density functional theory (DFT) calculations, we demonstrate that catalytic activities toward oxygen reduction and evolution reactions (ORR and OER) in a Li-O2 battery can be substantially improved with graphene-based materials. We accomplish the goal by calculating free energy diagrams for the redox reactions of oxygen to identify a rate-determining step controlling the overpotentials. We unveil that the catalytic performance is well described by the adsorption energies of the intermediates LiO2 and Li2O2 and propose that graphene-based materials can be substantially optimized through either by N doping or encapsulating Cu(111) single crystals. Furthermore, our systematic approach with DFT calculations applied to design of optimum catalysts enables screening of promising candidates for the oxygen electrochemistry leading to considerable improvement of efficiency of a range of renewable energy devices.

  14. Chemical and Electrochemical Properties of La0.58Sr0.4Fe0.8Co0.2O3-δ (LSCF) Thin Films upon Oxygen Reduction and Evolution Reactions

    DEFF Research Database (Denmark)

    Pitscheider, Simon; Machala, Michael; Guan, Zixuan

    conditions. In particular, NAP-XPS studies of the surface chemistry evolution under operation, as well as the correlation between surface potential changes in relation to the applied overpotential are addressed, in an attempt to determine the real driving force for the oxygen reactions.For this purpose, thin......The Oxygen Evolution and Oxygen Reduction Reactions (OER/ORR), occurring at the oxygen electrode of Solid Oxide Cells (SOCs) in the two possible ways of operation, require substantial overpotentials, therefore lowering the operating efficiency of the cells. The reaction mechanisms occurring...

  15. Probing S-state advancements and recombination pathways in photosystem II with a global fit program for flash-induced oxygen evolution pattern.

    Science.gov (United States)

    Pham, Long Vo; Messinger, Johannes

    2016-06-01

    The oxygen-evolving complex (OEC) in photosystem II catalyzes the oxidation of water to molecular oxygen. Four decades ago, measurements of flash-induced oxygen evolution have shown that the OEC steps through oxidation states S(0), S(1), S(2), S(3) and S(4) before O(2) is released and the S(0) state is reformed. The light-induced transitions between these states involve misses and double hits. While it is widely accepted that the miss parameter is S state dependent and may be further modulated by the oxidation state of the acceptor side, the traditional way of analyzing each flash-induced oxygen evolution pattern (FIOP) individually did not allow using enough free parameters to thoroughly test this proposal. Furthermore, this approach does not allow assessing whether the presently known recombination processes in photosystem II fully explain all measured oxygen yields during Si state lifetime measurements. Here we present a global fit program that simultaneously fits all flash-induced oxygen yields of a standard FIOP (2 Hz flash frequency) and of 11-18 FIOPs each obtained while probing the S(0), S(2) and S(3) state lifetimes in spinach thylakoids at neutral pH. This comprehensive data treatment demonstrates the presence of a very slow phase of S(2) decay, in addition to the commonly discussed fast and slow reduction of S(2) by YD and QB(-), respectively. Our data support previous suggestions that the S(0)→S(1) and S(1)→S(2) transitions involve low or no misses, while high misses occur in the S(2)→S(3) or S(3)→S(0) transitions. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Facile Method to Study Catalytic Oxygen Evolution Using a Dissolved Oxygen Optical Probe: An Undergraduate Chemistry Laboratory to Appreciate Artificial Photosynthesis

    Science.gov (United States)

    Renderos, Genesis; Aquino, Tawanda; Gutierrez, Kristian; Badiei, Yosra M.

    2017-01-01

    Artificial photosynthesis (AP) is a synthetic chemical process that replicates natural photosynthesis to mass produce hydrogen as a clean fuel from sunlight-driven water splitting (2H[subscript 2]O [right arrow] O[subscript 2] + H[subscript 2]). In both natural and artificial photosynthesis, an oxygen-evolving catalyst (OEC) is needed to catalyze…

  17. Oxygen produced by cyanobacteria in simulated Archaean conditions partly oxidizes ferrous iron but mostly escapes-conclusions about early evolution.

    Science.gov (United States)

    Rantamäki, Susanne; Meriluoto, Jussi; Spoof, Lisa; Puputti, Eeva-Maija; Tyystjärvi, Taina; Tyystjärvi, Esa

    2016-12-01

    The Earth has had a permanently oxic atmosphere only since the great oxygenation event (GOE) 2.3-2.4 billion years ago but recent geochemical research has revealed short periods of oxygen in the atmosphere up to a billion years earlier before the permanent oxygenation. If these "whiffs" of oxygen truly occurred, then oxygen-evolving (proto)cyanobacteria must have existed throughout the Archaean aeon. Trapping of oxygen by ferrous iron and other reduced substances present in Archaean oceans has often been suggested to explain why the oxygen content of the atmosphere remained negligible before the GOE although cyanobacteria produced oxygen. We tested this hypothesis by growing cyanobacteria in anaerobic high-CO2 atmosphere in a medium with a high concentration of ferrous iron. Microcystins are known to chelate iron, which prompted us also to test the effects of microcystins and nodularins on iron tolerance. The results show that all tested cyanobacteria, especially nitrogen-fixing species grown in the absence of nitrate, and irrespective of the ability to produce cyanotoxins, were iron sensitive in aerobic conditions but tolerated high concentrations of iron in anaerobicity. This result suggests that current cyanobacteria would have tolerated the high-iron content of Archaean oceans. However, only 1 % of the oxygen produced by the cyanobacterial culture was trapped by iron, suggesting that large-scale cyanobacterial photosynthesis would have oxygenated the atmosphere even if cyanobacteria grew in a reducing ocean. Recent genomic analysis suggesting that ability to colonize seawater is a secondary trait in cyanobacteria may offer a partial explanation for the sustained inefficiency of cyanobacterial photosynthesis during the Archaean aeon, as fresh water has always covered a very small fraction of the Earth's surface. If oxygenic photosynthesis originated in fresh water, then the GOE marks the adaptation of cyanobacteria to seawater, and the late-Proterozoic increase

  18. In situ one-step hydrothermal synthesis of oxygen-containing groups-modified g-C3N4 for the improved photocatalytic H2-evolution performance

    Science.gov (United States)

    Wu, Xinhe; Chen, Fengyun; Wang, Xuefei; Yu, Huogen

    2018-01-01

    Surface modification of g-C3N4 is one of the most effective strategies to boost its photocatalytic H2-evolution performance via promoting the interfacial catalytic reactions. In this study, an in situ one-step hydrothermal method was developed to prepare the oxygen-containing groups-modified g-C3N4 (OG/g-C3N4) by a facile and green hydrothermal treatment of bulk g-C3N4 in pure water without any additives. It was found that the hydrothermal treatment (180 °C) not only could greatly increase the specific surface area (from 2.3 to 69.8 m2 g-1), but also caused the formation of oxygen-containing groups (sbnd OH and Cdbnd O) on the OG/g-C3N4 surface, via the interlayer delamination and intralayer depolymerization of bulk g-C3N4. Photocatalytic experimental results indicated that after hydrothermal treatment, the resultant OG/g-C3N4 samples showed an obviously improved H2-evolution performance. Especially, when the hydrothermal time was 6 h, the resultant OG/g-C3N4(6 h) exhibited the highest photocatalytic activity, which was clearly higher than that of the bulk g-C3N4 by a factor of ca. 7. In addition to the higher specific surface area, the enhanced H2-evolution rate of OG/g-C3N4 photocatalysts can be mainly attributed to the formation of oxygen-containing groups, which possibly works as the effective H2-evolution active sites. Considering the facie and green synthesis method, the present work may provide a new insight for the development of highly efficient photocatalytic materials.

  19. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Cinco, Roehl M. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH2OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees ± 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and

  20. Earth-abundant oxygen evolution catalysts coupled onto ZnO nanowire arrays for efficient photoelectrochemical water cleavage.

    Science.gov (United States)

    Jiang, Chaoran; Moniz, Savio J A; Khraisheh, Majeda; Tang, Junwang

    2014-09-26

    ZnO has long been considered as a model UV-driven photoanode for photoelectrochemical water splitting, but its performance has been limited by fast charge-carrier recombination, extremely poor stability in aqueous solution, and slow kinetics of water oxidation. These issues were addressed by applying a strategy of optimization and passivation of hydrothermally grown 1D ZnO nanowire arrays. The length and diameter of bare ZnO nanowires were optimized by varying the growth time and precursor concentration to achieve optimal photoelectrochemical performance. The addition of earth-abundant cobalt phosphate (Co-Pi) and nickel borate (Ni-B) oxygen evolution catalysts onto ZnO nanowires resulted in substantial cathodic shifts in onset potential to as low as about 0.3 V versus the reversible hydrogen electrode (RHE) for Ni-B/ZnO, for which a maximum photocurrent density of 1.1 mA cm(-2) at 0.9 V (vs. RHE) with applied bias photon-to-current efficiency of 0.4 % and an unprecedented near-unity incident photon-to-current efficiency at 370 nm. In addition the potential required for saturated photocurrent was dramatically reduced from 1.6 to 0.9 V versus RHE. Furthermore, the stability of these ZnO nanowires was significantly enhanced by using Ni-B compared to Co-Pi due to its superior chemical robustness, and it thus has additional functionality as a stable protecting layer on the ZnO surface. These remarkable enhancements in both photocatalytic activity and stability directly address the current severe limitations in the use of ZnO-based photoelectrodes for water-splitting applications, and can be applied to other photoanodes for efficient solar-driven fuel synthesis. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  1. Evolution and Chemical State of Oxygen upon Acid Dissolution of YBa2Cu3O6.98

    NARCIS (Netherlands)

    Shafer, M.W.; Groot, R.A. de; Plechaty, M.M.; Scilla, G.J.; Cooper, E.I.

    1989-01-01

    Gas chromatography/mass spectrometry was used to analyze the oxygen evolved from normal and 18O enriched YBa2Cu3O6.98 upon dissolution in normal and 18O enriched acid. From the 18O/16O ratio we show that the oxide phase is the source of all the evolved oxygen. Our results indicate that some of the

  2. Efficient and stable photo-oxidation of water by a bismuth vanadate photoanode coupled with an iron oxyhydroxide oxygen evolution catalyst.

    Science.gov (United States)

    Seabold, Jason A; Choi, Kyoung-Shin

    2012-02-01

    BiVO(4) films were prepared by a simple electrodeposition and annealing procedure and studied as oxygen evolving photoanodes for application in a water splitting photoelectrochemical cell. The resulting BiVO(4) electrodes maintained considerable photocurrent for photo-oxidation of sulfite, but generated significantly reduced photocurrent for photo-oxidation of water to oxygen, also decaying over time, suggesting that the photoelectrochemical performance of BiVO(4) for water oxidation is mainly limited by its poor catalytic ablity to oxidize water. In order to improve the water oxidation kinetics of the BiVO(4) electrode, a layer of FeOOH was placed on the BiVO(4) surface as an oxygen evolution catalyst using a new photodeposition route. The resulting BiVO(4)/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date. In particular, the BiVO(4)/FeOOH photoanode showed an outstanding performance in the low bias region (i.e., E operating current density when assembling a complete p-n photoelectrochemical diode cell. The photocurrent-to-O(2) conversion efficiency of the BiVO(4)/FeOOH photoanode is ca. 96%, confirming that the photogenerated holes in the BiVO(4)/FeOOH photoanode are indeed excusively used for O(2) evolution. © 2012 American Chemical Society

  3. Crystal structure and surface characteristics of Sr-doped GdBaCo2O6−δ double perovskites: oxygen evolution reaction and conductivity

    KAUST Repository

    Pramana, Stevin S.

    2017-12-04

    A cheap and direct solution towards engineering better catalysts through identification of novel materials is required for a sustainable energy system. Perovskite oxides have emerged as potential candidates to replace the less economically attractive Pt and IrO2 water splitting catalysts. In this work, excellent electrical conductivity (980 S cm−1) was found for the double perovskite of composition GdBa0.6Sr0.4Co2O6−δ which is consistent with a better oxygen evolution reaction activity with the onset polarisation of 1.51 V with respect to a reversible hydrogen electrode (RHE). GdBa1−xSrxCo2O6−δ with increasing Sr content was found to crystallise in the higher symmetry tetragonal P4/mmm space group in comparison with the undoped GdBaCo2O6−δ which is orthorhombic (Pmmm), and yields higher oxygen uptake, accompanied by higher Co oxidation states. This outstanding electrochemical performance is explained by the wider carrier bandwidth, which is a function of Co–O–Co buckling angles and Co–O bond lengths. Furthermore the higher oxygen evolution activity was observed despite the formation of non-lattice oxides (mainly hydroxide species) and enrichment of alkaline earth ions on the surface.

  4. Evolution

    Science.gov (United States)

    Peter, Ulmschneider

    When we are looking for intelligent life outside the Earth, there is a fundamental question: Assuming that life has formed on an extraterrestrial planet, will it also develop toward intelligence? As this is hotly debated, we will now describe the development of life on Earth in more detail in order to show that there are good reasons why evolution should culminate in intelligent beings.

  5. Efficient Water Electrolysis Using Ni2P as a Bifunctional Catalyst: Unveiling the Oxygen Evolution Catalytic Properties of Ni2P.

    Science.gov (United States)

    Stern, Lucas-Alexandre; Hu, Xile

    2016-01-01

    The excellent bifunctional catalytic activity of nickel phosphide (Ni2P) for water splitting is reported. Ni2P, an active hydrogen evolving catalyst, is shown to be highly active for oxygen evolution. Only 290 mV of overpotential is required to generate a current density of 10 mA cm(-2) in 1 M KOH. Under oxygen evolving conditions, Ni2P undergoes structural modification to form a Ni2P/NiOx core-shell assembly, the catalytic active species. Ni2P is applied on both electrodes of an alkaline electrolyser and a current density of 10 mA cm(-2) is generated at 1.63 V.

  6. Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

    Science.gov (United States)

    Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

    2018-01-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

  7. Association between minor loading vein architecture and light- and CO2-saturated rates of photosynthetic oxygen evolution among Arabidopsis thaliana ecotypes from different latitudes

    Directory of Open Access Journals (Sweden)

    Christopher M Cohu

    2013-07-01

    Full Text Available Through microscopic analysis of veins and assessment of light- and CO2-saturated rates of photosynthetic oxygen evolution, we investigated the relationship between minor loading vein anatomy and photosynthesis of mature leaves in three ecotypes of Arabidopsis thaliana grown under four different combinations of temperature and photon flux density (PFD. All three ecotypes exhibited greater numbers and cross-sectional area of phloem cells as well as higher photosynthesis rates in response to higher PFD and especially lower temperature. The Swedish ecotype exhibited the strongest response to these conditions, the Italian ecotype the weakest response, and the Col-0 ecotype exhibited an intermediate response. Among all three ecotypes, strong linear relationships were found between light- and CO2-saturated rates of photosynthetic oxygen evolution and the number and area of either sieve elements or of companion and phloem parenchyma cells in foliar minor loading veins, with the Swedish ecotype showing the highest number of cells in minor loading veins (and largest minor veins coupled with unprecedented high rates of photosynthesis. Linear, albeit less significant, relationships were also observed between number and cross-sectional area of tracheids per minor loading vein versus light- and CO2-saturated rates of photosynthetic oxygen evolution. We suggest that sugar distribution infrastructure in the phloem is co-regulated with other features that set the upper limit for photosynthesis. The apparent genetic differences among Arabidopsis ecotypes should allow for future identification of the gene(s involved in augmenting sugar-loading and -transporting phloem cells and maximal rates of photosynthesis.

  8. Environmental TEM Study of Electron Beam Induced Electrochemistry of Pr0.64Ca0.36MnO3 Catalysts for Oxygen Evolution

    DEFF Research Database (Denmark)

    Mildner, Stephanie; Beleggia, Marco; Mierwaldt, Daniel

    2015-01-01

    an ETEM study of a Pr0.64Ca0.36MnO3 (PCMO) thin filth electrocatalySt for water splitting and Oxygen evolution in contact with water vapor: We show by means of off-axis electron holography and electrostatic modeling that the electron beam gives rise to a positive electric sample potential due to secondary....... The first reaction is an anodic oxidation of oxygen depleted amorphous PCMO which results in recrystallization of the oxide. The Second reaction is oxygen evolution which can be detected by the oxidation of a silane additive and formation of SiO2-gamma at catalytically active surfaces. The quantification...

  9. Effects of Gold Substrates on the Intrinsic and Extrinsic Activity of High-Loading Nickel-Based Oxyhydroxide Oxygen Evolution Catalysts

    DEFF Research Database (Denmark)

    Chakthranont, Pongkarn; Kibsgaard, Jakob; Gallo, Alessandro

    2017-01-01

    We systematically investigate the effects of Au substrates on the oxygen evolution activities of cathodically electrodeposited nickel oxyhydroxide (NiOOH), nickel–iron oxyhydroxide (NiFeOOH), and nickel–cerium oxyhydroxide (NiCeOOH) at varying loadings from 0 to 2000 nmol of metal/cm2. We determi...... high geometric current densities on flat substrates. By investigating the mass and site specific activities as a function of loading, we bridge the practical geometric activity to the fundamental intrinsic activity....

  10. Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

    Science.gov (United States)

    Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

    2018-02-01

    In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

  11. An example of molecular co-evolution: reactive oxygen species (ROS) and ROS scavenger levels in Schistosoma mansoni/Biomphalaria glabrata interactions.

    Science.gov (United States)

    Moné, Yves; Ribou, Anne-Cécile; Cosseau, Céline; Duval, David; Théron, André; Mitta, Guillaume; Gourbal, Benjamin

    2011-06-01

    The co-evolution between hosts and parasites involves huge reciprocal selective pressures on both protagonists. However, relatively few reports have evaluated the impact of these reciprocal pressures on the molecular determinants at the core of the relevant interaction, such as the factors influencing parasitic virulence and host resistance. Here, we address this question in a host-parasite model that allows co-evolution to be monitored in the field: the interaction between the mollusc, Biomphalaria glabrata, and its trematode parasite, Schistosoma mansoni. Reactive oxygen species (ROS) produced by the haemocytes of B. glabrata are known to play a crucial role in killing S. mansoni. Therefore, the parasite must defend itself against oxidative damage caused by ROS using ROS scavengers in order to survive. In this context, ROS and ROS scavengers are involved in a co-evolutionary arms race, and their respective production levels by sympatric host and parasite could be expected to be closely related. Here, we test this hypothesis by comparing host oxidant and parasite antioxidant capabilities between two S. mansoni/B. glabrata populations that have co-evolved independently. As expected, our findings show a clear link between the oxidant and antioxidant levels, presumably resulting from sympatric co-evolution. We believe this work provides the first supporting evidence of the Red Queen Hypothesis of reciprocal evolution for functional traits at the field-level in a model involving a host and a eukaryotic parasite. Copyright © 2011 Australian Society for Parasitology Inc. Published by Elsevier Ltd. All rights reserved.

  12. Cyanobacterial Diazotrophy and Earth's Delayed Oxygenation.

    Science.gov (United States)

    Olson, Stephanie L; Reinhard, Christopher T; Lyons, Timothy W

    2016-01-01

    The redox landscape of Earth's ocean-atmosphere system has changed dramatically throughout Earth history. Although Earth's protracted oxygenation is undoubtedly the consequence of cyanobacterial oxygenic photosynthesis, the relationship between biological O2 production and Earth's redox evolution remains poorly understood. Existing models for Earth's oxygenation cannot adequately explain the nearly 2.5 billion years delay between the origin of oxygenic photosynthesis and the oxygenation of the deep ocean, in large part owing to major deficiencies in our understanding of the coevolution of O2 and Earth's key biogeochemical cycles (e.g., the N cycle). For example, although possible links between O2 and N scarcity have been previously explored, the consequences of N2 limitation for net biological O2 production have not been examined thoroughly. Here, we revisit the prevailing view that N2 fixation has always been able to keep pace with P supply and discuss the possibility that bioavailable N, rather than P, limited export production for extended periods of Earth's history. Based on the observation that diazotrophy occurs at the expense of oxygenesis in the modern ocean, we suggest that an N-limited biosphere may be inherently less oxygenic than a P-limited biosphere-and that cyanobacterial diazotrophy was a primary control on the timing and tempo of Earth's oxygenation by modulating net biogenic O2 fluxes. We further hypothesize that negative feedbacks inhibit the transition between N and P limitation, with the implication that the pervasive accumulation of O2 in Earth's ocean-atmosphere system may not have been an inevitable consequence of oxygenic photosynthesis by marine cyanobacteria.

  13. Precambrian supercontinents, glaciations, atmospheric oxygenation, metazoan evolution and an impact that may have changed the second half of Earth history

    National Research Council Canada - National Science Library

    Grant M. Young

    2013-01-01

    ... homePage:www.eflsevie r.com/Iocate/gsf ■Review Precambrian superc0ntinents,glaciations,atmospheric oxygenation,metazoan evolution and an impact that may have changed the second...

  14. Dual-phase spinel MnCo2O4 and spinel MnCo2O4/nanocarbon hybrids for electrocatalytic oxygen reduction and evolution.

    Science.gov (United States)

    Ge, Xiaoming; Liu, Yayuan; Goh, F W Thomas; Hor, T S Andy; Zong, Yun; Xiao, Peng; Zhang, Zheng; Lim, Suo Hon; Li, Bing; Wang, Xin; Liu, Zhaolin

    2014-08-13

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential reactions for energy-storage and -conversion devices relying on oxygen electrochemistry. High-performance, nonprecious metal-based hybrid catalysts are developed from postsynthesis integration of dual-phase spinel MnCo2O4 (dp-MnCo2O4) nanocrystals with nanocarbon materials, e.g., carbon nanotube (CNT) and nitrogen-doped reduced graphene oxide (N-rGO). The synergic covalent coupling between dp-MnCo2O4 and nanocarbons effectively enhances both the bifunctional ORR and OER activities of the spinel/nanocarbon hybrid catalysts. The dp-MnCo2O4/N-rGO hybrid catalysts exhibited comparable ORR activity and superior OER activity compared to commercial 30 wt % platinum supported on carbon black (Pt/C). An electrically rechargeable zinc-air battery using dp-MnCo2O4/CNT hybrid catalysts on the cathode was successfully operated for 64 discharge-charge cycles (or 768 h equivalent), significantly outperforming the Pt/C counterpart, which could only survive up to 108 h under similar conditions.

  15. Pro ASP.NET MVC 4

    CERN Document Server

    Freeman, Adam

    2012-01-01

    The ASP.NET MVC 4 Framework is the latest evolution of Microsoft's ASP.NET web platform. It provides a high-productivity programming model that promotes cleaner code architecture, test-driven development, and powerful extensibility, combined with all the benefits of ASP.NET. ASP.NET MVC 4 contains a number of significant advances over previous versions. New mobile and desktop templates (employing adaptive rendering) are included together with support for jQuery Mobile for the first time. New display modes allow your application to select views based on the browser that's making the request whi

  16. Electrocatalytic properties of Ti/Pt–IrO2 anode for oxygen evolution in PEM water electrolysis

    DEFF Research Database (Denmark)

    Ye, Feng; Li, Jianling; Wang, Xindong

    2010-01-01

    surface had hardly discovered cracks and had compact structures, which contributed to stable nature of the electrode together with good conductivity and specific interaction between Pt and IrO2 formed during the calcination. Furthermore, the enhanced catalytic activity for O2 evolution at Ti/Pt–IrO2...

  17. Photocatalytic hydrogen evolution with a hydrogenase in a mediator-free system under high levels of oxygen.

    Science.gov (United States)

    Sakai, Tsubasa; Mersch, Dirk; Reisner, Erwin

    2013-11-18

    Take a breath: An oxygen-tolerant hydrogenase can be employed with a dye in a photocatalytic scheme for the generation of H2 . The homogeneous system does not require a redox mediator and visible-light irradiation yields high amounts of H2 even in the presence of air. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Oxygen safety

    Science.gov (United States)

    COPD - oxygen safety; Chronic obstructive pulmonary disease - oxygen safety; Chronic obstructive airways disease - oxygen safety; Emphysema - oxygen safety; Heart failure - oxygen-safety; Palliative care - oxygen safety; Hospice - oxygen safety

  19. Neoproterozoic Oxygenation of Earth Surface Environments Reflected in the Late Evolution of the O2-Dependent Vitamin B12 Biosynthesis Pathway

    Science.gov (United States)

    Saito, M. A.; Bertrand, E. M.; Anbar, A.

    2008-12-01

    There are multiple lines of evidence for a significant rise of O2 in the Earth's atmosphere ~2.4 Ga. A second oxygenation event in the Neoproterozoic is not as well constrained. These changes in environmental redox affected the abundances of bioessential elements. Trace elements such as Co, Fe, and Ni were likely favored in the early evolution of metalloenzymes, prior to the first oxidation event. Consistent with this expectation, vitamin B12 is a Co-containing biomolecule whose biosynthesis is thought to have evolved prior to the origin of oxygenic photosynthesis and the first rise in O2. However, biochemical characterization of the many enzymes involved in B12 biosynthesis has revealed two distinct pathways: an O2-independent pathway and an O2-dependant pathway. The major difference between these pathways involves the timing of the insertion of Co. We examined the amino acid sequences of enzymes in the B12 biosynthesis pathway from a set of 100 phylogenetically diverse microbial genomes, focusing on enzymes exclusive to each pathway as well as enzymes shared by both. Molecular clock and phylogenetic analyses were performed on alignments of the sequences obtained from these study genomes. This approach focused on functional genes rather than the phylogeny of microbes in an attempt to understand the evolution of the pathway itself, rather than its presence in individual phylogenetic groups. Clear differences in age are apparent between representatives of each pathway. The O2-independent pathway and enzymes shared in both pathways show the most ancient last common ancestors. In contrast, the enzymes associated exclusively with the O2-dependent pathway diverged from a common ancestor less than a billion years ago. Phylogenetic analysis suggests that these enzymes were recruited from other biochemical pathways. From these results it seems likely that the evolution of the O2-dependent pathway occurred long after the initial evolution of the B12 biosynthesis. This

  20. Cu(OH)2@CoCO3(OH)2·nH2O Core-Shell Heterostructure Nanowire Array: An Efficient 3D Anodic Catalyst for Oxygen Evolution and Methanol Electrooxidation.

    Science.gov (United States)

    Xie, Lisi; Tang, Chun; Wang, Kunyang; Du, Gu; Asiri, Abdullah M; Sun, Xuping

    2017-02-01

    A Cu(OH) 2 @CoCO 3 (OH) 2 ·nH 2 O (CCHH) core-shell heterostructure nanowire array acts as robust 3D oxygen evolution reaction catalyst. It needs an overpotential of 270 mV to drive 50 mA cm -2 in 1.0 m KOH, outperforming CCHH nanowire arrays on copper foam and most reported Co-based oxygen evolution reaction catalysts in alkaline media. It is also efficient for methanol electrooxidation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like shape for oxygen evolution reaction with enhanced catalytic activity

    Directory of Open Access Journals (Sweden)

    Tao Ding

    2016-01-01

    Full Text Available Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like wire shape has been achieved via a facile and moderate hydrothermal process at 120 °C for 1 h from the reaction of nickel nitrate and chloroplatinic acid in alkaline solution in the presence of ethanediamine and hydrazine hydrate. The holothuria-like alloyed NiPt wires are Ni-rich in composition (Ni23.6Pt and uniform in diameter with many tiny tips outstretched from the wires surface. The holothuria-like wires are assembled from granular subunits with the assistance of capping molecular of ethanediamine and the wires display an improved oxygen evolution reaction catalytic activity.

  2. Metal-Organic-Framework-Derived Yolk-Shell-Structured Cobalt-Based Bimetallic Oxide Polyhedron with High Activity for Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Yu, Zhou; Bai, Yu; Liu, Yuxuan; Zhang, Shimin; Chen, Dandan; Zhang, Naiqing; Sun, Kening

    2017-09-20

    The development of inexpensive, efficient, and environmentally friendly catalysts for oxygen evolution reaction (OER) is of great significant for green energy utilization. Herein, binary metal oxides (MxCo3-xO4, M = Zn, Ni, and Cu) with yolk-shell polyhedron (YSP) structure were fabricated by facile pyrolysis of bimetallic zeolitic imidazolate frameworks (MCo-ZIFs). Benefiting from the synergistic effects of metal ions and the unique yolk-shell structure, MxCo3-xO4 YSP displays good OER catalytic activity in alkaline media. Impressively, ZnxCo3-xO4 YSP shows a comparable overpotential of 337 mV at 10 mA cm-2 to commercial RuO2 and exhibits superior long-term durability. The high activity and good stability reveals its promising application.

  3. Reactive oxygen species drive evolution of pro-biofilm variants in pathogens by modulating cyclic-di-GMP levels

    DEFF Research Database (Denmark)

    Chua, Song Lin; Ding, Yichen; Liu, Yang

    2016-01-01

    an experimental evolution strategy, we show that exposure of the opportunistic pathogen Pseudomonas aeruginosa to sub-lethal hydrogen peroxide (H2O2) levels over 120 generations led to the emergence of pro-biofilm rough small colony variants (RSCVs), which could be abrogated by l-glutathione antioxidants....... Comparative genomic analysis of the RSCVs revealed that mutations in the wspF gene, which encodes for a repressor of WspR diguanylate cyclase (DGC), were responsible for increased intracellular cyclic-di-GMP content and production of Psl exopolysaccharide. Psl provides the first line of defence against ROS...

  4. Effect of pure oxygen fine bubbles on the organic matter removal and bacterial community evolution treating coal gasification wastewater by membrane bioreactor.

    Science.gov (United States)

    Zhuang, Haifeng; Hong, Xiaoting; Han, Hongjun; Shan, Shengdao

    2016-12-01

    A lab-scale study was investigated to evaluate the effect of pure oxygen fine bubbles on membrane bioreactor (O2-MBR) performance of treating coal gasification wastewater. Compared with conventional MBR using aeration source of air (CMBR), the removal efficiencies of COD and total phenols increased by 28% and 36%, and the organic compositions of treated effluent represented significant difference that was mainly attributed to the controlled the foam expansion and enhanced the enzymatic activities in O2-MBR. Moreover, membrane fouling mitigation was observed in O2-MBR, probably owing to the less EPS amount and larger PSD. It was notable that the pure oxygen with fine bubbles promoted marked evolution of bacterial community from CMBR to O2-MBR, particularly, the bacterial community richness and diversity in O2-MBR was lower than CMBR, and the genera Phycisphaera, Comamonas, Thauera and Ohtaekwangia composed the top four most relative abundance genera in O2-MBR, giving the total relative abundance of 26.7%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. [Photosynthetic oxygen evolution and CO2 photoassimilation by cyanobacteria that form water-bloom spots in a sulfur spring with a high sulfide content].

    Science.gov (United States)

    Barskiĭ, E L; Nikitina, K A; Belogurova, N G; Gorskaia, N V; Gusev, M B

    1980-01-01

    Cyanobacteria belonging mainly to the genera Anabaena and Oscillatoria were isolated from water-bloom spots of a sulfur spring in Staraya Matsesta. Their suspensions evolved O2 at a rate of 6--8 nM/min per 1 mg of dry cell weight at an intensity of solar radiation being 60--75 mV/cm2 per 1 sec. The cells were also capable of CO2 photoassimilation in the presence of solfide at a rate of 10(-4) mg C per mg per hour. DCMU at a concentration of 10(-5) M completely inhibited O2 evolution and inhibited CO2 fixation by 80%. Oxygen assimilation in dark by the suspensions did not depend on the addition of cyanide and was caused apparently by nonenzymatic reduction of O2 with sulfide dissolved in the spring water. Oxygen assimilation by the suspensions in light in the presence of DCMU was by 20--30% greater than in dark. Therefore, the cells of cyanobacteria are characterized by photorespiration at the level of photosystem I. Presumably, sulfide at a concentration of 9 mM cannot significantly inhibit the photosynthetic processes in cyanobacteria producing water-bloom spots in the sulfur spring.

  6. Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

    Science.gov (United States)

    He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

    2017-12-13

    We report on the new facile synthesis of mesoporous NiO/MnO2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm-2 for the OER and -3 mA cm-2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

  7. From Chlorella to Nestlike Framework Constructed with Doped Carbon Nanotubes: A Biomass-Derived, High-Performance, Bifunctional Oxygen Reduction/Evolution Catalyst.

    Science.gov (United States)

    Wang, Guanghua; Deng, Yijie; Yu, Jinnan; Zheng, Long; Du, Li; Song, Huiyu; Liao, Shijun

    2017-09-20

    The development of effective bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is significant for energy conversion systems, such as Li-air batteries, fuel cells, and water splitting technologies. Herein, a Chlorella-derived catalyst with a nestlike framework, composed of bamboolike nanotubes that encapsulate cobalt nanoparticles, has been prepared through a facile pyrolysis process. It achieves perfect bifunctional catalysis both in ORR and OER on a single catalyst. For our optimal catalyst Co/M-Chlorella-900, its ORR half-wave potential is positively shifted by 40 mV compared to that of a commercial Pt/C catalyst, and the overpotential at 10 mA cm -2 for the OER is 23 mV lower than that of a commercial IrO 2 /C catalyst in an alkaline medium. This superior bifunctional catalytic performance is benefited from the simultaneous increase of pyridinic N sites for ORR and graphitic N sites for OER. In addition, N-doped carbon-encapsulated Co nanoparticles improve both ORR and OER performance by forming new active centers. The unique nestlike carbon nanotube framework not only afforded highly dense ORR and OER active sites but also promoted the electron and mass transfer. Our catalyst also displays notable durability during the ORR and OER, making it promising for use in ORR/OER-related energy conversion systems.

  8. Ni-Fe Nitride Nanoplates on Nitrogen-Doped Graphene as a Synergistic Catalyst for Reversible Oxygen Evolution Reaction and Rechargeable Zn-Air Battery.

    Science.gov (United States)

    Fan, Yuchi; Ida, Shintaro; Staykov, Aleksandar; Akbay, Taner; Hagiwara, Hidehisa; Matsuda, Junko; Kaneko, Kenji; Ishihara, Tatsumi

    2017-07-01

    Obtaining bifunctional electrocatalysts with high activity for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is a main hurdle in the application of rechargeable metal-air batteries. Earth-abundant 3d transition metal-based catalysts have been developed for the OER and ORR; however, most of these are based on oxides, whose insulating nature strongly restricts their catalytic performance. This study describes a metallic Ni-Fe nitride/nitrogen-doped graphene hybrid in which 2D Ni-Fe nitride nanoplates are strongly coupled with the graphene support. Electronic structure of the Ni-Fe nitride is changed by hybridizing with the nitrogen-doped graphene. The unique heterostructure of this hybrid catalyst results in very high OER activity with the lowest onset overpotential (150 mV) reported, and good ORR activity comparable to that for commercial Pt/C. The high activity and durability of this bifunctional catalyst are also confirmed in rechargeable zinc-air batteries that are stable for 180 cycles with an overall overpotential of only 0.77 V at 10 mA -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. In situ Formed Co(TCNQ)2 Metal-Organic Framework Array as a High-Efficiency Catalyst for Oxygen Evolution Reactions.

    Science.gov (United States)

    Wei, Yicheng; Ren, Xiang; Ma, Hongmin; Sun, Xu; Zhang, Yong; Kuang, Xuan; Yan, Tao; Wu, Dan; Wei, Qin

    2018-01-04

    Energy conversion and storage systems such as water splitting devices and metal-air batteries need excellent and energy-efficiency oxygen evolution reaction (OER) catalysts. This work reports the in situ development of sawtooth-like Co(TCNQ)2 (TCNQ=tetracyanoquinodimethane) metal-organic framework array on Co foil (Co(TCNQ)2 /Co) by means of a solution immersion method at room temperature. As an oxygen-evolving catalyst, the resulting Co(TCNQ)2 /Co demonstrates superior OER activity with overpotential of 310 mV to drive a geometrical catalytic current density of 15 mA cm-2 in 1.0 M KOH. Notably, it also shows good long-term electrochemical durability with its activity being retained for at least 20 h and achieves a high turnover frequency of 0.66 mol O2  s-1 at overpotential of 380 mV. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Fabrication of modified g-C3N4 nanorod/Ag3PO4 nanocomposites for solar-driven photocatalytic oxygen evolution from water splitting

    Science.gov (United States)

    Tian, Lin; Xian, Xiaozhai; Cui, Xingkai; Tang, Hua; Yang, Xiaofei

    2018-02-01

    Semiconductor-based photocatalysis has been considered as one of the most effective techniques to achieve the conversion of clean and sustainable sunlight to solar fuel, in which the construction of novel solar-driven photocatalytic systems is the key point. Here, we report initially the synthesis of modified graphitic carbon nitride (g-C3N4) nanorods via the calcination of intermediates obtained from the co-polymerization of precursors, and the in-situ hybridization of Ag3PO4 with as-prepared modified g-C3N4 to produce g-C3N4 nanorod/Ag3PO4 composite materials. The diameter of modified rod-like g-C3N4 materials is determined to be around 1 μm. Subsequently the morphological features, crystal and chemical structures of the assembled g-C3N4 nanorod/Ag3PO4 composites were systematically investigated by SEM, XRD, XPS, UV-vis diffuse reflectance spectra (DRS). Furthermore, the use of as-prepared composite materials as the catalyst for photocatalytic oxygen evolution from water splitting was studied. The oxygen-generating results showed that the composite photocatalyst modified with 600 mg rod-like g-C3N4 demonstrates 2.5 times higher efficiency than that of bulk Ag3PO4. The mechanism behind the enhancement in the oxygen-evolving activity is proposed on the basis of in-situ electron spin resonance (ESR) measurement as well as theoretical analysis. The study provides new insights into the design and development of new photocatalytic composite materials for energy and environmental applications.

  11. Photocatalytic Hydrogen or Oxygen Evolution from Water over S- or N-Doped TiO2 under Visible Light

    Directory of Open Access Journals (Sweden)

    Kazumoto Nishijima

    2008-01-01

    Full Text Available S- or N-doping of TiO2 powder having an anatase or rutile phase extended the photocatalytic activity for water oxidation and reduction under UV light and visible light irradiation. For the reduction of water, anatase-doped TiO2 showed higher level of activity than that of doped TiO2 having a rutile phase using ethanol as an electron donor. Furthermore, the activity level of S-doped TiO2 for hydrogen evolution was higher than that of N-doped TiO2 photocatalysts under visible light. Photocatalytic oxidation of water on doped TiO2 having a rutile phase proceeded with fairly high efficiency when Fe3+ ions were used as electron acceptors compared to that on doped TiO2 having an anatase phase. In addition, water splitting under visible light irradiation was achieved by construction of a Z-scheme photocatalysis system employing the doped TiO2 having anatase and rutile phases for H2 and O2 evolution and the I−/IO3− redox couple as an electron relay.

  12. Mixed-Metal-Organic Framework Self-Template Synthesis of Porous Hybrid Oxyphosphides for Efficient Oxygen Evolution Reaction.

    Science.gov (United States)

    Babu, Dickson D; Huang, Yiyin; Anandhababu, Ganesan; Ghausi, Muhammad Arsalan; Wang, Yaobing

    2017-11-08

    Developing an efficient, stable yet cost-effective electrocatalyst is the key link along the path to hydrogen fuels produced by water splitting. The current bottleneck in the water electrolysis technology is the sluggish oxygen-evolving reaction (OER) which is also central to the rechargeable metal-air batteries. Herein, we report a promising mixed-metal-organic framework (MMOF) self-template strategy to synthesize CoFe hybrid oxyphosphides with highly porous morphology. Aided by the porous hybrid bulk structure beneficial to fast-ion diffusion to abundant highly active sites, the as-synthesized Co3FePxO exhibited excellent electrocatalytic activity toward OER, with an overpotential of 291 mV at 10 mA cm-2 and a low Tafel slope of 85 mV dec-1. With the underpinnings of MMOF maintaining the structural rigidity and stability, the material also showed long life for OER without  discernible activity decay.

  13. Ultrathin Co3O4 nanofilm as an efficient bifunctional catalyst for oxygen evolution and reduction reaction in rechargeable zinc-air batteries.

    Science.gov (United States)

    He, Yu; Zhang, Jinfeng; He, Guowei; Han, Xiaopeng; Zheng, Xuerong; Zhong, Cheng; Hu, Wenbin; Deng, Yida

    2017-06-29

    Two-dimensional (2D) nanocatalysts with a large specific surface area and efficient charge conductivity are promising candidates for catalyzing the sluggish oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), which are at the heart of various electrochemical energy conversion and storage technologies. Here, we report the synthesis of an ultrathin Co3O4 nanofilm with a thickness of nearly 1.8 nm via a surfactant- and template-free facile hydrothermal route. The proposed synthesis strategy can be extended to the preparation of 2D NixCo3-xO4 and FexCo3-xO4 nanostructures. The synthesized Co3O4 nanofilm exhibited bifunctional activity that was superior to that of the counterpart Co3O4 nanoparticles, including a lower overpotential and higher reduction and evolution current densities, and demonstrated faster catalytic kinetics over the 2D nanofilm surface. In comparison with precious metal-based catalysts, to achieve an OER current density of 40 mA cm-2 the overpotential of the nanofilm (461 mV) was lower than that of RuO2 (526 mV), whereas the ORR on the nanofilm proceeded via a dominant 4e- transfer mechanism, which is similar to that of commercial carbon-supported Pt (Pt/C). The Co3O4 nanofilm enabled the assembly of rechargeable Zn-air batteries with a lower overpotential (0.72 V), higher round-trip efficiency (62.7%), and a longer cycle lifetime (175 cycles). The remarkable bifunctional activity contributes to an increase in the number of electrochemically active sites, a large interfacial contact area with the electrolyte, and the enrichment of Co3+ ions on the surface, which facilitates the adsorption and activation of oxygen-containing species. This study should shed light on the future development of new electroactive materials with optimized 2D nanostructures to enhance the overall bifunctional ORR/OER performance of rechargeable metal-air batteries.

  14. SkyNet: Modular nuclear reaction network library

    Science.gov (United States)

    Lippuner, Jonas; Roberts, Luke F.

    2017-10-01

    The general-purpose nuclear reaction network SkyNet evolves the abundances of nuclear species under the influence of nuclear reactions. SkyNet can be used to compute the nucleosynthesis evolution in all astrophysical scenarios where nucleosynthesis occurs. Any list of isotopes can be evolved and SkyNet supports various different types of nuclear reactions. SkyNet is modular, permitting new or existing physics, such as nuclear reactions or equations of state, to be easily added or modified.

  15. An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

    KAUST Repository

    Garcia Esparza, Angel T.

    2017-04-13

    For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

  16. NA-NET numerical analysis net

    Energy Technology Data Exchange (ETDEWEB)

    Dongarra, J. [Tennessee Univ., Knoxville, TN (United States). Dept. of Computer Science]|[Oak Ridge National Lab., TN (United States); Rosener, B. [Tennessee Univ., Knoxville, TN (United States). Dept. of Computer Science

    1991-12-01

    This report describes a facility called NA-NET created to allow numerical analysts (na) an easy method of communicating with one another. The main advantage of the NA-NET is uniformity of addressing. All mail is addressed to the Internet host ``na-net.ornl.gov`` at Oak Ridge National Laboratory. Hence, members of the NA-NET do not need to remember complicated addresses or even where a member is currently located. As long as moving members change their e-mail address in the NA-NET everything works smoothly. The NA-NET system is currently located at Oak Ridge National Laboratory. It is running on the same machine that serves netlib. Netlib is a separate facility that distributes mathematical software via electronic mail. For more information on netlib consult, or send the one-line message ``send index`` to netlib{at}ornl.gov. The following report describes the current NA-NET system from both a user`s perspective and from an implementation perspective. Currently, there are over 2100 members in the NA-NET. An average of 110 mail messages pass through this facility daily.

  17. NA-NET numerical analysis net

    Energy Technology Data Exchange (ETDEWEB)

    Dongarra, J. (Tennessee Univ., Knoxville, TN (United States). Dept. of Computer Science Oak Ridge National Lab., TN (United States)); Rosener, B. (Tennessee Univ., Knoxville, TN (United States). Dept. of Computer Science)

    1991-12-01

    This report describes a facility called NA-NET created to allow numerical analysts (na) an easy method of communicating with one another. The main advantage of the NA-NET is uniformity of addressing. All mail is addressed to the Internet host na-net.ornl.gov'' at Oak Ridge National Laboratory. Hence, members of the NA-NET do not need to remember complicated addresses or even where a member is currently located. As long as moving members change their e-mail address in the NA-NET everything works smoothly. The NA-NET system is currently located at Oak Ridge National Laboratory. It is running on the same machine that serves netlib. Netlib is a separate facility that distributes mathematical software via electronic mail. For more information on netlib consult, or send the one-line message send index'' to netlib{at}ornl.gov. The following report describes the current NA-NET system from both a user's perspective and from an implementation perspective. Currently, there are over 2100 members in the NA-NET. An average of 110 mail messages pass through this facility daily.

  18. Operando XAS Study of the Surface Oxidation State on a Monolayer IrOx on RuOx and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

    2017-01-01

    that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

  19. Role of composition and oxygen partial pressure on microstructural and crystalline phase evolution in aluminosilicate derived aggregates

    Science.gov (United States)

    Luscher, Walter G.

    Spherical aggregates, approximately 1mm in diameter, derived from either kaolinite or bauxite are used in tonnage quantities to aid the extraction of oil and natural gas. Aggregates intended for this application are referred to as proppants and key characteristics include low density and high strength, which are influenced by processing temperature and variation in raw ore chemistry. Kaolinite and bauxite ores doped with varying concentrations of K2O and Fe2O3 were sintered at different temperatures to elucidate composition-processing-property relationships. The dopants are known to form low temperature ternary eutectics with Al2O3 and SiO2 and are anticipated to facilitate low temperature densification and enhance mullite formation. In addition, proppants doped with Fe2 O3 were studied under varying oxygen partial pressures to further enhance low temperature densification by manipulating the valence state of iron. Microstructure and crystalline phase assemblage were evaluated by scanning electron microscopy and X-ray diffraction, respectively, and correlated with results of density and strength measurements obtained by gas pycnometry and diametral compression, respectively. Results indicate that dopant enhanced densification can simultaneously improve strength and processing economy of proppants by lowering sintering temperatures up to 100°C. Controlled atmosphere studies revealed that manipulating the valence of iron produces unique microstructures that may be useful in a number of different applications. These microstructures include aggregates with metallic coatings and aggregates with core-shell microstructures, which exhibit a porous core enclosed by a relatively dense outer shell.

  20. Evidence in pre-2.2 Ga paleosols for the early evolution of atmospheric oxygen and terrestrial biota

    Science.gov (United States)

    Ohmoto, H

    1996-12-01

    The loss of Fe from some pre-2.2 Ga paleosols has been considered by previous investigators as the best evidence for a reduced atmosphere prior to 2.2 Ga. I have examined the behavior of Fe in both pre- and post-2.2 Ga paleosols from depth profiles of Fe3+/Ti, Fe2+/Ti, and sigma Fe/Ti ratios, and Fe3+/Ti vs. Fe2+/Ti plots. This new approach reveals a previously unrecognized history of paleosols. Essentially all paleosols, regardless of age, retain some characteristics of soils formed under an oxic atmosphere, such as increased Fe3+/Ti ratios from their parental rocks. The minimum oxygen pressure (PO2) for the 3.0-2.2 Ga atmosphere is calculated to be about 1.5% of the present atmospheric level, which is the same as that for the post-1.9 Ga atmosphere. The loss of sigma Fe, common in paleosol sections of all ages, was not due to a reducing atmosphere, but to reductive dissolution of ferric hydroxides formed under an oxic atmosphere. This reductive dissolution of ferric hydroxides occurred either (1) after soil formation by hydrothermal fluids or (2) during and/or after soil formation by organic acids generated from the decay of terrestrial organic matter. Terrestrial biomass on the early continents may have been more extensive than previously recognized.

  1. An oxygen-insensitive hydrogen evolution catalyst coated by a molybdenum-based layer for overall water splitting

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Takanabe, Kazuhiro [KAUST Catalysis Center (KCC) and Physical Science and Engineering Division - PSE, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Wei, Nini; Anjum, Dalaver H. [Advanced Nanofabrication, Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Clo, Alain [Research Computing, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Weng, Tsu-Chien [Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Nordlund, Dennis; Sokaras, Dimosthenis [Stanford Synchrotron Radiation Lightsource, Menlo Park, CA (United States); Kubota, Jun [Department of Chemical Engineering, Fukuoka University (Japan); Domen, Kazunari [Department of Chemical System Engineering, School of Engineering, The University of Tokyo (Japan)

    2017-05-15

    For overall water-splitting systems, it is essential to establish O{sub 2}-insensitive cathodes that allow cogeneration of H{sub 2} and O{sub 2}. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H{sub 2} evolution in the presence of O{sub 2}. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O{sub 2} gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO{sub x}/Pt/SrTiO{sub 3} with inhibited water formation from H{sub 2} and O{sub 2}, which is the prevailing back reaction on the bare Pt/SrTiO{sub 3} photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Efficient and durable oxygen reduction and evolution of a hydrothermally synthesized La(Co0.55Mn0.45)0.99O3-δ nanorod/graphene hybrid in alkaline media

    Science.gov (United States)

    Ge, Xiaoming; Goh, F. W. Thomas; Li, Bing; Hor, T. S. Andy; Zhang, Jie; Xiao, Peng; Wang, Xin; Zong, Yun; Liu, Zhaolin

    2015-05-01

    The increasing global energy demand and the depletion of fossil fuels have stimulated intense research on fuel cells and batteries. Oxygen electrocatalysis plays essential roles as the electrocatalytic reduction and evolution of di-oxygen are always the performance-limiting factors of these devices relying on oxygen electrochemistry. A novel perovskite with the formula La(Co0.55Mn0.45)0.99O3-δ (LCMO) is designed from molecular orbital principles. The hydrothermally synthesized LCMO nanorods have unique structural and chemical properties and possess high intrinsic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergic covalent coupling between LCMO and NrGO enhances the bifunctional ORR and OER activities of the novel LCMO/NrGO hybrid catalyst. The ORR activity of LCMO/NrGO is comparable to the state-of-the-art Pt/C catalyst and its OER activity is competitive to the state-of-the-art Ir/C catalyst. LCMO/NrGO generally outperforms Pt/C and Ir/C with better bifunctional ORR and OER performance and operating durability. LCMO/NrGO represents a new class of low-cost, efficient and durable electrocatalysts for fuel cells, water electrolysers and batteries.The increasing global energy demand and the depletion of fossil fuels have stimulated intense research on fuel cells and batteries. Oxygen electrocatalysis plays essential roles as the electrocatalytic reduction and evolution of di-oxygen are always the performance-limiting factors of these devices relying on oxygen electrochemistry. A novel perovskite with the formula La(Co0.55Mn0.45)0.99O3-δ (LCMO) is designed from molecular orbital principles. The hydrothermally synthesized LCMO nanorods have unique structural and chemical properties and possess high intrinsic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergic covalent coupling between LCMO and NrGO enhances the bifunctional ORR and OER activities of the novel LCMO/NrGO hybrid

  3. Net Ecosystem Carbon Flux

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Net Ecosystem Carbon Flux is defined as the year-over-year change in Total Ecosystem Carbon Stock, or the net rate of carbon exchange between an ecosystem and the...

  4. Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction

    Science.gov (United States)

    Zhang, Tingting; He, Chuansheng; Sun, Fengzhan; Ding, Yongqi; Wang, Manchao; Peng, Lin; Wang, Jiahui; Lin, Yuqing

    2017-03-01

    This study describes a facile and effective route to synthesize hybrid material consisting of Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide (Co3O4/N-rGO) as a high-performance tri-functional catalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and H2O2 sensing. Electrocatalytic activity of Co3O4/N-rGO to hydrogen peroxide reduction was tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry. Under a reduction potential at -0.6 V to H2O2, this constructing H2O2 sensor exhibits a linear response ranging from 0.2 to 17.5 mM with a detection limit to be 0.1 mM. Although Co3O4/rGO or nitrogen-doped reduced graphene oxide (N-rGO) alone has little catalytic activity, the Co3O4/N-rGO exhibits high ORR activity. The Co3O4/N-rGO hybrid demonstrates satisfied catalytic activity with ORR peak potential to be -0.26 V (vs. Ag/AgCl) and the number of electron transfer number is 3.4, but superior stability to Pt/C in alkaline solutions. The same hybrid is also highly active for OER with the onset potential, current density and Tafel slope to be better than Pt/C. The unusual catalytic activity of Co3O4/N-rGO for hydrogen peroxide reduction, ORR and OER may be ascribed to synergetic chemical coupling effects between Co3O4, nitrogen and graphene.

  5. Proterozoic atmospheric oxygen

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    2014-01-01

    This article is concerned with the evolution of atmospheric oxygen concentrations through the Proterozoic Eon. In particular, this article will seek to place the history of atmospheric oxygenation through the Proterozoic Eon in the context of the evolving physical environment including the history...

  6. Professional Enterprise NET

    CERN Document Server

    Arking, Jon

    2010-01-01

    Comprehensive coverage to help experienced .NET developers create flexible, extensible enterprise application code If you're an experienced Microsoft .NET developer, you'll find in this book a road map to the latest enterprise development methodologies. It covers the tools you will use in addition to Visual Studio, including Spring.NET and nUnit, and applies to development with ASP.NET, C#, VB, Office (VBA), and database. You will find comprehensive coverage of the tools and practices that professional .NET developers need to master in order to build enterprise more flexible, testable, and ext

  7. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Science.gov (United States)

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  8. Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

    Science.gov (United States)

    Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

    2017-03-01

    High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found.

  9. One-pot synthesis of hollow AgPt alloyed nanocrystals with enhanced electrocatalytic activity for hydrogen evolution and oxygen reduction reactions.

    Science.gov (United States)

    Shao, Fang-Qi; Zhu, Xiao-Yan; Wang, Ai-Jun; Fang, Ke-Ming; Yuan, Junhua; Feng, Jiu-Ju

    2017-11-01

    Herein, a simple one-pot aqueous method was developed for the fabrication of uniform hollow bimetallic AgPt alloyed nanocrystals (H-AgPt NCs) by using 5-aminoorotic acid (5-amino-2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid) as a growth-directing agent, without any seed, organic solvent or template involved. The prepared H-AgPt NCs displayed enhanced electrocatalytic activity for hydrogen evolution reaction (HER) with a more positive onset overpotential (ηonset) of -28mV and a smaller Tafel slope of 40mVdec(-1) relative to commercial Pt black (-34mV, 50mVdec(-1)) and Pt/C (20wt.%, -33mV, 33mVdec(-1)) in 0.5M H2SO4. Meanwhile, the obtained catalyst exhibited improved catalytic features toward oxygen reduction reaction (ORR) with a positive ηonset (0.916V) and enhanced kinetic current density (243.23mAmg(-1)Pt) in 0.1M HClO4 at 0.850V compared with Pt black (0.876V, 25.85mAmg(-1)Pt). Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

    KAUST Repository

    AlYami, Noktan Mohammed

    2016-05-17

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  11. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  12. Strengthened Synergistic Effect of Metallic Mx Py (M = Co, Ni, and Cu) and Carbon Layer via Peapod-Like Architecture for Both Hydrogen and Oxygen Evolution Reactions.

    Science.gov (United States)

    Bai, Yuanjuan; Fang, Ling; Xu, Haitao; Gu, Xiao; Zhang, Huijuan; Wang, Yu

    2017-04-01

    The smooth electric transmission is crucial for the high-efficient electrocatalysis. Herein, a series of peapod-like metallic Mx Py /C (M = Co, Ni, and Cu) composites is developed as bifunctional catalysts toward hydrogen and oxygen evolution reactions. For the first time, the metallic property of Cu3 P is confirmed through the theoretical calculation. The in-depth composition, structural and catalytic mechanism analysis of Mx Py /C discloses that the comparable activity and considerable durability of these catalysts mainly result from the strengthened synergistic effect between metallic Mx Py and carbon layer based on the unique peapod-like architecture. Especially, the atomic contact between Mx Py and carbon not only provides an open channel for electronic transmission but also ensures the integrity of peapod-like structure. Furthermore, the high electric conductivity of the inner metallic Mx Py and the outer carbon layer endows the Mx Py /C catalyst with rapid charge migration during the electrocatalytic pathway. These findings shed light on the origin of high catalytic activity of Mx Py /C and open a path for purposefully rationally synthesizing superior electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Oxygen levels and the regulation of cell adhesion in the nervous system: a control point for morphogenesis in development, disease and evolution?

    Science.gov (United States)

    Crossin, Kathryn L

    2012-01-01

    In this article, I discuss the hallmarks of hypoxia in vitro and in vivo and review work showing that many types of stem cell proliferate more robustly in lowered oxygen. I then discuss recent studies showing that alterations in the levels and the types of cell and substrate adhesion molecules are a notable response to reduced O(2) levels in both cultured primary neural stem cells and brain tissues in response to hypoxia in vivo. The ability of O(2) levels to regulate adhesion molecule expression is linked to the Wnt signaling pathway, which can control and be controlled by adhesion events. The ability of O(2) levels to influence cell adhesion also has far-reaching implications for development, ischemic trauma and neural regeneration, as well as for cancer and other diseases. Finally I discuss the possibility that the fluctuations in O(2) levels known to have occurred over evolutionary time could, by influencing adhesion systems, have contributed to early symbiotic events in unicellular organisms and to the emergence of multicellularity. It is not my intention to be exhaustive in these domains, which are far from my own field of study. Rather this article is meant to provoke and stimulate thinking about molecular evolution involving O(2) sensing and signaling during eras of geologic and atmospheric change that might inform modern studies on development and disease.

  14. Cyanobacterial Diazotrophy and Earth’s Delayed Oxygenation

    Science.gov (United States)

    Olson, Stephanie L.; Reinhard, Christopher T.; Lyons, Timothy W.

    2016-01-01

    The redox landscape of Earth’s ocean-atmosphere system has changed dramatically throughout Earth history. Although Earth’s protracted oxygenation is undoubtedly the consequence of cyanobacterial oxygenic photosynthesis, the relationship between biological O2 production and Earth’s redox evolution remains poorly understood. Existing models for Earth’s oxygenation cannot adequately explain the nearly 2.5 billion years delay between the origin of oxygenic photosynthesis and the oxygenation of the deep ocean, in large part owing to major deficiencies in our understanding of the coevolution of O2 and Earth’s key biogeochemical cycles (e.g., the N cycle). For example, although possible links between O2 and N scarcity have been previously explored, the consequences of N2 limitation for net biological O2 production have not been examined thoroughly. Here, we revisit the prevailing view that N2 fixation has always been able to keep pace with P supply and discuss the possibility that bioavailable N, rather than P, limited export production for extended periods of Earth’s history. Based on the observation that diazotrophy occurs at the expense of oxygenesis in the modern ocean, we suggest that an N-limited biosphere may be inherently less oxygenic than a P-limited biosphere—and that cyanobacterial diazotrophy was a primary control on the timing and tempo of Earth’s oxygenation by modulating net biogenic O2 fluxes. We further hypothesize that negative feedbacks inhibit the transition between N and P limitation, with the implication that the pervasive accumulation of O2 in Earth’s ocean-atmosphere system may not have been an inevitable consequence of oxygenic photosynthesis by marine cyanobacteria. PMID:27721813

  15. A facile strategy for the synthesis of NiSe@CoOOH core-shell nanowires on nickel foam with high surface area as efficient electrocatalyst for oxygen evolution reaction

    Science.gov (United States)

    Xu, Yuan-Zi; Yuan, Cheng-Zong; Chen, Xue-Ping

    2017-12-01

    In this article, we describe a NiSe@CoOOH core-shell nanostructure nanowires supported on nickel foam(NiSe@CoOOH NWs/NF) have been successfully synthesized by a facile approach for the first time. The NiSe@CoOOH NWs/NF has been confirmed by XRD, SEM images, TEM images, XPS, EDX and HRTEM. The NiSe@CoOOH NWs/NF, as a 3D oxygen-evolving and nonprecious-metal catalyst, shows high catalytic performance for oxygen evolution reaction.

  16. Evolution of N2(A3 \\Sigma _{u}^{+} ) in streamer discharges: influence of oxygen admixtures on formation of low vibrational levels

    Science.gov (United States)

    Šimek, M.; Ambrico, P. F.; Prukner, V.

    2017-12-01

    The formation of N2(A3 Σ u+ ) metastable species, produced by cathode-directed streamer discharge, was investigated using the technique of laser-induced fluorescence. A triggered single streamer filament was periodically produced in pure nitrogen (and in nitrogen with admixtures of oxygen) at total pressure of 50 Torr and metastable species were monitored during the streamer channel decay in the centre of the discharge gap. We revealed the dynamics of individual vibrational (v  =  0–8) levels of N2(A3 Σ u+ ) for various oxygen admixtures (0–20%). In pure nitrogen, the observed evolution of the N2(A3 Σ u+ ) during the decaying streamer channel is evidence of initial vibrational relaxation of high vibrational levels towards the v  =  2 and 3 levels, followed by a delayed increase of terminal (v  =  0, 1) levels. A calibration procedure based on the rate of energy-pooling processes was used to place all detected vibronic levels in pure nitrogen on the absolute scale. Population maxima exceeding 1  ×  1014 cm‑3 were fixed for the v  =  2 and 3 vibrational levels, while the lowest v  =  0 level reaches only 3  ×  1013 cm‑3. Populations of v  =  2–5 vibrational levels were also estimated for N2  +  O2 mixtures after scaling of laser-induced fluorescence signals obtained at various oxygen admixtures. The total N2(A3 Σ u+ ) population in an air-like mixture is formed mainly by v  =  3–4 vibronic levels with the population maximum of ~3  ×  1013 cm‑3 fixed at the shortest analyzed delay. This observation, together with the fact that we were unable to detect v  =  0 and 1 levels (fluorescence signals below detection threshold), gives a strong evidence of the inhibition of Δv  =  2 vibrational relaxation towards terminal v  =  0 and 1 levels, causing much lower populations of the lowest v  =  0–1 levels. By analyzing data obtained in

  17. WaveNet

    Science.gov (United States)

    2015-10-30

    Coastal Inlets Research Program WaveNet WaveNet is a web-based, Graphical-User-Interface ( GUI ) data management tool developed for Corps coastal...generates tabular and graphical information for project planning and design documents. The WaveNet is a web-based GUI designed to provide users with a...data from different sources, and employs a combination of Fortran, Python and Matlab codes to process and analyze data for USACE applications

  18. Coloured Petri Nets

    DEFF Research Database (Denmark)

    Jensen, Kurt

    1991-01-01

    This paper describes how Coloured Petri Nets (CP-nets) have been developed — from being a promising theoretical model to being a full-fledged language for the design, specification, simulation, validation and implementation of large software systems (and other systems in which human beings and...... use of CP-nets — because it means that the function representation and the translations (which are a bit mathematically complex) no longer are parts of the basic definition of CP-nets. Instead they are parts of the invariant method (which anyway demands considerable mathematical skills...

  19. Game Coloured Petri Nets

    DEFF Research Database (Denmark)

    Westergaard, Michael

    2006-01-01

    This paper introduces the notion of game coloured Petri nets. This allows the modeler to explicitly model what parts of the model comprise the modeled system and what parts are the environment of the modeled system. We give the formal definition of game coloured Petri nets, a means of reachability...... analysis of this net class, and an application of game coloured Petri nets to automatically generate easy-to-understand visualizations of the model by exploiting the knowledge that some parts of the model are not interesting from a visualization perspective (i.e. they are part of the environment...

  20. Programming NET Web Services

    CERN Document Server

    Ferrara, Alex

    2007-01-01

    Web services are poised to become a key technology for a wide range of Internet-enabled applications, spanning everything from straight B2B systems to mobile devices and proprietary in-house software. While there are several tools and platforms that can be used for building web services, developers are finding a powerful tool in Microsoft's .NET Framework and Visual Studio .NET. Designed from scratch to support the development of web services, the .NET Framework simplifies the process--programmers find that tasks that took an hour using the SOAP Toolkit take just minutes. Programming .NET

  1. Annotating Coloured Petri Nets

    DEFF Research Database (Denmark)

    Lindstrøm, Bo; Wells, Lisa Marie

    2002-01-01

    -net. An example of such auxiliary information is a counter which is associated with a token to be able to do performance analysis. Modifying colour sets and arc inscriptions in a CP-net to support a specific use may lead to creation of several slightly different CP-nets – only to support the different uses...... a method which makes it possible to associate auxiliary information, called annotations, with tokens without modifying the colour sets of the CP-net. Annotations are pieces of information that are not essential for determining the behaviour of the system being modelled, but are rather added to support...

  2. Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)

    2016-10-15

    Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

  3. Role of Short-Range Chemical Ordering in (GaN) 1–x (ZnO) x for Photodriven Oxygen Evolution

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dennis P. [Department; Neuefeind, Joerg C. [Chemical; Koczkur, Kallum M. [Department; Bish, David L. [Department; Skrabalak, Sara E. [Department

    2017-07-21

    (GaN)1–x(ZnO)x (GZNO) is capable of visible-light driven water splitting, but its bandgap at x ≤ 0.15 (>2.7 eV) results in poor visible-light absorption. Unfortunately, methods to narrow its bandgap by incorporating higher ZnO concentrations are accompanied by extensive Urbach tailing near the absorption-edge, which is indicative of structural disorder or chemical inhomogeneities. We evaluated whether this disorder is intrinsic to the bond-length distribution in GZNO or is a result of defects introduced from the loss of Zn during nitridation. Here, the synthesis of GZNO derived from layered double hydroxide (LDH) precursors is described which minimizes Zn loss and chemical inhomogeneities and enhances visible-light absorption. The average and local atomic structures of LDH-derived GZNO were investigated using X-ray and neutron scattering and are correlated with their oxygen evolution rates. An isotope-contrasted neutron-scattering experiment was conducted in conjunction with reverse Monte Carlo (RMC) simulations. We showed that a bond-valence bias in the RMC refinements reproduces the short-range ordering (SRO) observed in structure refinements using isotope-contrasted neutron data. The findings suggest that positional disorder of cation–anion pairs in GZNO partially arises from SRO and influences local bond relaxations. Furthermore, particle-based oxygen evolution reactions (OERs) in AgNO3 solution reveal that the crystallite size of GZNO correlates more than positional disorder with oxygen evolution rate. These findings illustrate the importance of examining the local structure of multinary photocatalysts to identify dominant factors in particulate-based photodriven oxygen evolution.

  4. Rational Construction of Hollow Core-Branch CoSe2 Nanoarrays for High-Performance Asymmetric Supercapacitor and Efficient Oxygen Evolution.

    Science.gov (United States)

    Chen, Tian; Li, Songzhan; Wen, Jian; Gui, Pengbin; Guo, Yaxiong; Guan, Cao; Liu, Jinping; Fang, Guojia

    2017-12-18

    Metal selenides have great potential for electrochemical energy storage, but are relatively scarce investigated. Herein, a novel hollow core-branch CoSe2 nanoarray on carbon cloth is designed by a facile selenization reaction of predesigned CoO nanocones. And the electrochemical reaction mechanism of CoSe2 in supercapacitor is studied in detail for the first time. Compared with CoO, the hollow core-branch CoSe2 has both larger specific surface area and higher electrical conductivity. When tested as a supercapacitor positive electrode, the CoSe2 delivers a high specific capacitance of 759.5 F g-1 at 1 mA cm-2 , which is much larger than that of CoO nanocones (319.5 F g-1 ). In addition, the CoSe2 electrode exhibits excellent cycling stability in that a capacitance retention of 94.5% can be maintained after 5000 charge-discharge cycles at 5 mA cm-2 . An asymmetric supercapacitor using the CoSe2 as cathode and an N-doped carbon nanowall as anode is further assembled, which show a high energy density of 32.2 Wh kg-1 at a power density of 1914.7 W kg-1 , and maintains 24.9 Wh kg-1 when power density increased to 7354.8 W kg-1 . Moreover, the CoSe2 electrode also exhibits better oxygen evolution reaction activity than that of CoO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni-Fe Oxide Water Splitting Electrocatalysts.

    Science.gov (United States)

    Görlin, Mikaela; Chernev, Petko; Ferreira de Araújo, Jorge; Reier, Tobias; Dresp, Sören; Paul, Benjamin; Krähnert, Ralph; Dau, Holger; Strasser, Peter

    2016-05-04

    Mixed Ni-Fe oxides are attractive anode catalysts for efficient water splitting in solar fuels reactors. Because of conflicting past reports, the catalytically active metal redox state of the catalyst has remained under debate. Here, we report an in operando quantitative deconvolution of the charge injected into the nanostructured Ni-Fe oxyhydroxide OER catalysts or into reaction product molecules. To achieve this, we explore the oxygen evolution reaction dynamics and the individual faradaic charge efficiencies using operando differential electrochemical mass spectrometry (DEMS). We further use X-ray absorption spectroscopy (XAS) under OER conditions at the Ni and Fe K-edges of the electrocatalysts to evaluate oxidation states and local atomic structure motifs. DEMS and XAS data consistently reveal that up to 75% of the Ni centers increase their oxidation state from +2 to +3, while up to 25% arrive in the +4 state for the NiOOH catalyst under OER catalysis. The Fe centers consistently remain in the +3 state, regardless of potential and composition. For mixed Ni100-xFex catalysts, where x exceeds 9 atomic %, the faradaic efficiency of O2 sharply increases from ∼30% to 90%, suggesting that Ni atoms largely remain in the oxidation state +2 under catalytic conditions. To reconcile the apparent low level of oxidized Ni in mixed Ni-Fe catalysts, we hypothesize that a kinetic competition between the (i) metal oxidation process and the (ii) metal reduction step during O2 release may account for an insignificant accumulation of detectable high-valent metal states if the reaction rate of process (ii) outweighs that of (i). We conclude that a discussion of the superior catalytic OER activity of Ni-FeOOH electrocatalysts in terms of surface catalysis and redox-inactive metal sites likely represents an oversimplification that fails to capture essential aspects of the synergisms at highly active Ni-Fe sites.

  6. Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2TxNanosheets for Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Zhao, Li; Dong, Biliang; Li, Shaozhou; Zhou, Lijun; Lai, Linfei; Wang, Zhiwei; Zhao, Shulin; Han, Min; Gao, Kai; Lu, Min; Xie, Xiaoji; Chen, Bo; Liu, Zhengdong; Wang, Xiangjing; Zhang, Hao; Li, Hai; Liu, Juqing; Zhang, Hua; Huang, Xiao; Huang, Wei

    2017-06-27

    Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti 3 C 2 T x (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm -2 at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec -1 in 0.1 M KOH. These results outperform those obtained by the standard IrO 2 -based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti 3 C 2 T x nanosheets enabled the rapid charge and ion transfer across the well-defined Ti 3 C 2 T x -CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

  7. Net zero water

    CSIR Research Space (South Africa)

    Lindeque, M

    2013-01-01

    Full Text Available Is it possible to develop a building that uses a net zero amount of water? In recent years it has become evident that it is possible to have buildings that use a net zero amount of electricity. This is possible when the building is taken off...

  8. SolNet

    DEFF Research Database (Denmark)

    Jordan, Ulrike; Vajen, Klaus; Bales, Chris

    2014-01-01

    SolNet, founded in 2006, is the first coordinated International PhD education program on Solar Thermal Engineering. The SolNet network is coordinated by the Institute of Thermal Engineering at Kassel University, Germany. The network offers PhD courses on solar heating and cooling, conference...

  9. Kunstige neurale net

    DEFF Research Database (Denmark)

    Hørning, Annette

    1994-01-01

    Artiklen beskæftiger sig med muligheden for at anvende kunstige neurale net i forbindelse med datamatisk procession af naturligt sprog, specielt automatisk talegenkendelse.......Artiklen beskæftiger sig med muligheden for at anvende kunstige neurale net i forbindelse med datamatisk procession af naturligt sprog, specielt automatisk talegenkendelse....

  10. Pro NET Best Practices

    CERN Document Server

    Ritchie, Stephen D

    2011-01-01

    Pro .NET Best Practices is a practical reference to the best practices that you can apply to your .NET projects today. You will learn standards, techniques, and conventions that are sharply focused, realistic and helpful for achieving results, steering clear of unproven, idealistic, and impractical recommendations. Pro .NET Best Practices covers a broad range of practices and principles that development experts agree are the right ways to develop software, which includes continuous integration, automated testing, automated deployment, and code analysis. Whether the solution is from a free and

  11. Getting to Net Zero

    Energy Technology Data Exchange (ETDEWEB)

    2016-09-01

    The technology necessary to build net zero energy buildings (NZEBs) is ready and available today, however, building to net zero energy performance levels can be challenging. Energy efficiency measures, onsite energy generation resources, load matching and grid interaction, climatic factors, and local policies vary from location to location and require unique methods of constructing NZEBs. It is recommended that Components start looking into how to construct and operate NZEBs now as there is a learning curve to net zero construction and FY 2020 is just around the corner.

  12. Instant Lucene.NET

    CERN Document Server

    Heydt, Michael

    2013-01-01

    Filled with practical, step-by-step instructions and clear explanations for the most important and useful tasks. A step-by-step guide that helps you to index, search, and retrieve unstructured data with the help of Lucene.NET.Instant Lucene.NET How-to is essential for developers new to Lucene and Lucene.NET who are looking to get an immediate foundational understanding of how to use the library in their application. It's assumed you have programming experience in C# already, but not that you have experience with search techniques such as information retrieval theory (although there will be a l

  13. Oxygen isotope evolution of the Lake Owyhee volcanic field, Oregon, and implications for low-δ18O magmas of the Snake River Plain - Yellowstone hotspot

    Science.gov (United States)

    Blum, T.; Kitajima, K.; Nakashima, D.; Valley, J. W.

    2013-12-01

    The Snake River Plain - Yellowstone (SRP-Y) hotspot trend is one of the largest known low-δ18O magmatic provinces, yet the timing and distribution of hydrothermal alteration relative to hotspot magmatism remains incompletely understood. Existing models for SRP-Y low-δ18O magma genesis differ regarding the timing of protolith alteration (e.g. Eocene vs. present), depth at which alteration occurs (e.g. 15 km vs. caldera collapse, crustal scale fluid flow, etc.). We expand the existing oxygen isotope data set for zircon in the Lake Owyhee volcanic field (LOVF) of east central Oregon to further identify magmatic oxygen isotope trends within the field. These data offer insight into the timing of alteration and the extent of the greater SRP-Y low-δ18O province, as well as the conditions that generate large low-δ18O provinces. 16-14 Ma silicic volcanism in the LOVF is linked to the pre-14 Ma SRP-Y hotspot, with volcanism partially overlapping extension in the north-south trending Oregon-Idaho Graben (OIG). Ion microprobe analyses of zircons from 16 LOVF silicic lavas and tuffs reveal homogeneous zircons on both the single grain and hand sample scales: individual samples have 2 S.D. for δ18O ranging from 0.27 to 0.96‰ (SMOW), and sample averages ranging from 1.8 to 6.0‰, excluding texturally chaotic and/or porous zircons which have δ18O values as low as 0.0‰. All low-δ18O LOVF magmas, including the caldera-forming Tuff of Leslie Gulch and Tuff of Spring Creek, are confined to the OIG, although not all zircons from within the OIG have low δ18O values. The presence and sequence of low-δ18O magmas in the LOVF and adjacent central Snake River Plain (CSRP) cannot be explained by existing caldera subsidence or pre-hotspot source models. These data, however, combined with volumetrically limited low-δ18O material in the adjacent Idaho Batholith and Basin and Range, are consistent with low-δ18O magmas generated by the superposition of high hotspot-derived thermal

  14. Tuning crystal phase of NiS{sub x} through electro-oxidized nickel foam: A novel route for preparing efficient electrocatalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Rao, Yi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580, PR China (China); Hu, Wen-Hui; Liu, Yan-Ru; Yan, Kai-Li; Chi, Jing-Qi; Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-02-28

    Highlights: • Electro-oxidized nickel foam as a support has been used to prepare NiS{sub x} phases. • Ni(OH){sub 2} layer on electro-oxidized NF is responsible for the growth of β-NiS. • NiS{sub x}/NF(Ox) composed of β-NiS and Ni{sub 3}S{sub 2} has enhanced electrocatalytic activity. • The growth mechanisms of mixed NiS{sub x} phases of NiS{sub x}/NF(Ox) have been discussed. - Abstract: A facile solvothermal sulfurization using electro-oxidized nickel foam (NF(Ox)) as support has been applied to prepare NiS{sub x}/NF(Ox) electrocatalyst with highly efficient activity for oxygen evolution reaction (OER). XRD patterns confirm the composition of NiS{sub x}/NF(Ox): two kinds of crystal phase including β-NiS and Ni{sub 3}S{sub 2}. While using bare NF as support under identical conditions, only Ni{sub 3}S{sub 2} phase can be detected. SEM images reveal two kinds of morphologies of NiS{sub x}/NF(Ox) including pyramids structure of β-NiS and nanorod-like structure of Ni{sub 3}S{sub 2}, which implies the tuning effect of electro-pretreatment of NF on the selective preparation of NiS{sub x} crystal phase. It can be speculated that Ni(OH){sub 2} layer derived from electro-oxidized NF is responsible for the growth of β-NiS while metallic Ni is transformed into Ni{sub 2}S{sub 3} during sulfurization. Electrochemical measurements for OER indicate the enhanced electrocatalytic activity of NiS{sub x}/NF(Ox) with a small overpotential of 72 mV to reach 10 mA cm{sup −2} compared with Ni{sub 3}S{sub 2}/NF, which may be ascribed to the improved electron-transfer kinetics relating to the unique atomic configurations and crystalline structures of β-NiS. The electro-oxidation pretreatment of nickel foam provides a simple and convenient method by tuning different NiS{sub x} crystal phases for preparing excellent OER eletrocatalysts.

  15. Highly effective Ir(x)Sn(1-x)O2 electrocatalysts for oxygen evolution reaction in the solid polymer electrolyte water electrolyser.

    Science.gov (United States)

    Li, Guangfu; Yu, Hongmei; Wang, Xunying; Sun, Shucheng; Li, Yongkun; Shao, Zhigang; Yi, Baolian

    2013-02-28

    We developed an advanced surfactant-assistant method for the Ir(x)Sn(1-x)O(2) (0 < x ≤ 1) nanoparticle (NP) preparation, and examined the OER performances by a series of half-cell and full-cell tests. In contrast to the commercial Ir black, the collective data confirmed the outstanding activity and stability of the fabricated Ir(x)Sn(1-x)O(2) (x = 1, 0.67 and 0.52) NPs, which could be ascribed to the amorphous structure, good dispersion, high pore volume, solid-solution state and Ir-rich surface for bi-metal oxides, and relatively large size (10-11 nm), while Ir(0.31)Sn(0.69) exhibited poor electro-catalytic activity because of the separated two phases, a SnO(2)-rich phase and an IrO(2)-rich phase. Furthermore, compared with highly active IrO(2), the improved durability, precious-metal Ir utilization efficiency and correspondingly reduced Ir loading were realized by the addition of Sn component. When the Ir(0.52)Sn(0.48)O(2) cell operated at 80 °C using Nafion® 115 membrane and less than 0.8 mg cm(-2) of the noble-metal Ir loading, the cell voltages we achieved were 1.631 V at 1000 mA cm(-2), and 1.821 V at 2000 mA cm(-2). The IR-free voltage at the studied current density was very close to the onset voltage of oxygen evolution. The only 50 μV h(-1) of voltage increased for the 500 h durability test at 500 mA cm(-2). In fact, these results are exceptional compared to the performances for OER in SPEWE cells known so far. This work highlights the potential of using highly active and stable IrO(2)-SnO(2) amorphous NPs to enhance the electrolysis efficiency, reduce the noble-metal Ir loading and thus the cost of hydrogen production from the solid polymer electrolyte water electrolysis.

  16. Recovered spinel MnCo2O4 from spent lithium-ion batteries for enhanced electrocatalytic oxygen evolution in alkaline medium.

    Science.gov (United States)

    Natarajan, Subramanian; Anantharaj, S; Tayade, Rajesh J; Bajaj, Hari C; Kundu, Subrata

    2017-10-24

    A facile way of recovering 3d transition metals of industrial importance from spent lithium-ion batteries (LIBs) without using any surfactants has been developed. Mn- and Co-rich spent LIBs were chosen as sustainable sources for recovering the oxides of the respective elements. The physical dismantling of Li-ion batteries, chemical leaching with 2 M acetic acid, precipitation with ammonium carbonate, hydrothermal conditioning and calcination at 650 °C led to the facile formation of spherical spinel MnCo2O4 with very high morphological selectivity. The obtained spherical MnCo2O4 was identified by various advanced characterization techniques. Detailed electrochemical characterization revealed that the recovered spheres of spinel MnCo2O4 were effective in catalyzing the oxygen evolution reaction (OER) in 1 M KOH and required an overpotential of 358 and 400 mV to generate a current density of 5 and 10 mA cm-2, respectively, with a relatively low catalyst loading (0.001025 g cm-2). Comparative electrocatalytic studies carried out with recovered LiCoO2, recovered LiXMnOX+1 and commercially available catalysts such as RuO2 (c-RuO2), Co3O4 (c-Co3O4) and MnO2 (c-MnO2) revealed that the recovered spheres of spinel MnCo2O4 were more effective OER catalysts than the recovered LiCoO2, recovered LiXMnOX+1, c-Co3O4 and c-MnO2 and exhibited comparable activity to that of c-RuO2 with very little difference in overpotential (∼50 mV) at current densities of 5 and 10 mA cm-2. With such a low catalyst loading, the observed electrocatalytic performance in water oxidation of a material recovered from waste is highly significant and will surely attain greater industrial importance when the recycling of spent LIBs from electronic wastes is considered.

  17. Net Zero Energy Buildings

    DEFF Research Database (Denmark)

    Marszal, Anna Joanna; Bourrelle, Julien S.; Musall, Eike

    2010-01-01

    and identify possible renewable energy supply options which may be considered in calculations. Finally, the gap between the methodology proposed by each organisation and their respective national building code is assessed; providing an overview of the possible changes building codes will need to undergo......The international cooperation project IEA SHC Task 40 / ECBCS Annex 52 “Towards Net Zero Energy Solar Buildings”, attempts to develop a common understanding and to set up the basis for an international definition framework of Net Zero Energy Buildings (Net ZEBs). The understanding of such buildings...... parameters used in the calculations are discussed and the various renewable supply options considered in the methodologies are summarised graphically. Thus, the paper helps to understand different existing approaches to calculate energy balance in Net ZEBs, highlights the importance of variables selection...

  18. PhysioNet

    Data.gov (United States)

    U.S. Department of Health & Human Services — The PhysioNet Resource is intended to stimulate current research and new investigations in the study of complex biomedical and physiologic signals. It offers free...

  19. NetSig

    DEFF Research Database (Denmark)

    Horn, Heiko; Lawrence, Michael S; Chouinard, Candace R

    2018-01-01

    Methods that integrate molecular network information and tumor genome data could complement gene-based statistical tests to identify likely new cancer genes; but such approaches are challenging to validate at scale, and their predictive value remains unclear. We developed a robust statistic (Net......Sig) that integrates protein interaction networks with data from 4,742 tumor exomes. NetSig can accurately classify known driver genes in 60% of tested tumor types and predicts 62 new driver candidates. Using a quantitative experimental framework to determine in vivo tumorigenic potential in mice, we found that Net......Sig candidates induce tumors at rates that are comparable to those of known oncogenes and are ten-fold higher than those of random genes. By reanalyzing nine tumor-inducing NetSig candidates in 242 patients with oncogene-negative lung adenocarcinomas, we find that two (AKT2 and TFDP2) are significantly amplified...

  20. Earliest land plants created modern levels of atmospheric oxygen

    Science.gov (United States)

    Lenton, Timothy M.; Dahl, Tais W.; Daines, Stuart J.; Mills, Benjamin J. W.; Ozaki, Kazumi; Saltzman, Matthew R.; Porada, Philipp

    2016-01-01

    The progressive oxygenation of the Earth’s atmosphere was pivotal to the evolution of life, but the puzzle of when and how atmospheric oxygen (O2) first approached modern levels (∼21%) remains unresolved. Redox proxy data indicate the deep oceans were oxygenated during 435–392 Ma, and the appearance of fossil charcoal indicates O2 >15–17% by 420–400 Ma. However, existing models have failed to predict oxygenation at this time. Here we show that the earliest plants, which colonized the land surface from ∼470 Ma onward, were responsible for this mid-Paleozoic oxygenation event, through greatly increasing global organic carbon burial—the net long-term source of O2. We use a trait-based ecophysiological model to predict that cryptogamic vegetation cover could have achieved ∼30% of today’s global terrestrial net primary productivity by ∼445 Ma. Data from modern bryophytes suggests this plentiful early plant material had a much higher molar C:P ratio (∼2,000) than marine biomass (∼100), such that a given weathering flux of phosphorus could support more organic carbon burial. Furthermore, recent experiments suggest that early plants selectively increased the flux of phosphorus (relative to alkalinity) weathered from rocks. Combining these effects in a model of long-term biogeochemical cycling, we reproduce a sustained +2‰ increase in the carbonate carbon isotope (δ13C) record by ∼445 Ma, and predict a corresponding rise in O2 to present levels by 420–400 Ma, consistent with geochemical data. This oxygen rise represents a permanent shift in regulatory regime to one where fire-mediated negative feedbacks stabilize high O2 levels. PMID:27528678

  1. TideNet

    Science.gov (United States)

    2015-10-30

    query tide data sources in a desired geographic region of USA and its territories (Figure 1). Users can select a tide data source through the Google Map ...select data sources according to the desired geographic region. It uses the Google Map interface to display data from different sources. Recent...Coastal Inlets Research Program TideNet The TideNet is a web-based Graphical User Interface (GUI) that provides users with GIS mapping tools to

  2. Building Neural Net Software

    OpenAIRE

    Neto, João Pedro; Costa, José Félix

    1999-01-01

    In a recent paper [Neto et al. 97] we showed that programming languages can be translated on recurrent (analog, rational weighted) neural nets. The goal was not efficiency but simplicity. Indeed we used a number-theoretic approach to machine programming, where (integer) numbers were coded in a unary fashion, introducing a exponential slow down in the computations, with respect to a two-symbol tape Turing machine. Implementation of programming languages in neural nets turns to be not only theo...

  3. Interaction Nets in Russian

    OpenAIRE

    Salikhmetov, Anton

    2013-01-01

    Draft translation to Russian of Chapter 7, Interaction-Based Models of Computation, from Models of Computation: An Introduction to Computability Theory by Maribel Fernandez. "In this chapter, we study interaction nets, a model of computation that can be seen as a representative of a class of models based on the notion of 'computation as interaction'. Interaction nets are a graphical model of computation devised by Yves Lafont in 1990 as a generalisation of the proof structures of linear logic...

  4. Programming NET 35

    CERN Document Server

    Liberty, Jesse

    2009-01-01

    Bestselling author Jesse Liberty and industry expert Alex Horovitz uncover the common threads that unite the .NET 3.5 technologies, so you can benefit from the best practices and architectural patterns baked into the new Microsoft frameworks. The book offers a Grand Tour" of .NET 3.5 that describes how the principal technologies can be used together, with Ajax, to build modern n-tier and service-oriented applications. "

  5. MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Biaohua [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; He, Xiaobo [Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China; Yin, Fengxiang [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China; Wang, Hao [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Liu, Di-Jia [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Shi, Ruixing [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Chen, Jinnan [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Yin, Hongwei [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China

    2017-06-14

    A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-x and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO2.

  6. Activation of PAD4 in NET formation

    Directory of Open Access Journals (Sweden)

    Amanda eRohrbach

    2012-11-01

    Full Text Available Peptidyl arginine deiminases, or PADs, convert arginine residues to the non-ribosomally encoded amino acid citrulline in a variety of protein substrates. PAD4 is expressed in granulocytes and is essential for the formation of neutrophil extracellular traps (NETs via PAD4-mediated histone citrullination. Citrullination of histones is thought to promote NET formation by inducing chromatin decondensation and facilitating the expulsion of chromosomal DNA that is coated with antimicrobial molecules. Numerous stimuli have been reported to lead to PAD4 activation and NET formation. However, how this signaling process proceeds and how PAD4 becomes activated in cells is largely unknown. Herein, we describe the various stimuli and signaling pathways that have been implicated in PAD4 activation and NET formation, including the role of reactive oxygen species generation. To provide a foundation for the above discussion, we first describe PAD4 structure and function, and how these studies led to the development of PAD-specific inhibitors. A comprehensive survey of the receptors and signaling pathways that regulate PAD4 activation will be important for our understanding of innate immunity, and the identification of signaling intermediates in PAD4 activation may also lead to the generation of pharmaceuticals to target NET-related pathogenesis.

  7. Modest net autotrophy in the oligotrophic ocean

    Science.gov (United States)

    Letscher, Robert T.; Moore, J. Keith

    2017-04-01

    The metabolic state of the oligotrophic subtropical ocean has long been debated. Net community production (NCP) represents the balance of autotrophic carbon fixation with heterotrophic respiration. Many in vitro NCP estimates based on oxygen incubation methods and the corresponding scaling relationships used to predict the ecosystem metabolic balance have suggested the ocean gyres to be net heterotrophic; however, all in situ NCP methods find net autotrophy. Reconciling net heterotrophy requires significant allochthonous inputs of organic carbon to the oligotrophic gyres to sustain a preponderance of respiration over in situ production. Here we use the first global ecosystem-ocean circulation model that contains representation of the three allochthonous carbon sources to the open ocean, to show that the five oligotrophic gyres exhibit modest net autotrophy throughout the seasonal cycle. Annually integrated rates of NCP vary in the range 1.5-2.2 mol O2 m-2 yr-1 across the five gyre systems; however, seasonal NCP rates are as low as 1 ± 0.5 mmol O2 m-2 d-1 for the North Atlantic. Volumetric NCP rates are heterotrophic below the 10% light level; however, they become net autotrophic when integrated over the euphotic zone. Observational uncertainties when measuring these modest autotrophic NCP rates as well as the metabolic diversity encountered across space and time complicate the scaling up of in vitro measurements to the ecosystem scale and may partially explain the previous reports of net heterotrophy. The oligotrophic ocean is autotrophic at present; however, it could shift toward seasonal heterotrophy in the future as rising temperatures stimulate respiration.

  8. La plataforma .NET

    OpenAIRE

    Fornas Estrada, Miquel

    2008-01-01

    L'aparició de la plataforma .NET Framework ha suposat un canvi molt important en la forma de crear i distribuir aplicacions, degut a que incorpora una sèrie d'innovacions tècniques i productives que simplifiquen molt les tasques necessàries per desenvolupar un projecte. La aparición de la plataforma. NET Framework ha supuesto un cambio muy importante en la forma de crear y distribuir aplicaciones, debido a que incorpora una serie de innovaciones técnicas y productivas que simplifican mucho...

  9. Biological Petri Nets

    CERN Document Server

    Wingender, E

    2011-01-01

    It was suggested some years ago that Petri nets might be well suited to modeling metabolic networks, overcoming some of the limitations encountered by the use of systems employing ODEs (ordinary differential equations). Much work has been done since then which confirms this and demonstrates the usefulness of this concept for systems biology. Petri net technology is not only intuitively understood by scientists trained in the life sciences, it also has a robust mathematical foundation and provides the required degree of flexibility. As a result it appears to be a very promising approach to mode

  10. Oxygen Therapy

    Science.gov (United States)

    ... of oxygen rather than a continuous flow. Before purchasing or renting a portable oxygen concentrator, ask your ... and with activity when using your oxygen delivery system. ✔ ✔ Do not smoke, especially around any oxygen devices. ✔ ✔ Avoid being around ... information is a public service of the American Thoracic ...

  11. Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

    Science.gov (United States)

    Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

    2017-10-01

    Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

  12. Petri Nets-Applications

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 4; Issue 9. Petri Nets - Applications. Y Narahari. General Article Volume 4 Issue 9 September 1999 pp 44-52. Fulltext. Click here to view fulltext PDF. Permanent link: http://www.ias.ac.in/article/fulltext/reso/004/09/0044-0052. Author Affiliations. Y Narahari ...

  13. Safety nets or straitjackets?

    DEFF Research Database (Denmark)

    Ilsøe, Anna

    2012-01-01

    Does regulation of working hours at national and sector level impose straitjackets, or offer safety nets to employees seeking working time flexibility? This article compares legislation and collective agreements in the metal industries of Denmark, Germany and the USA. The industry has historically...

  14. Coloured Petri Nets

    CERN Document Server

    Jensen, Kurt

    2009-01-01

    Coloured Petri Nets (CPN) is a graphical language for modelling and validating concurrent and distributed systems, and other systems in which concurrency plays a major role. This book introduces the constructs of the CPN modelling language and presents the related analysis methods. It provides a comprehensive road map for the practical use of CPN.

  15. Boom Booom Net Radio

    DEFF Research Database (Denmark)

    Grimshaw, Mark Nicholas; Yong, Louisa; Dobie, Ian

    1999-01-01

    of an existing Internet radio station; Boom Booom Net Radio. Whilst necessity dictates some use of technology-related terminology, wherever possible we have endeavoured to keep such jargon to a minimum and to either explain it in the text or to provide further explanation in the appended glossary....

  16. Game Theory .net.

    Science.gov (United States)

    Shor, Mikhael

    2003-01-01

    States making game theory relevant and accessible to students is challenging. Describes the primary goal of GameTheory.net is to provide interactive teaching tools. Indicates the site strives to unite educators from economics, political and computer science, and ecology by providing a repository of lecture notes and tests for courses using…

  17. Coloured Petri Nets

    DEFF Research Database (Denmark)

    Jensen, Kurt; Kristensen, Lars Michael

    Coloured Petri Nets (CPN) is a graphical language for modelling and validating concurrent and distributed systems, and other systems in which concurrency plays a major role. The development of such systems is particularly challenging because of inherent intricacies like possible nondeterminism...

  18. In Situ Derived NixFe1-xOOH/NiFe/NixFe1-xOOH Nanotube Arrays from NiFe Alloys as Efficient Electrocatalysts for Oxygen Evolution.

    Science.gov (United States)

    Wang, An-Liang; Dong, Yu-Tao; Li, Mei; Liang, Chaolun; Li, Gao-Ren

    2017-10-11

    Herein, Ni x Fe 1-x OOH/NiFe/Ni x Fe 1-x OOH sandwich-structured nanotube arrays (SNTAs) supported on carbon fiber cloth (CFC) (Ni x Fe 1-x OOH/NiFe/Ni x Fe 1-x OOH SNTAs-CFC) have been developed as flexible high-performance oxygen evolution reaction (OER) catalysts by a facile in situ electrochemical oxidation of NiFe metallic alloy nanotube arrays during oxygen evolution process. Benefiting from the advantages of high conductivity, hollow nanotube array, and porous structure, Ni x Fe 1-x OOH/NiFe/Ni x Fe 1-x OOH SNTAs-CFC exhibited a low overpotential of ∼220 mV at the current density of 10 mA cm -2 and a small Tafel slope of 57 mV dec -1 in alkaline solution, both of which are smaller than those of most OER electrocatalysts. Furthermore, Ni x Fe 1-x OOH/NiFe/Ni x Fe 1-x OOH SNTAs-CFC exhibits excellent stability at 100 mA cm -2 for more than 30 h. It is believed that the present work can provide a valuable route for the design and synthesis of inexpensive and efficient OER electrocatalysts.

  19. Cyanobacterial diazotrophy and Earth's delayed oxygenation

    OpenAIRE

    Olson, Stephanie L.; Reinhard, Christopher T.; Lyons, Timothy W.

    2016-01-01

    The redox landscape of Earth’s ocean-atmosphere system has changed dramatically throughout Earth history. Although Earth’s protracted oxygenation is undoubtedly the consequence of cyanobacterial oxygenic photosynthesis, the relationship between biological O2 production and Earth’s redox evolution remains poorly understood. Existing models for Earth’s oxygenation cannot adequately explain the nearly 2.5 billion year delay between the origin of oxygenic photosynthesis and the oxygenation of the...

  20. Genetic and epigenetic drivers of neuroendocrine tumours (NET).

    Science.gov (United States)

    Di Domenico, Annunziata; Wiedmer, Tabea; Marinoni, Ilaria; Perren, Aurel

    2017-09-01

    Neuroendocrine tumours (NET) of the gastrointestinal tract and the lung are a rare and heterogeneous group of tumours. The molecular characterization and the clinical classification of these tumours have been evolving slowly and show differences according to organs of origin. Novel technologies such as next-generation sequencing revealed new molecular aspects of NET over the last years. Notably, whole-exome/genome sequencing (WES/WGS) approaches underlined the very low mutation rate of well-differentiated NET of all organs compared to other malignancies, while the engagement of epigenetic changes in driving NET evolution is emerging. Indeed, mutations in genes encoding for proteins directly involved in chromatin remodelling, such as DAXX and ATRX are a frequent event in NET. Epigenetic changes are reversible and targetable; therefore, an attractive target for treatment. The discovery of the mechanisms underlying the epigenetic changes and the implication on gene and miRNA expression in the different subgroups of NET may represent a crucial change in the diagnosis of this disease, reveal new therapy targets and identify predictive markers. Molecular profiles derived from omics data including DNA mutation, methylation, gene and miRNA expression have already shown promising results in distinguishing clinically and molecularly different subtypes of NET. In this review, we recapitulate the major genetic and epigenetic characteristics of pancreatic, lung and small intestinal NET and the affected pathways. We also discuss potential epigenetic mechanisms leading to NET development. © 2017 Society for Endocrinology.

  1. Food Safety Nets:

    OpenAIRE

    Haggblade, Steven; Diallo, Boubacar; Staatz, John; Theriault, Veronique; Traoré, Abdramane

    2013-01-01

    Food and social safety nets have a history as long as human civilization. In hunter gatherer societies, food sharing is pervasive. Group members who prove unlucky in the short run, hunting or foraging, receive food from other households in anticipation of reciprocal consideration at a later time (Smith 1988). With the emergence of the first large sedentary civilizations in the Middle East, administrative systems developed specifically around food storage and distribution. The ancient Egyptian...

  2. Net technical assessment

    OpenAIRE

    Wegmann, David G.

    1989-01-01

    Approved for public release; distribution is unlimited. The present and near term military balance of power between the U.S. and the Soviet Union can be expressed in a variety of net assessments. One can examine the strategic nuclear balance, the conventional balance in Europe, the maritime balance, and many others. Such assessments are essential not only for policy making but for arms control purposes and future force structure planning. However, to project the future military balance, on...

  3. Using WordNet for Building WordNets

    CERN Document Server

    Farreres, X; Farreres, Xavier; Rodriguez, Horacio; Rigau, German

    1998-01-01

    This paper summarises a set of methodologies and techniques for the fast construction of multilingual WordNets. The English WordNet is used in this approach as a backbone for Catalan and Spanish WordNets and as a lexical knowledge resource for several subtasks.

  4. Surface Characterization and Electrocatalytic Properties of the Ti/Ir0.3Ti(0.7-xPbx O2-Coated Electrodes for Oxygen Evolution Reaction in Acidic Media

    Directory of Open Access Journals (Sweden)

    Oliveira-Sousa Adriana de

    2002-01-01

    Full Text Available In this work a systematic investigation was carried out of the surface characterization and electrocatalytic activity of Ti/Ir0.3Ti(0.7-xPb x O2-coated electrodes (0 <= x <= 0.7, using the oxygen evolution reaction (OER in 0.5 mol dm-3 H2SO4 as model. The electrodes were prepared by thermal decomposition of IrCl3, TiCl3 and Pb(NO32 at 600 °C for 1 h using Ti as support. X-ray diffraction shows that the layers are crystalline and that the corresponding metal oxides are present. The surface morphology of the samples, before and after use under extensive oxygen evolution (Tafel experiment, was characterized by Scanning Electron Microscopy and the micrograph analyses show that the OER promotes the dissolution of the oxide layer. The redox processes occurring on the surface were characterized by cyclic voltammetry at 20 mV s-1 in 0.5 mol dm-3 aqueous H2SO4, at room temperature, and were controlled by the Ir3+/Ir4+ couple. The measured anodic voltammetric charge is related to the active area of the electrode showing that the replacement of TiO2 by PbO2 increases the surface area with the higher value being at 50 mol% PbO2. After oxygen evolution, the surface area increases slightly. Tafel slopes are independent of Pb content with the values around 60 mV decade-1, which suggest that only Ir sites are active for OER. The values of normalized current (i/q a show some inhibition of the OER as TiO2 is replaced by PbO2 suggesting that PbO2, can be a good choice, with potential to improve the selectivity of the system. The reaction order with respect to H+ ion is zero at constant overpotential and ionic strength. The values of Tafel slope and reaction order indicate that a single reaction mechanism is operating.

  5. Proof nets for lingusitic analysis

    NARCIS (Netherlands)

    Moot, R.C.A.

    2002-01-01

    This book investigates the possible linguistic applications of proof nets, redundancy free representations of proofs, which were introduced by Girard for linear logic. We will adapt the notion of proof net to allow the formulation of a proof net calculus which is soundand complete for the

  6. Teaching Tennis for Net Success.

    Science.gov (United States)

    Young, Bryce

    1989-01-01

    A program for teaching tennis to beginners, NET (Net Easy Teaching) is described. The program addresses three common needs shared by tennis students: active involvement in hitting the ball, clearing the net, and positive reinforcement. A sample lesson plan is included. (IAH)

  7. Net4Care Ecosystem Website

    DEFF Research Database (Denmark)

    Christensen, Henrik Bærbak; Hansen, Klaus Marius; Rasmussen, Morten

    2012-01-01

    is a tele-monitoring scenario in which Net4Care clients are deployed in a gateway in private homes. Medical devices then connect to these gateways and transmit their observations to a Net4Care server. In turn the Net4Care server creates valid clinical HL7 documents, stores them in a national XDS repository...

  8. One-pot Synthesis of CdS Irregular Nanospheres Hybridized with Oxygen-Incorporated Defect-Rich MoS2Ultrathin Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Zhang, Shouwei; Yang, Hongcen; Gao, Huihui; Cao, Ruya; Huang, Jinzhao; Xu, Xijin

    2017-07-19

    Robust and highly active photocatalysts, CdS@MoS 2 , for hydrogen evolution were successfully fabricated by one-step growth of oxygen-incorporated defect-rich MoS 2 ultrathin nanosheets on the surfaces of CdS with irregular fissures. Under optimized experimental conditions, the CdS@MoS 2 displayed a quantum yield of ∼24.2% at 420 nm and the maximum H 2 generation rate of ∼17203.7 umol/g/h using Na 2 S-Na 2 SO 3 as sacrificial agents (λ ≥ 420 nm), which is ∼47.3 and 14.7 times higher than CdS (∼363.8 μmol/g/h) and 3 wt % Pt/CdS (∼1173.2 μmol/g/h), respectively, and far exceeds all previous hydrogen evolution reaction photocatalysts with MoS 2 as co-catalysts using Na 2 S-Na 2 SO 3 as sacrificial agents. Large volumes of hydrogen bubbles were generated within only 2 s as the photocatalysis started, as demonstrated by the photocatalytic video. The high hydrogen evolution activity is attributed to several merits: (1) the intimate heterojunctions formed between the MoS 2 and CdS can effectively enhance the charge transfer ability and retard the recombination of electron-hole pairs; and (2) the defects in the MoS 2 provide additional active S atoms on the exposed edge sites, and the incorporation of O reduces the energy barrier for H 2 evolution and increases the electric conductivity of the MoS 2 . Considering its low cost and high efficiency, this highly efficient hybrid photocatalysts would have great potential in energy-generation and environment-restoration fields.

  9. Oxygen - A Four Billion Year History

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    the records of oxygen concentrations through time. Readers learn about the great oxidation event, the tipping point 2.3 billion years ago when the oxygen content of the Earth increased dramatically, and Canfield examines how oxygenation created a favorable environment for the evolution of large animals. He...

  10. Multi-net optimization of VLSI interconnect

    CERN Document Server

    Moiseev, Konstantin; Wimer, Shmuel

    2015-01-01

    This book covers layout design and layout migration methodologies for optimizing multi-net wire structures in advanced VLSI interconnects. Scaling-dependent models for interconnect power, interconnect delay and crosstalk noise are covered in depth, and several design optimization problems are addressed, such as minimization of interconnect power under delay constraints, or design for minimal delay in wire bundles within a given routing area. A handy reference or a guide for design methodologies and layout automation techniques, this book provides a foundation for physical design challenges of interconnect in advanced integrated circuits.  • Describes the evolution of interconnect scaling and provides new techniques for layout migration and optimization, focusing on multi-net optimization; • Presents research results that provide a level of design optimization which does not exist in commercially-available design automation software tools; • Includes mathematical properties and conditions for optimal...

  11. Master Robotic Net

    Directory of Open Access Journals (Sweden)

    Vladimir Lipunov

    2010-01-01

    Full Text Available The main goal of the MASTER-Net project is to produce a unique fast sky survey with all sky observed over a single night down to a limiting magnitude of 19-20. Such a survey will make it possible to address a number of fundamental problems: search for dark energy via the discovery and photometry of supernovae (including SNIa, search for exoplanets, microlensing effects, discovery of minor bodies in the Solar System, and space-junk monitoring. All MASTER telescopes can be guided by alerts, and we plan to observe prompt optical emission from gamma-ray bursts synchronously in several filters and in several polarization planes.

  12. Art/Net/Work

    DEFF Research Database (Denmark)

    Andersen, Christian Ulrik; Lindstrøm, Hanne

    2006-01-01

    The seminar Art|Net|Work deals with two important changes in our culture. On one side, the network has become essential in the latest technological development. The Internet has entered a new phase, Web 2.0, including the occurrence of as ‘Wiki’s’, ‘Peer-2-Peer’ distribution, user controlled...... the praxis of the artist. We see different kinds of interventions and activism (including ‘hacktivism’) using the network as a way of questioning the invisible rules that govern public and semi-public spaces. Who ‘owns’ them? What kind of social relationships do they generate? On what principle...

  13. Oxygen levels and the regulation of cell adhesion in the nervous system: A control point for morphogenesis in development, disease and evolution?

    OpenAIRE

    Crossin, Kathryn

    2012-01-01

    In this article, I discuss the hallmarks of hypoxia in vitro and in vivo and review work showing that many types of stem cell proliferate more robustly in lowered oxygen. I then discuss recent studies showing that alterations in the levels and the types of cell and substrate adhesion molecules are a notable response to reduced O2 levels in both cultured primary neural stem cells and brain tissues in response to hypoxia in vivo. The ability of O2 levels to regulate adhesion molecule expression...

  14. Oxygen radicals shaping evolution: why fatty acid catabolism leads to peroxisomes while neurons do without it: FADH₂/NADH flux ratios determining mitochondrial radical formation were crucial for the eukaryotic invention of peroxisomes and catabolic tissue differentiation.

    Science.gov (United States)

    Speijer, Dave

    2011-02-01

    Oxygen radical formation in mitochondria is a highly important, but incompletely understood, attribute of eukaryotic cells. I propose a kinetic model in which the ratio between electrons entering the respiratory chain via FADH₂ or NADH is a major determinant in radical formation. During the breakdown of glucose, this ratio is low; during fatty acid breakdown, this ratio is much higher. The longer the fatty acid, the higher the ratio and the higher the level of radical formation. This means that very long chain fatty acids should be broken down without generation of FADH₂ for mitochondria. This is accomplished in peroxisomes, thus explaining their role and evolution. The model explains many recent observations regarding radical formation by the respiratory chain. It also sheds light on the reasons for the lack of neuronal fatty acid (beta-) oxidation and for beneficial aspects of unsaturated fatty acids. Last but not least, it has very important implications for all models describing eukaryotic origins.

  15. Helminth.net: expansions to Nematode.net and an introduction to Trematode.net

    Science.gov (United States)

    Martin, John; Rosa, Bruce A.; Ozersky, Philip; Hallsworth-Pepin, Kymberlie; Zhang, Xu; Bhonagiri-Palsikar, Veena; Tyagi, Rahul; Wang, Qi; Choi, Young-Jun; Gao, Xin; McNulty, Samantha N.; Brindley, Paul J.; Mitreva, Makedonka

    2015-01-01

    Helminth.net (http://www.helminth.net) is the new moniker for a collection of databases: Nematode.net and Trematode.net. Within this collection we provide services and resources for parasitic roundworms (nematodes) and flatworms (trematodes), collectively known as helminths. For over a decade we have provided resources for studying nematodes via our veteran site Nematode.net (http://nematode.net). In this article, (i) we provide an update on the expansions of Nematode.net that hosts omics data from 84 species and provides advanced search tools to the broad scientific community so that data can be mined in a useful and user-friendly manner and (ii) we introduce Trematode.net, a site dedicated to the dissemination of data from flukes, flatworm parasites of the class Trematoda, phylum Platyhelminthes. Trematode.net is an independent component of Helminth.net and currently hosts data from 16 species, with information ranging from genomic, functional genomic data, enzymatic pathway utilization to microbiome changes associated with helminth infections. The databases’ interface, with a sophisticated query engine as a backbone, is intended to allow users to search for multi-factorial combinations of species’ omics properties. This report describes updates to Nematode.net since its last description in NAR, 2012, and also introduces and presents its new sibling site, Trematode.net. PMID:25392426

  16. The Net Physiological Cost of Dribbling a Soccer Ball.

    Science.gov (United States)

    Reilly, Thomas; Ball, David

    1984-01-01

    To establish the net energy cost of dribbling a soccer ball, eight males ran on a treadmill while dribbling a ball against a rebound box. Oxygen uptake, perceived exertion, and blood lactate levels were measured and compared with results from subjects running without dribbling. Results are discussed. (Author/DF)

  17. NETS FOR PEACH PROTECTED CULTIVATION

    Directory of Open Access Journals (Sweden)

    Evelia Schettini

    2012-06-01

    Full Text Available The aim of this paper was to investigate the radiometric properties of coloured nets used to protect a peach cultivation. The modifications of the solar spectral distribution, mainly in the R and FR wavelength band, influence plant photomorphogenesis by means of the phytochrome and cryptochrome. The phytochrome response is characterized in terms of radiation rate in the red wavelengths (R, 600-700 nm to that in the farred radiation (FR, 700-800 nm, i.e. the R/FR ratio. The effects of the blue radiation (B, 400-500 nm is investigated by the ratio between the blue radiation and the far-red radiation, i.e. the B/FR ratio. A BLUE net, a RED net, a YELLOW net, a PEARL net, a GREY net and a NEUTRAL net were tested in Bari (Italy, latitude 41° 05’ N. Peach trees were located in pots inside the greenhouses and in open field. The growth of the trees cultivated in open field was lower in comparison to the growth of the trees grown under the nets. The RED, PEARL, YELLOW and GREY nets increased the growth of the trees more than the other nets. The nets positively influenced the fruit characteristics, such as fruit weight and flesh firmness.

  18. The equivalency between logic Petri workflow nets and workflow nets.

    Science.gov (United States)

    Wang, Jing; Yu, ShuXia; Du, YuYue

    2015-01-01

    Logic Petri nets (LPNs) can describe and analyze batch processing functions and passing value indeterminacy in cooperative systems. Logic Petri workflow nets (LPWNs) are proposed based on LPNs in this paper. Process mining is regarded as an important bridge between modeling and analysis of data mining and business process. Workflow nets (WF-nets) are the extension to Petri nets (PNs), and have successfully been used to process mining. Some shortcomings cannot be avoided in process mining, such as duplicate tasks, invisible tasks, and the noise of logs. The online shop in electronic commerce in this paper is modeled to prove the equivalence between LPWNs and WF-nets, and advantages of LPWNs are presented.

  19. Room Temperature Optical Constants and Band Gap Evolution of Phase Pure M1-VO2 Thin Films Deposited at Different Oxygen Partial Pressures by Reactive Magnetron Sputtering

    Directory of Open Access Journals (Sweden)

    Meng Jiang

    2014-01-01

    Full Text Available Spectroscopic ellipsometry study was employed for phase pure VO2(M1 thin films grown at different oxygen partial pressures by reactive magnetron sputtering. The optical constants of the VO2(M1 thin films have been determined in a photon energy range between 0.73 and 5.05 eV. The near-infrared extinction coefficient and optical conductivity of VO2(M1 thin films rapidly increase with decreasing O2-Ar ratios. Moreover, two electronic transitions can be uniquely assigned. The energy gaps correlated with absorption edge (E1 at varied O2-Ar ratios are almost the same (~2.0 eV; consequently, the absorption edge is not significantly changed. However, the optical band gap corresponding to semiconductor-to-metal phase transition (E2 decreases from 0.53 to 0.18 eV with decreasing O2-Ar ratios.

  20. Coloured Petri Nets

    DEFF Research Database (Denmark)

    Jensen, Kurt; Kristensen, Lars Michael

    studies that illustrate the practical use of CPN modelling and validation for design, specification, simulation, verification and implementation in various application domains. Their presentation primarily aims at readers interested in the practical use of CPN. Thus all concepts and constructs are first......Coloured Petri Nets (CPN) is a graphical language for modelling and validating concurrent and distributed systems, and other systems in which concurrency plays a major role. The development of such systems is particularly challenging because of inherent intricacies like possible nondeterminism...... and the immense number of possible execution sequences. In this textbook, Jensen and Kristensen introduce the constructs of the CPN modelling language and present the related analysis methods in detail. They also provide a comprehensive road map for the practical use of CPN by showcasing selected industrial case...

  1. Is the Neoproterozoic oxygen burst a supercontinent legacy?

    Directory of Open Access Journals (Sweden)

    Melina eMacouin

    2015-09-01

    Full Text Available The Neoproterozoic (1000–542 Myr ago witnessed the dawn of Earth as we know it with modern-style plate tectonics, high levels of O2 in atmosphere and oceans and a thriving fauna. Yet, the processes leading to the fully oxygenation of the external envelopes, its exact timing and its link with the inner workings of the planet remain poorly understood. In some ways, it is a chicken and egg question: did the Neoproterozoic Oxygenation Event (NOE cause life blooming, low-latitudes glaciations and perturbations in geochemical cycles or is it a consequence of these phenomena? Here, we suggest that the NOE may have been triggered by multi-million years oxic volcanic emissions along a protracted period at the end of the Neoproterozoic when continents were assembled in the Rodinia supercontinent. We report a very oxidized magma source at the upper mantle beneath a ring of subducting margins around Rodinia, and detail here the evidence at the margin of the Arabian shield. We investigate the 780 Ma Biotite and Pink granites and associated rocks of the Socotra Island with rock magnetic and petrographic methods. Magnetic susceptibility and isothermal remanent magnetization acquisitions show that, in these granites, both magnetite and hematite are present. Hematite subdivides magnetite grains into small grains. Magnetite and hematite are found to be primary, and formed at the early magmatic evolution of the granite at very high oxygen fugacity. Massive degassing of these oxidized magmas would reduce the sink for oxygen, and consequently contribute to its rise in the atmosphere with a net O2 flux of at least 2.25 x 107 Tmol. Our conceptual model provides a deep Earth link to the NOE and implies the oxygenation burst has occurred earlier than previously envisaged, paving the way for later changes in the outer envelopes of the planet epitomized on the extreme Neoproterozoic glaciations and the appearance of the first animals.

  2. Linear Logic on Petri Nets

    DEFF Research Database (Denmark)

    Engberg, Uffe Henrik; Winskel, Glynn

    This article shows how individual Petri nets form models of Girard's intuitionistic linear logic. It explores questions of expressiveness and completeness of linear logic with respect to this interpretation. An aim is to use Petri nets to give an understanding of linear logic and give some apprai...

  3. Reference Guide Microsoft.NET

    NARCIS (Netherlands)

    Zee M van der; Verspaij GJ; Rosbergen S; IMP; NMD

    2003-01-01

    Developers, administrators and managers can get more understanding of the .NET technology with this report. They can also make better choices how to use this technology. The report describes the results and conclusions of a study of the usability for the RIVM of this new generation .NET development

  4. Net neutrality and audiovisual services

    NARCIS (Netherlands)

    van Eijk, N.; Nikoltchev, S.

    2011-01-01

    Net neutrality is high on the European agenda. New regulations for the communication sector provide a legal framework for net neutrality and need to be implemented on both a European and a national level. The key element is not just about blocking or slowing down traffic across communication

  5. LTE HetNet Mobility Performance Through Emulation with Commercial Smartphones

    DEFF Research Database (Denmark)

    Jensen, Anders Riis; Pedersen, Klaus I.; Lauridsen, Mads

    2014-01-01

    In this paper we introduce a laboratory emulation setup for evaluation of Long Term Evolution (LTE) mobility performance in a co-channel heterogeneous network (HetNet). The setup consists of two eNodeB emulators, signal faders and release 9 LTE User Equipment (UE). It is shown how the LTE HetNet ...

  6. A Small Universal Petri Net

    Directory of Open Access Journals (Sweden)

    Dmitry A. Zaitsev

    2013-09-01

    Full Text Available A universal deterministic inhibitor Petri net with 14 places, 29 transitions and 138 arcs was constructed via simulation of Neary and Woods' weakly universal Turing machine with 2 states and 4 symbols; the total time complexity is exponential in the running time of their weak machine. To simulate the blank words of the weakly universal Turing machine, a couple of dedicated transitions insert their codes when reaching edges of the working zone. To complete a chain of a given Petri net encoding to be executed by the universal Petri net, a translation of a bi-tag system into a Turing machine was constructed. The constructed Petri net is universal in the standard sense; a weaker form of universality for Petri nets was not introduced in this work.

  7. Dissolved oxygen

    National Research Council Canada - National Science Library

    1981-01-01

    Dissolved oxygen concentrations in the waters of Botany Bay and Georges and Cooks Rivers vary mainly as a result of tidal water movements, algal and macrophytic growth and decay, and effects of storms...

  8. High-level Petri Nets

    DEFF Research Database (Denmark)

    High-level Petri nets are now widely used in both theoretical analysis and practical modelling of concurrent systems. The main reason for the success of this class of net models is that they make it possible to obtain much more succinct and manageable descriptions than can be obtained by means...... of low-level Petri nets - while, on the other hand, they still offer a wide range of analysis methods and tools. The step from low-level nets to high-level nets can be compared to the step from assembly languages to modern programming languages with an elaborated type concept. In low-level nets...... there is only one kind of token and this means that the state of a place is described by an integer (and in many cases even by a boolean). In high-level nets each token can carry a complex information/data - which, e.g., may describe the entire state of a process or a data base. Today most practical...

  9. Pro asynchronous programming with .NET

    CERN Document Server

    Blewett, Richard; Ltd, Rock Solid Knowledge

    2014-01-01

    Pro Asynchronous Programming with .NET teaches the essential skill of asynchronous programming in .NET. It answers critical questions in .NET application development, such as: how do I keep my program responding at all times to keep my users happy how do I make the most of the available hardware how can I improve performanceIn the modern world, users expect more and more from their applications and devices, and multi-core hardware has the potential to provide it. But it takes carefully crafted code to turn that potential into responsive, scalable applications.With Pro Asynchronous Programming

  10. Conformal Nets II: Conformal Blocks

    Science.gov (United States)

    Bartels, Arthur; Douglas, Christopher L.; Henriques, André

    2017-08-01

    Conformal nets provide a mathematical formalism for conformal field theory. Associated to a conformal net with finite index, we give a construction of the `bundle of conformal blocks', a representation of the mapping class groupoid of closed topological surfaces into the category of finite-dimensional projective Hilbert spaces. We also construct infinite-dimensional spaces of conformal blocks for topological surfaces with smooth boundary. We prove that the conformal blocks satisfy a factorization formula for gluing surfaces along circles, and an analogous formula for gluing surfaces along intervals. We use this interval factorization property to give a new proof of the modularity of the category of representations of a conformal net.

  11. Characterization and Electrocatalytic Properties of Titanium-Based Ru0.3Co0.7−xCex Mixed Oxide Electrodes for Oxygen Evolution in Alkaline Solution

    Directory of Open Access Journals (Sweden)

    Hongjun Wu

    2011-01-01

    Full Text Available Ti-supported RuO2-Co3O4-CeO2 (Ru0.3Co0.7−xCex oxide, 0≤x≤0.7 electrodes were prepared by sol-gel process. The phase structure, surface morphology, and microstructure of the oxide layer were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Electrocatalytic activity and oxygen evolution reaction (OER kinetics on these electrodes in 1.0 mol⋅dm−3 KOH solution were studied by recording open-circuit potential, cyclic voltammetry, and polarisation curves. The results showed that the appropriate content of CeO2 could reduce the grain size and increase active surface area. The electrocatalytic activity shows a strong dependence on the CeO2 content in the film. Catalytic performance of mixed oxide electrodes with 40 mol % CeO2 was the best, with the greatest voltammetric charge, 86.23 mC⋅cm−2, and the smallest apparent activation energy for OER at 0.60 V was 22.76 kJ⋅mol−1.

  12. OXYGEN TRANSPORT CERAMIC MEMBRANES

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2003-01-01

    In the present quarter, the possibility of using a more complex interfacial engineering approach to the development of reliable and stable oxygen transport perovskite ceramic membranes/metal seals is discussed. Experiments are presented and ceramic/metal interactions are characterized. Crack growth and fracture toughness of the membrane in the reducing conditions are also discussed. Future work regarding this approach is proposed are evaluated for strength and fracture in oxygen gradient conditions. Oxygen gradients are created in tubular membranes by insulating the inner surface from the reducing environment by platinum foils. Fracture in these test conditions is observed to have a gradient in trans and inter-granular fracture as opposed to pure trans-granular fracture observed in homogeneous conditions. Fracture gradients are reasoned to be due to oxygen gradient set up in the membrane, variation in stoichiometry across the thickness and due to varying decomposition of the parent perovskite. The studies are useful in predicting fracture criterion in actual reactor conditions and in understanding the initial evolution of fracture processes.

  13. Petri Net Tool Overview 1986

    DEFF Research Database (Denmark)

    Jensen, Kurt; Feldbrugge, Frits

    1987-01-01

    This paper provides an overview of the characteristics of all currently available net based tools. It is a compilation of information provided by tool authors or contact persons. A concise one page overview is provided as well....

  14. Understanding Net Zero Energy Buildings

    DEFF Research Database (Denmark)

    Salom, Jaume; Widén, Joakim; Candanedo, José

    2011-01-01

    Although several alternative definitions exist, a Net-Zero Energy Building (Net ZEB) can be succinctly described as a grid-connected building that generates as much energy as it uses over a year. The “net-zero” balance is attained by applying energy conservation and efficiency measures...... and by incorporating renewable energy systems. While based on annual balances, a complete description of a Net ZEB requires examining the system at smaller time-scales. This assessment should address: (a) the relationship between power generation and building loads and (b) the resulting interaction with the power grid....... This paper presents and categorizes quantitative indicators suitable to describe both aspects of the building’s performance. These indicators, named LMGI - Load Matching and Grid Interaction indicators, are easily quantifiable and could complement the output variables of existing building simulation tools...

  15. PolicyNet Publication System

    Data.gov (United States)

    Social Security Administration — The PolicyNet Publication System project will merge the Oracle-based Policy Repository (POMS) and the SQL-Server CAMP system (MSOM) into a new system with an Oracle...

  16. KM3NeT

    CERN Multimedia

    KM3NeT is a large scale next-generation neutrino telescope located in the deep waters of the Mediterranean Sea, optimized for the discovery of galactic neutrino sources emitting in the TeV energy region.

  17. Net Neutrality: Background and Issues

    National Research Council Canada - National Science Library

    Gilroy, Angele A

    2006-01-01

    .... The move to place restrictions on the owners of the networks that compose and provide access to the Internet, to ensure equal access and nondiscriminatory treatment, is referred to as "net neutrality...

  18. Petri Nets in Cryptographic Protocols

    DEFF Research Database (Denmark)

    Crazzolara, Federico; Winskel, Glynn

    2001-01-01

    A process language for security protocols is presented together with a semantics in terms of sets of events. The denotation of process is a set of events, and as each event specifies a set of pre and postconditions, this denotation can be viewed as a Petri net. By means of an example we illustrate...... how the Petri-net semantics can be used to prove security properties....

  19. The Economics of Net Neutrality

    OpenAIRE

    Hahn, Robert W.; Wallsten, Scott

    2006-01-01

    This essay examines the economics of "net neutrality" and broadband Internet access. We argue that mandating net neutrality would be likely to reduce economic welfare. Instead, the government should focus on creating competition in the broadband market by liberalizing more spectrum and reducing entry barriers created by certain local regulations. In cases where a broadband provider can exercise market power the government should use its antitrust enforcement authority to police anticompetitiv...

  20. Lithium-Oxygen Batteries: At a Crossroads?

    DEFF Research Database (Denmark)

    Vegge, Tejs; García Lastra, Juan Maria; Siegel, Donald Jason

    2017-01-01

    In this current opinion, we critically review and discuss some of the most important recent findings in the field of rechargeable lithium-oxygen batteries. We discuss recent discoveries like the evolution of reactive singlet oxygen and the use of organic additives to bypass reactive LiO2 reaction...

  1. 26 CFR 1.904(f)-3 - Allocation of net operating losses and net capital losses.

    Science.gov (United States)

    2010-04-01

    ... 26 Internal Revenue 9 2010-04-01 2010-04-01 false Allocation of net operating losses and net....904(f)-3 Allocation of net operating losses and net capital losses. For rules relating to the allocation of net operating losses and net capital losses, see § 1.904(g)-3T. ...

  2. 29 CFR 4204.13 - Net income and net tangible assets tests.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false Net income and net tangible assets tests. 4204.13 Section....13 Net income and net tangible assets tests. (a) General. The criteria under this section are that either— (1) Net income test. The purchaser's average net income after taxes for its three most recent...

  3. Cyanobacterial Diazotrophy and Earth?s Delayed Oxygenation

    OpenAIRE

    Olson, Stephanie L.; Reinhard, Christopher T.; Lyons, Timothy W.

    2016-01-01

    The redox landscape of Earth’s ocean-atmosphere system has changed dramatically throughout Earth history. Although Earth’s protracted oxygenation is undoubtedly the consequence of cyanobacterial oxygenic photosynthesis, the relationship between biological O2 production and Earth’s redox evolution remains poorly understood. Existing models for Earth’s oxygenation cannot adequately explain the nearly 2.5 billion years delay between the origin of oxygenic photosynthesis and the oxygenation of th...

  4. Temperature, salinity, transmissivity, pressure, plankton, oxygen, nutrients, chlorophyll, and primary productivity data collected using CTD, bottle, and plankton net from the R/V Italica in the Ross Sea and Magellan Strait during 10th Italian Antarctic Expedition from 1994-11-13 to 1995-04-02 (NCEI Accession 0068289)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Temperature, salinity, transmissivity, pressure, plankton, oxygen, nutrients, chlorophyll, and primary productivity data collected using CTD, bottle, and plankton...

  5. Entamoeba histolytica induces human neutrophils to form NETs.

    Science.gov (United States)

    Ventura-Juarez, J; Campos-Esparza, Mr; Pacheco-Yepez, J; López-Blanco, J A; Adabache-Ortíz, A; Silva-Briano, M; Campos-Rodríguez, R

    2016-08-01

    Entamoeba histolytica invades the intestine and other organs during the pathogenesis of amoebiasis. In the early stages, the host organism responds with an inflammatory infiltrate composed mostly of neutrophils. It has been reported that these immune cells, activated by E. histolytica, exert a protective role by releasing proteolytic enzymes and generating reactive oxygen/nitrogen species (ROS/RNS) and antimicrobial peptides. It is now known that neutrophils also produce neutrophil extracellular traps (NETs), which are able to damage and kill pathogens. Studies have shown that intracellular protozoan pathogens, including Toxoplasma gondi, Plasmodium falciparum and Leishmania spp, induce neutrophils to release NETs and are damaged by them. However, the action of this mechanism has not been explored in relation to E. histolytica trophozoites. Through scanning electron, epifluorescence microscopy and viability assays, we show for first time that during in vitro interaction with E. histolytica trophozoites, human neutrophils released NETs that covered amoebas and reduced amoebic viability. These NETs presented histones, myeloperoxidase and decondensed chromatin. The results suggest that NETs participate in the elimination of the parasite. © 2016 John Wiley & Sons Ltd.

  6. Oxygen - A Four Billion Year History

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    Canfield--one of the world's leading authorities on geochemistry, earth history, and the early oceans--covers this vast history, emphasizing its relationship to the evolution of life and the evolving chemistry of the Earth. With an accessible and colorful first-person narrative, he draws from a variety...... the records of oxygen concentrations through time. Readers learn about the great oxidation event, the tipping point 2.3 billion years ago when the oxygen content of the Earth increased dramatically, and Canfield examines how oxygenation created a favorable environment for the evolution of large animals. He...

  7. Construction of hierarchically porous graphitized carbon-supported NiFe layered double hydroxides with a core-shell structure as an enhanced electrocatalyst for the oxygen evolution reaction.

    Science.gov (United States)

    Ni, Yuanman; Yao, Lihua; Wang, Yin; Liu, Bing; Cao, Minhua; Hu, Changwen

    2017-08-17

    The oxygen evolution reaction (OER) is a vital half-reaction in water splitting and metal-air batteries. Developing earth-abundant, highly efficient and durable OER catalysts has faced huge challenges until now, because OER is a strict kinetic sluggish process. Herein, we report the construction of hierarchically porous graphitized carbon (HPGC) supported NiFe layered double hydroxides (LDHs) with a core-shell structure (denoted as HPGC@NiFe) by a facile strategy. The HPGC was first obtained by pyrolysing phenolic resin nanospheres with FeCl 3 and ZnCl 2 as the catalyst and the activator, respectively. Then the NiFe LDH arrays were directly grown on the HPGC by a one-step hydrothermal method. The as-synthesized HPGC@NiFe reveals excellent OER properties with a low onset potential, a lower overpotential of 265 mV (corresponding to the current density at 10 mA cm -2 ) and a small Tafel slope (56 mV per decade). And its catalytic activity is even superior to that of the start-of-the-art noble-metal catalyst IrO 2 /C. Notably, the HPGC@NiFe electrode shows admirable stability measured by performing 2000 cycle CVs and long-term electrolysis for 50 h. The prominent performance can be attributed to the synergistic effect between the NiFe-LDHs and the hierarchically porous graphitized carbon, in which the former can increase the exposure of the active sites, while the latter can increase the charge transfer efficiency. Our research implies the possibility for the development of low-cost layered double hydroxides as a promising candidate in electrochemical energy storage and conversion equipment.

  8. NiSe@NiOOH Core-Shell Hyacinth-like Nanostructures on Nickel Foam Synthesized by in Situ Electrochemical Oxidation as an Efficient Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Li, Xiao; Han, Guan-Qun; Liu, Yan-Ru; Dong, Bin; Hu, Wen-Hui; Shang, Xiao; Chai, Yong-Ming; Liu, Chen-Guang

    2016-08-10

    NiSe@NiOOH core-shell hyacinth-like nanostructures supported on nickel foam (NF) have been successfully synthesized by a facile solvothermal selenization and subsequent in situ electrochemical oxidation (ISEO). First, the unique NiSe/NF nanopillar arrays were prepared in N,N-dimethylformamide (DMF) as a precursor template that can provide a large surface area, excellent conductivity, and robust support. Next, amorphous NiOOH covering the surface of NiSe nanopillars was fabricated by ISEO, as confirmed by XPS andEDX spectroscopy. SEM images revealed the hyacinth-like morphology of NiSe@NiOOH/NF with NiOOH as the shell and NiSe as the core. The electrochemical performance of NiSe@NiOOH/NF for the oxygen evolution reaction (OER) was investigated. NiSe@NiOOH/NF demonstrates an obviously enhanced OER activity with much lower overpotential of 332 mV at 50 mA cm(-2) compared to other Ni-based electrocatalysts. The low charge-transfer resistance (Rct), large electrochemical double-layer capacitance (Cdl) of electrochemically active surface areas (ECSAs), and excellent long-term stability of NiSe@NiOOH/NF confirm the enhancement of its electrochemical performance for the OER, which can be ascribed to the large amount of active sites derived from the amorphous NiOOH shell and the good conductivity and stability derived from the NiSe core. In addition, the synergistic effect between the NiSe core and NiOOH shell could serve for a highly efficient OER electrocatalyst.

  9. Vascular smooth muscle sensitivity to varying oxygen tensions, Bay ...

    African Journals Online (AJOL)

    With the suggestion that while high oxygen levels may alter the response beyond the receptor, with wrong information about excitation-contracton coupling; it was observed that levels of oxygen affect both the calcium channel blockers and facilitators with net reduction ofinflux or utilization of external calcium. I this our study, ...

  10. Enhancing Activity for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

    2014-01-01

    of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... on a hydrogen acceptor concept. This concept comprises a stabilization of an *-OOH intermediate, which effectively lowers the potential needed for breaking bonds to the surface. On this basis, we investigate the interactions between the oxides and gold by using DFT calculations. The results suggest...

  11. TimeNET Optimization Environment

    Directory of Open Access Journals (Sweden)

    Christoph Bodenstein

    2015-12-01

    Full Text Available In this paper a novel tool for simulation-based optimization and design-space exploration of Stochastic Colored Petri nets (SCPN is introduced. The working title of this tool is TimeNET Optimization Environment (TOE. Targeted users of this tool are people modeling complex systems with SCPNs in TimeNET who want to find parameter sets that are optimal for a certain performance measure (fitness function. It allows users to create and simulate sets of SCPNs and to run different optimization algorithms based on parameter variation. The development of this tool was motivated by the need to automate and speed up tests of heuristic optimization algorithms to be applied for SCPN optimization. A result caching mechanism is used to avoid recalculations.

  12. Implementing NetScaler VPX

    CERN Document Server

    Sandbu, Marius

    2014-01-01

    An easy-to-follow guide with detailed step-by step-instructions on how to implement the different key components in NetScaler, with real-world examples and sample scenarios.If you are a Citrix or network administrator who needs to implement NetScaler in your virtual environment to gain an insight on its functionality, this book is ideal for you. A basic understanding of networking and familiarity with some of the different Citrix products such as XenApp or XenDesktop is a prerequisite.

  13. Net4Care PHMR Library

    DEFF Research Database (Denmark)

    2014-01-01

    The Net4Care PHMR library contains a) A GreenCDA approach for constructing a data object representing a PHMR document: SimpleClinicalDocument, and b) A Builder which can produce a XML document representing a valid Danish PHMR (following the MedCom profile) document from the SimpleClinicalDocument......The Net4Care PHMR library contains a) A GreenCDA approach for constructing a data object representing a PHMR document: SimpleClinicalDocument, and b) A Builder which can produce a XML document representing a valid Danish PHMR (following the MedCom profile) document from the Simple...

  14. Pro DLR in NET 4

    CERN Document Server

    Wu, Chaur

    2011-01-01

    Microsoft's Dynamic Language Runtime (DLR) is a platform for running dynamic languages such as Ruby and Python on an equal footing with compiled languages such as C#. Furthermore, the runtime is the foundation for many useful software design and architecture techniques you can apply as you develop your .NET applications. Pro DLR in .NET 4 introduces you to the DLR, showing how you can use it to write software that combines dynamic and static languages, letting you choose the right tool for the job. You will learn the core DLR components such as LINQ expressions, call sites, binders, and dynami

  15. Hierarchies in Coloured Petri Nets

    DEFF Research Database (Denmark)

    Huber, Peter; Jensen, Kurt; Shapiro, Robert M.

    1991-01-01

    The paper shows how to extend Coloured Petri Nets with a hierarchy concept. The paper proposes five different hierarchy constructs, which allow the analyst to structure large CP-nets as a set of interrelated subnets (called pages). The paper discusses the properties of the proposed hierarchy...... constructs, and it illustrates them by means of two examples. The hierarchy constructs can be used for theoretical considerations, but their main use is to describe and analyse large real-world systems. All of the hierarchy constructs are supported by the editing and analysis facilities in the CPN Palette...

  16. SkyNet: A Modular Nuclear Reaction Network Library

    Science.gov (United States)

    Lippuner, Jonas; Roberts, Luke F.

    2017-12-01

    Almost all of the elements heavier than hydrogen that are present in our solar system were produced by nuclear burning processes either in the early universe or at some point in the life cycle of stars. In all of these environments, there are dozens to thousands of nuclear species that interact with each other to produce successively heavier elements. In this paper, we present SkyNet, a new general-purpose nuclear reaction network that evolves the abundances of nuclear species under the influence of nuclear reactions. SkyNet can be used to compute the nucleosynthesis evolution in all astrophysical scenarios where nucleosynthesis occurs. SkyNet is free and open source, and aims to be easy to use and flexible. Any list of isotopes can be evolved, and SkyNet supports different types of nuclear reactions. SkyNet is modular so that new or existing physics, like nuclear reactions or equations of state, can easily be added or modified. Here, we present in detail the physics implemented in SkyNet with a focus on a self-consistent transition to and from nuclear statistical equilibrium to non-equilibrium nuclear burning, our implementation of electron screening, and coupling of the network to an equation of state. We also present comprehensive code tests and comparisons with existing nuclear reaction networks. We find that SkyNet agrees with published results and other codes to an accuracy of a few percent. Discrepancies, where they exist, can be traced to differences in the physics implementations.

  17. Net Neutrality Regulation and the Evolution of the Internet Economy

    OpenAIRE

    David Evans

    2011-01-01

    Do we know enough to be sure that there are market failures that should be corrected or that policymakers could know enough about the present and future of the internet economy to devise regulations that would improve social welfare? (David S. Evans, Global Economics Group & UCL)

  18. Earliest land plants created modern levels of atmospheric oxygen

    DEFF Research Database (Denmark)

    Lenton, Timothy M.; Dahl, Tais Wittchen; Daines, Stuart J.

    2016-01-01

    The progressive oxygenation of the Earth's atmosphere was pivotal to the evolution of life, but the puzzle of when and how atmospheric oxygen (O2) first approached modern levels (∼21%) remains unresolved. Redox proxy data indicate the deep oceans were oxygenated during 435-392 Ma, and the appeara...

  19. D.NET case study

    International Development Research Centre (IDRC) Digital Library (Canada)

    lremy

    developing products, marketing tools and building capacity of the grass root telecentre workers. D.Net recognized that it had several ideas worth developing into small interventions that would make big differences, but resource constraints were a barrier for scaling-up these initiatives. More demands, limited resources.

  20. Surgery for GEP-NETs

    DEFF Research Database (Denmark)

    Knigge, Ulrich; Hansen, Carsten Palnæs

    2012-01-01

    Surgery is the only treatment that may cure the patient with gastroentero-pancreatic (GEP) neuroendocrine tumours (NET) and neuroendocrine carcinomas (NEC) and should always be considered as first line treatment if R0/R1 resection can be achieved. The surgical and interventional procedures for GEP...

  1. Net Neutrality in the Netherlands

    NARCIS (Netherlands)

    van Eijk, N.

    2014-01-01

    The Netherlands is among the first countries that have put specific net neutrality standards in place. The decision to implement specific regulation was influenced by at least three factors. The first was the prevailing social and academic debate, partly due to developments in the United States. The

  2. Complexity Metrics for Workflow Nets

    DEFF Research Database (Denmark)

    Lassen, Kristian Bisgaard; van der Aalst, Wil M.P.

    2009-01-01

    Process modeling languages such as EPCs, BPMN, flow charts, UML activity diagrams, Petri nets, etc.\\ are used to model business processes and to configure process-aware information systems. It is known that users have problems understanding these diagrams. In fact, even process engineers and system...

  3. Oxygen - A Four Billion Year History

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    The air we breathe is twenty-one percent oxygen, an amount higher than on any other known world. While we may take our air for granted, Earth was not always an oxygenated planet. How did it become this way? Oxygen is the most current account of the history of atmospheric oxygen on Earth. Donald...... Canfield--one of the world's leading authorities on geochemistry, earth history, and the early oceans--covers this vast history, emphasizing its relationship to the evolution of life and the evolving chemistry of the Earth. With an accessible and colorful first-person narrative, he draws from a variety...

  4. Caught in the Net: Perineuronal Nets and Addiction

    Directory of Open Access Journals (Sweden)

    Megan Slaker

    2016-01-01

    Full Text Available Exposure to drugs of abuse induces plasticity in the brain and creates persistent drug-related memories. These changes in plasticity and persistent drug memories are believed to produce aberrant motivation and reinforcement contributing to addiction. Most studies have explored the effect drugs of abuse have on pre- and postsynaptic cells and astrocytes; however, more recently, attention has shifted to explore the effect these drugs have on the extracellular matrix (ECM. Within the ECM are unique structures arranged in a net-like manner, surrounding a subset of neurons called perineuronal nets (PNNs. This review focuses on drug-induced changes in PNNs, the molecules that regulate PNNs, and the expression of PNNs within brain circuitry mediating motivation, reward, and reinforcement as it pertains to addiction.

  5. Temperature profile, dissolved oxygen, phosphate and other measurements collected using bottle, net, CTD casts from the NEW HORIZON, NOAA Ship DAVID STARR JORDAN, ROGER REVELLE in the North East Pacific Ocean as part of the California Cooperative Fisheries Investigation (CALCOFI) project, from 2000-06-29 to 2004-01-20 (NODC Accession 0002116)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Temperature, dissolved oxygen, phosphate and other data were collected using water pumps, SIMBAD radiometer, 150 kHz Acoustic Doppler Current Profiler (ADCP),...

  6. Formation of neutrophil extracellular traps under low oxygen level

    Directory of Open Access Journals (Sweden)

    Katja Branitzki-Heinemann

    2016-11-01

    Full Text Available Since their discovery, neutrophil extracellular traps (NETs have been characterized as a fundamental host innate immune defense mechanism. Conversely, excessive NET release may have a variety of detrimental consequences for the host. A fine balance between NET formation and elimination is necessary to sustain a protective effect during an infectious challenge. Our own recently published data revealed that stabilization of hypoxia inducible factor 1α (HIF-1α by the iron chelating HIF-1α-agonist desferoxamine or AKB-4924 enhanced the release of phagocyte extracellular traps. Since HIF-1α is a global regulator of the cellular response to low oxygen, we hypothesized that NET formation may be similarly increased under low oxygen conditions. Hypoxia occurs in tissues during infection or inflammation, mostly due to overconsumption of oxygen by pathogens and recruited immune cells. Therefore, experiments were performed to characterize the formation of NETs under hypoxic oxygen conditions compared to normoxia. Human blood-derived neutrophils were isolated and incubated under normoxic (21% oxygen level and compared to hypoxic (1% conditions. Dissolved oxygen levels were monitored in the primary cell culture using a Fibox4-PSt3 measurement system. The formation of NETs was quantified by fluorescence microscopy in response to the known NET-inducer phorbol 12-myristate 13-acetate (PMA or S. aureus wildtype and a nuclease-deficient mutant. In contrast to our hypothesis, spontaneous NET formation of neutrophils incubated under hypoxia was distinctly reduced compared to control neutrophils incubated under normoxia. Furthermore, neutrophils incubated under hypoxia showed significantly reduced formation of NETs in response to PMA. Gene expression analysis revealed that mRNA level of hif-1α as well as hif-1α target genes was not altered. However, in good correlation to the decreased NET formation under hypoxia, the cholesterol content of the neutrophils was

  7. Army Net Zero Prove Out. Army Net Zero Training Report

    Science.gov (United States)

    2014-11-20

    sensors were strategically placed throughout the installation by magnetically attaching them to water main valve stems. The sensors check sound...Recycle Wrap  Substitutes for Packaging Materials  Re-Use of Textiles and Linens  Setting Printers to Double-Sided Printing Net Zero Waste...can effectively achieve source reduction. Clean and Re-Use Shop Rags - Shop rags represent a large textile waste stream at many installations. As a

  8. Army Net Zero Prove Out. Net Zero Waste Best Practices

    Science.gov (United States)

    2014-11-20

    Anaerobic Digesters – Although anaerobic digestion is not a new technology and has been used on a large-scale basis in wastewater treatment , the...technology and has been used on a large-scale basis in wastewater treatment , the use of the technology should be demonstrated with other...approaches can be used for cardboard and cellulose -based packaging materials. This approach is in line with the Net Zero Waste hierarchy in terms of

  9. Low content of Pt supported on Ni-MoC{sub x}/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui, E-mail: diamond_wangyanhui@163.com

    2017-08-01

    Highlights: • Ni-MoC{sub x}/C catalyst support was synthesized by a two-step method. • 10Pt/Ni-MoC{sub x}/C was an active and durable low Pt catalyst for MOR, ORR and HER. • The high stability of 10Pt/Ni-MoC{sub x}/C was ascribed to the anchoring effect of MoC{sub x}. • High activity of 10Pt/Ni-MoC{sub x}/C was due to a synergistic of Pt, Ni, MoO{sub x} and MoC{sub x}. - Abstract: Nickel and molybdenum carbide modified carbon black (Ni-MoC{sub x}/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoC{sub x}/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoC{sub x}/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoC{sub x}/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoC{sub x}/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoC{sub x}/C reached 68.4 m{sup 2} g{sup −1}, which was higher than that of 20Pt/C (63.2 m{sup 2} g{sup −1}). The enhanced stability and activity of 10Pt/Ni-MoC{sub x}/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoC{sub x} formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoO{sub x} and MoC{sub x}. These findings indicated that 10Pt/Ni-MoC{sub x}/C was a promising electrocatalyst for direct methanol fuel cells.

  10. HANPP Collection: Human Appropriation of Net Primary Productivity as a Percentage of Net Primary Productivity

    Data.gov (United States)

    National Aeronautics and Space Administration — The Human Appropriation of Net Primary Productivity (HANPP) as a Percentage of Net Primary Productivity (NPP) portion of the Human Appropriation of Net Primary...

  11. Hydrodynamic characteristics of plane netting used for aquaculture net cages in uniform current

    National Research Council Canada - National Science Library

    DONG, SHUCHUANG; HU, FUXIANG; KUMAZAWA, TAISEI; SIODE, DAISUKE; TOKAI, TADASHI

    2016-01-01

      The hydrodynamic characteristics of polyethylene (PE) netting and chain link wire netting with different types of twine diameter and mesh size for aquaculture net cages were examined by experiments in a flume tank...

  12.  NET and NETosis – new phenomenon in immunology

    Directory of Open Access Journals (Sweden)

    Natalia Matoszka

    2012-06-01

    Full Text Available  Neutrophils are one of the first cells of the immune system recruited to the site of infection, representing the host’s most effective and numerous front-line defenders. Recently, a novel antimicrobial mechanism of neutrophils has been described: upon activation, they release DNA and a subset of their granule content, forming neutrophil extracellular traps (NETs. These extracellular, chromatin structures, which contain histones and neutrophil granule proteins, can trap and kill a broad spectrum of microbes, including Gram-positive and Gram-negative bacteria, fungi, protozoa and viruses. Some of the pathogens, which are trapped and exposed to high local concentrations of antimicrobial compounds, employ strategies against NET binding, including surface modification and/or degradation of NET by DNases. It has been suggested that NETs are formed during active cell death, recently named NETosis. New data indicate that this novel mechanism of cell death requires interaction between three processes – reactive oxygen species generation, histone citrullination and autophagy – and significantly differs from previously known types of cell death, including apoptosis and necrosis. Moreover, the release of nuclear chromatin was also described for other types of cells – mast cells and eosinophils. Mast cells, like neutrophils, under certain conditions release nuclear chromatin and may undergo a similar active cell death program, while eosinophils release only mitochondrial chromatin, and its release does not lead to the death of these cells.

  13. Isolated unit tests in .Net

    OpenAIRE

    Haukilehto, Tero

    2013-01-01

    In this thesis isolation in unit testing is studied to get a precise picture of the isolation frameworks available for .Net environment. At the beginning testing is discussed in theory with the benefits and the problems it may have been linked with. The theory includes software development in general in connection with testing. Theory of isolation is also described before the actual isolation frameworks are represented. Common frameworks are described in more detail and comparable informa...

  14. Oxygen - A Four Billion Year History

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    The air we breathe is twenty-one percent oxygen, an amount higher than on any other known world. While we may take our air for granted, Earth was not always an oxygenated planet. How did it become this way? Oxygen is the most current account of the history of atmospheric oxygen on Earth. Donald...... Canfield--one of the world's leading authorities on geochemistry, earth history, and the early oceans--covers this vast history, emphasizing its relationship to the evolution of life and the evolving chemistry of the Earth. With an accessible and colorful first-person narrative, he draws from a variety...... of fields, including geology, paleontology, geochemistry, biochemistry, animal physiology, and microbiology, to explain why our oxygenated Earth became the ideal place for life. Describing which processes, both biological and geological, act to control oxygen levels in the atmosphere, Canfield traces...

  15. Moderate hyperventilation during intravenous anesthesia increases net cerebral lactate efflux.

    Science.gov (United States)

    Grüne, Frank; Kazmaier, Stephan; Sonntag, Hans; Stolker, Robert Jan; Weyland, Andreas

    2014-02-01

    Hyperventilation is known to decrease cerebral blood flow (CBF) and to impair cerebral metabolism, but the threshold in patients undergoing intravenous anesthesia is unknown. The authors hypothesized that reduced CBF associated with moderate hyperventilation might impair cerebral aerobic metabolism in patients undergoing intravenous anesthesia. Thirty male patients scheduled for coronary surgery were included in a prospective, controlled crossover trial. Measurements were performed under fentanyl-midazolam anesthesia in a randomized sequence aiming at partial pressures of carbon dioxide of 30 and 50 mmHg. Endpoints were CBF, blood flow velocity in the middle cerebral artery, and cerebral metabolic rates for oxygen, glucose, and lactate. Global CBF was measured using a modified Kety-Schmidt technique with argon as inert gas tracer. CBF velocity of the middle cerebral artery was recorded by transcranial Doppler sonography. Data were presented as mean (SD). Two-sided paired t tests and one-way ANOVA for repeated measures were used for statistical analysis. Moderate hyperventilation significantly decreased CBF by 60%, blood flow velocity by 41%, cerebral oxygen delivery by 58%, and partial pressure of oxygen of the jugular venous bulb by 45%. Cerebral metabolic rates for oxygen and glucose remained unchanged; however, net cerebral lactate efflux significantly increased from -0.38 (2.18) to -2.41(2.43) µmol min 100 g. Moderate hyperventilation, when compared with moderate hypoventilation, in patients with cardiovascular disease undergoing intravenous anesthesia increased net cerebral lactate efflux and markedly reduced CBF and partial pressure of oxygen of the jugular venous bulb, suggesting partial impairment of cerebral aerobic metabolism at clinically relevant levels of hypocapnia.

  16. Event hierarchies in DanNet

    DEFF Research Database (Denmark)

    Pedersen, Bolette Sandford; Nimb, Sanni

    2008-01-01

    Artiklen omhandler udarbejdelsen af et verbumshierarki i det leksikalsk-semantiske ordnet, DanNet.......Artiklen omhandler udarbejdelsen af et verbumshierarki i det leksikalsk-semantiske ordnet, DanNet....

  17. The Uniframe .Net Web Service Discovery Service

    National Research Council Canada - National Science Library

    Berbeco, Robert W

    2003-01-01

    Microsoft .NET allows the creation of distributed systems in a seamless manner Within NET small, discrete applications, referred to as Web services, are utilized to connect to each other or larger applications...

  18. Long Term RadNet Quality Data

    Data.gov (United States)

    U.S. Environmental Protection Agency — This RadNet Quality Data Asset includes all data since initiation and when ERAMS was expanded to become RadNet, name changed to reflect new mission. This includes...

  19. Oxygen measurements to improve singlet oxygen dosimetry

    Science.gov (United States)

    Kim, Michele M.; Penjweini, Rozhin; Ong, Yi Hong; Finlay, Jarod C.; Zhu, Timothy C.

    2017-02-01

    Photodynamic therapy (PDT) involves interactions between the three main components of light fluence, photosensitizer concentration, and oxygenation. Currently, singlet oxygen explicit dosimetry (SOED) has focused on the first two of these components. The macroscopic model to calculate reacted singlet oxygen has previously involved a fixed initial ground state oxygen concentration. A phosphorescence-based oxygen probe was used to measure ground state oxygen concentration throughout treatments for mice bearing radioactively induced fibroscarcoma tumors. Photofrin-, BPD-, and HPPH-mediated PDT was performed on mice. Model-calculated oxygen and measured oxygen was compared to evaluate the macroscopic model as well as the photochemical parameters involved. Oxygen measurements at various depths were compared to calculated values. Furthermore, we explored the use of noninvasive diffuse correlation spectroscopy (DCS) to measure tumor blood flow changes in response to PDT to improve the model calculation of reacted singlet oxygen. Mice were monitored after treatment to see the effect of oxygenation on long-term recurrence-free survival as well as the efficacy of using reacted singlet oxygen as a predictive measure of outcome. Measurement of oxygenation during treatment helps to improve SOED as well as confirm the photochemical parameters involved in the macroscopic model. Use of DCS in predicting oxygenation changes was also investigated.

  20. PsychoNet: a psycholinguistc commonsense ontology

    OpenAIRE

    Mohtasseb, Haytham; Ahmed, Amr

    2010-01-01

    Ontologies have been widely accepted as the most advanced knowledge representation model. This paper introduces PsychoNet, a new knowledgebase that forms the link between psycholinguistic taxonomy, existing in LIWC, and its semantic textual representation in the form of commonsense semantic ontology, represented by ConceptNet. The integration of LIWC and ConceptNet and the added functionalities facilitate employing ConceptNet in psycholinguistic studies. Furthermore, it simplifies utilization...

  1. The timetable of evolution

    Science.gov (United States)

    Knoll, Andrew H.; Nowak, Martin A.

    2017-01-01

    The integration of fossils, phylogeny, and geochronology has resulted in an increasingly well-resolved timetable of evolution. Life appears to have taken root before the earliest known minimally metamorphosed sedimentary rocks were deposited, but for a billion years or more, evolution played out beneath an essentially anoxic atmosphere. Oxygen concentrations in the atmosphere and surface oceans first rose in the Great Oxygenation Event (GOE) 2.4 billion years ago, and a second increase beginning in the later Neoproterozoic Era [Neoproterozoic Oxygenation Event (NOE)] established the redox profile of modern oceans. The GOE facilitated the emergence of eukaryotes, whereas the NOE is associated with large and complex multicellular organisms. Thus, the GOE and NOE are fundamental pacemakers for evolution. On the time scale of Earth’s entire 4 billion–year history, the evolutionary dynamics of the planet’s biosphere appears to be fast, and the pace of evolution is largely determined by physical changes of the planet. However, in Phanerozoic ecosystems, interactions between new functions enabled by the accumulation of characters in a complex regulatory environment and changing biological components of effective environments appear to have an important influence on the timing of evolutionary innovations. On the much shorter time scale of transient environmental perturbations, such as those associated with mass extinctions, rates of genetic accommodation may have been limiting for life. PMID:28560344

  2. 78 FR 72451 - Net Investment Income Tax

    Science.gov (United States)

    2013-12-02

    ... Revenue Service 26 CFR Part 1 RIN 1545-BL74 Net Investment Income Tax AGENCY: Internal Revenue Service...). These regulations provide guidance on the computation of net investment income. The regulations affect... lesser of: (A) The individual's net investment income for such taxable year, or (B) the excess (if any...

  3. 47 CFR 69.302 - Net investment.

    Science.gov (United States)

    2010-10-01

    ... 47 Telecommunication 3 2010-10-01 2010-10-01 false Net investment. 69.302 Section 69.302... Apportionment of Net Investment § 69.302 Net investment. (a) Investment in Accounts 2001, 1220 and Class B Rural...) Investment in Accounts 2002, 2003 and to the extent such inclusions are allowed by this Commission, Account...

  4. 47 CFR 65.450 - Net income.

    Science.gov (United States)

    2010-10-01

    ... 47 Telecommunication 3 2010-10-01 2010-10-01 false Net income. 65.450 Section 65.450... OF RETURN PRESCRIPTION PROCEDURES AND METHODOLOGIES Exchange Carriers § 65.450 Net income. (a) Net income shall consist of all revenues derived from the provision of interstate telecommunications services...

  5. 47 CFR 65.500 - Net income.

    Science.gov (United States)

    2010-10-01

    ... 47 Telecommunication 3 2010-10-01 2010-10-01 false Net income. 65.500 Section 65.500... OF RETURN PRESCRIPTION PROCEDURES AND METHODOLOGIES Interexchange Carriers § 65.500 Net income. The net income methodology specified in § 65.450 shall be utilized by all interexchange carriers that are...

  6. NetBeans IDE 8 cookbook

    CERN Document Server

    Salter, David

    2014-01-01

    If you're a Java developer of any level using NetBeans and want to learn how to get the most out of NetBeans, then this book is for you. Learning how to utilize NetBeans will provide a firm foundation for your Java application development.

  7. Characterizing behavioural congruences for Petri nets

    DEFF Research Database (Denmark)

    Nielsen, Mogens; Priese, Lutz; Sassone, Vladimiro

    1995-01-01

    We exploit a notion of interface for Petri nets in order to design a set of net combinators. For such a calculus of nets, we focus on the behavioural congruences arising from four simple notions of behaviour, viz., traces, maximal traces, step, and maximal step traces, and from the corresponding...

  8. 27 CFR 4.37 - Net contents.

    Science.gov (United States)

    2010-04-01

    ... the volume of wine within the container, except that the following tolerances shall be allowed: (1... THE TREASURY LIQUORS LABELING AND ADVERTISING OF WINE Labeling Requirements for Wine § 4.37 Net contents. (a) Statement of net contents. The net contents of wine for which a standard of fill is...

  9. Effects of oxygen concentration on atmospheric pressure dielectric barrier discharge in Argon-Oxygen Mixture

    Science.gov (United States)

    Li, Xuechun; Li, Dian; Wang, Younian

    2016-09-01

    A dielectric barrier discharge (DBD) can generate a low-temperature plasma easily at atmospheric pressure and has been investigated for applications in trials in cancer therapy, sterilization, air pollution control, etc. It has been confirmed that reactive oxygen species (ROS) play a key role in the processes. In this work, we use a fluid model to simulate the plasma characteristics for DBD in argon-oxygen mixture. The effects of oxygen concentration on the plasma characteristics have been discussed. The evolution mechanism of ROS has been systematically analyzed. It was found that the ground state oxygen atoms and oxygen molecular ions are the dominated oxygen species under the considered oxygen concentrations. With the oxygen concentration increasing, the densities of electrons, argon atomic ions, resonance state argon atoms, metastable state argon atoms and excited state argon atoms all show a trend of decline. The oxygen molecular ions density is high and little influenced by the oxygen concentration. Ground state oxygen atoms density tends to increase before falling. The ozone density increases significantly. Increasing the oxygen concentration, the discharge mode begins to change gradually from the glow discharge mode to Townsend discharge mode. Project supported by the National Natural Science Foundation of China (Grant No. 11175034).

  10. Reação de geração de oxigênio em eletrodos de Mn2O3 suportados em aço inoxidável Oxygen evolution reaction on Mn2O3 electrodes supported on stainless steel

    Directory of Open Access Journals (Sweden)

    Hamilton Varela

    2000-12-01

    Full Text Available A study of the kinetics of oxygen evolution in alkaline conditions from ceramic films of Mn2O3 supported on stainless steel was carried out. This study has been done through the determination of transfer coefficients, Tafel slopes and exchange currents using potentiodynamic and quasi-potentiostatic measurements. The activation energy was determined as a function of the overpotential and, additionally, the electrode active surface was estimated. The results are consistent with data already published for other electrodes, implying that the methods used in this work were reliable and precise.

  11. NET 40 Generics Beginner's Guide

    CERN Document Server

    Mukherjee, Sudipta

    2012-01-01

    This is a concise, practical guide that will help you learn Generics in .NET, with lots of real world and fun-to-build examples and clear explanations. It is packed with screenshots to aid your understanding of the process. This book is aimed at beginners in Generics. It assumes some working knowledge of C# , but it isn't mandatory. The following would get the most use out of the book: Newbie C# developers struggling with Generics. Experienced C++ and Java Programmers who are migrating to C# and looking for an alternative to other generic frameworks like STL and JCF would find this book handy.

  12. The Net Reclassification Index (NRI)

    DEFF Research Database (Denmark)

    Pepe, Margaret S.; Fan, Jing; Feng, Ziding

    2015-01-01

    The Net Reclassification Index (NRI) is a very popular measure for evaluating the improvement in prediction performance gained by adding a marker to a set of baseline predictors. However, the statistical properties of this novel measure have not been explored in depth. We demonstrate the alarming...... marker is proven to erroneously yield a positive NRI. Some insight into this phenomenon is provided. Since large values for the NRI statistic may simply be due to use of poorly fitting risk models, we suggest caution in using the NRI as the basis for marker evaluation. Other measures of prediction...

  13. High Selectivity Oxygen Delignification

    Energy Technology Data Exchange (ETDEWEB)

    Arthur J. Ragauskas

    2005-09-30

    The overall objective of this program was to develop improved extended oxygen delignification (EOD) technologies for current U.S. pulp mill operations. This was accomplished by: (1) Identifying pulping conditions that optimize O and OO performance; (2) Identifying structural features of lignin that enhance reactivity towards EOD of high kappa pulps; (3) Identifying factors minimizing carbohydrate degradation and improve pulp strength of EOD high kappa pulps; (4) Developing a simple, reproducible method of quantifying yield gains from EOD; and (5) Developing process conditions that significantly reduce the capital requirements of EOD while optimizing the yield benefits. Key research outcomes included, demonstrating the use of a mini-O sequence such as (E+O)Dkf:0.05(E+O) or Dkf:0.05(E+O)(E+O) without interstage washing could capture approximately 60% of the delignification efficiency of a conventional O-stage without the major capital requirements associated with an O-stage for conventional SW kraft pulps. The rate of formation and loss of fiber charge during an O-stage stage can be employed to maximize net fiber charge. Optimal fiber charge development and delignification are two independent parameters and do not parallel each other. It is possible to utilize an O-stage to enhance overall cellulosic fiber charge of low and high kappa SW kraft pulps which is beneficial for physical strength properties. The application of NIR and multi-variant analysis was developed into a rapid and simple method of determining the yield of pulp from an oxygen delignification stage that has real-world mill applications. A focus point of this program was the demonstration that Kraft pulping conditions and oxygen delignification of high and low-kappa SW and HW pulps are intimately related. Improved physical pulp properties and yield can be delivered by controlling the H-factor and active alkali charge. Low AA softwood kraft pulp with a kappa number 30 has an average improvement of 2% in

  14. Oxygen - A Four Billion Year History

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    The air we breathe is twenty-one percent oxygen, an amount higher than on any other known world. While we may take our air for granted, Earth was not always an oxygenated planet. How did it become this way? Oxygen is the most current account of the history of atmospheric oxygen on Earth. Donald...... Canfield--one of the world's leading authorities on geochemistry, earth history, and the early oceans--covers this vast history, emphasizing its relationship to the evolution of life and the evolving chemistry of the Earth. With an accessible and colorful first-person narrative, he draws from a variety...... on a remarkable journey through the history of the oxygenation of our planet....

  15. -Net Approach to Sensor -Coverage

    Directory of Open Access Journals (Sweden)

    Fusco Giordano

    2010-01-01

    Full Text Available Wireless sensors rely on battery power, and in many applications it is difficult or prohibitive to replace them. Hence, in order to prolongate the system's lifetime, some sensors can be kept inactive while others perform all the tasks. In this paper, we study the -coverage problem of activating the minimum number of sensors to ensure that every point in the area is covered by at least sensors. This ensures higher fault tolerance, robustness, and improves many operations, among which position detection and intrusion detection. The -coverage problem is trivially NP-complete, and hence we can only provide approximation algorithms. In this paper, we present an algorithm based on an extension of the classical -net technique. This method gives an -approximation, where is the number of sensors in an optimal solution. We do not make any particular assumption on the shape of the areas covered by each sensor, besides that they must be closed, connected, and without holes.

  16. NETS - Danish participation. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Alsen, S. (Grontmij - Carl Bro, Glostrup (Denmark)); Theel, C. (Baltic Sea Solutions, Holeby (Denmark))

    2008-12-15

    Within the NICe-funded project 'Nordic Environmental Technology Solutions (NETS)' a new type of networking at the Nordic level was organized in order to jointly exploit the rapidly growing market potential in the environmental technology sector. The project aimed at increased and professionalized commercialization of Nordic Cleantech in energy and water business segments through 1) closer cooperation and joint marketing activities, 2) a website, 3) cleantech product information via brochures and publications 4) and participating in relevant trade fairs and other industry events. Facilitating business-to-business activities was another core task for the NETS project partners from Norway, Sweden, Finland and Denmark with the aim to encourage total solutions for combined Cleantech system offers. The project has achieved to establish a Cleantech register of 600 Nordic Cleantech companies, a network of 86 member enterprises, produced several publications and brochures for direct technology promotion and a website for direct access to company profiles and contact data. The project partners have attended 14 relevant international Cleantech trade fairs and conferences and facilitated business-to-business contacts added by capacity building offers through two company workshops. The future challenge for the project partners and Nordic Cleantech will be to coordinate the numerous efforts within the Nordic countries in order to reach concerted action and binding of member companies for reliable services, an improved visibility and knowledge exchange. With Cleantech's growing market influence and public awareness, the need to develop total solutions is increasing likewise. Marketing efforts should be encouraged cross-sectional and cross-border among the various levels of involved actors from both the public and the private sector. (au)

  17. Oxygen Transport Ceramic Membranes

    Energy Technology Data Exchange (ETDEWEB)

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-11-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In the current research, the electrical conductivity and Seebeck coefficient were measured as a function of temperature in air. Based on these measurements, the charge carrier concentration, net acceptor dopant concentration, activation energy of conduction and mobility were estimated. The studies on the fracture toughness of the LSFT and dual phase membranes at room temperature have been completed and reported previously. The membranes that are exposed to high temperatures at an inert and a reactive atmosphere undergo many structural and chemical changes which affects the mechanical properties. To study the effect of temperature on the membranes when exposed to an inert environment, the membranes (LAFT and Dual phase) were heat treated at 1000 C in air and N{sub 2} atmosphere and hardness and fracture toughness of the membranes were studied after the treatment. The indentation method was used to find the fracture toughness and the effect of the heat treatment on the mechanical properties of the membranes. Further results on the investigation of the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appears to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. 2-D modeling of oxygen movement has been undertaken in order to fit isotope data. The model will serve to study ''frozen'' profiles in patterned or composite membranes.

  18. Application and Theory of Petri Nets

    DEFF Research Database (Denmark)

    This volume contains the proceedings of the 13th International Conference onApplication and Theory of Petri Nets, held in Sheffield, England, in June 1992. The aim of the Petri net conferences is to create a forum for discussing progress in the application and theory of Petri nets. Typically....... Balbo and W. Reisig, 18 submitted papers, and seven project papers. The submitted papers and project presentations were selectedby the programme committee and a panel of referees from a large number of submissions....

  19. Are You Neutral About Net Neutrality

    Science.gov (United States)

    2007-06-20

    Information Resources Management College National Defense University Are You Neutral About Net Neutrality ? A presentation for Systems & Software...author uses Verizon FiOS for phone, TV, and internet service 3 Agenda Net Neutrality —Through 2 Lenses Who Are the Players & What Are They Saying...Medical Treatment Mini-Case Studies Updates Closing Thoughts 4 Working Definitions of Net Neutrality "Network Neutrality" is the concept that

  20. Texture Based Image Analysis With Neural Nets

    Science.gov (United States)

    Ilovici, Irina S.; Ong, Hoo-Tee; Ostrander, Kim E.

    1990-03-01

    In this paper, we combine direct image statistics and spatial frequency domain techniques with a neural net model to analyze texture based images. The resultant optimal texture features obtained from the direct and transformed image form the exemplar pattern of the neural net. The proposed approach introduces an automated texture analysis applied to metallography for determining the cooling rate and mechanical working of the materials. The results suggest that the proposed method enhances the practical applications of neural nets and texture extraction features.

  1. Factors associated with mosquito net use by individuals in households owning nets in Ethiopia

    Directory of Open Access Journals (Sweden)

    Graves Patricia M

    2011-12-01

    Full Text Available Abstract Background Ownership of insecticidal mosquito nets has dramatically increased in Ethiopia since 2006, but the proportion of persons with access to such nets who use them has declined. It is important to understand individual level net use factors in the context of the home to modify programmes so as to maximize net use. Methods Generalized linear latent and mixed models (GLLAMM were used to investigate net use using individual level data from people living in net-owning households from two surveys in Ethiopia: baseline 2006 included 12,678 individuals from 2,468 households and a sub-sample of the Malaria Indicator Survey (MIS in 2007 included 14,663 individuals from 3,353 households. Individual factors (age, sex, pregnancy; net factors (condition, age, net density; household factors (number of rooms [2006] or sleeping spaces [2007], IRS, women's knowledge and school attendance [2007 only], wealth, altitude; and cluster level factors (rural or urban were investigated in univariate and multi-variable models for each survey. Results In 2006, increased net use was associated with: age 25-49 years (adjusted (a OR = 1.4, 95% confidence interval (CI 1.2-1.7 compared to children U5; female gender (aOR = 1.4; 95% CI 1.2-1.5; fewer nets with holes (Ptrend = 0.002; and increasing net density (Ptrend [all nets in HH good] = 1.6; 95% CI 1.2-2.1; increasing net density (Ptrend [per additional space] = 0.6, 95% CI 0.5-0.7; more old nets (aOR [all nets in HH older than 12 months] = 0.5; 95% CI 0.3-0.7; and increasing household altitude (Ptrend Conclusion In both surveys, net use was more likely by women, if nets had fewer holes and were at higher net per person density within households. School-age children and young adults were much less likely to use a net. Increasing availability of nets within households (i.e. increasing net density, and improving net condition while focusing on education and promotion of net use, especially in school-age children

  2. Artificial oxygen transport protein

    Science.gov (United States)

    Dutton, P. Leslie

    2014-09-30

    This invention provides heme-containing peptides capable of binding molecular oxygen at room temperature. These compounds may be useful in the absorption of molecular oxygen from molecular oxygen-containing atmospheres. Also included in the invention are methods for treating an oxygen transport deficiency in a mammal.

  3. Pro Agile NET Development with Scrum

    CERN Document Server

    Blankenship, Jerrel; Millett, Scott

    2011-01-01

    Pro Agile .NET Development with SCRUM guides you through a real-world ASP.NET project and shows how agile methodology is put into practice. There is plenty of literature on the theory behind agile methodologies, but no book on the market takes the concepts of agile practices and applies these in a practical manner to an end-to-end ASP.NET project, especially the estimating, requirements and management aspects of a project. Pro Agile .NET Development with SCRUM takes you through the initial stages of a project - gathering requirements and setting up an environment - through to the development a

  4. Professional Visual Basic 2010 and .NET 4

    CERN Document Server

    Sheldon, Bill; Sharkey, Kent

    2010-01-01

    Intermediate and advanced coverage of Visual Basic 2010 and .NET 4 for professional developers. If you've already covered the basics and want to dive deep into VB and .NET topics that professional programmers use most, this is your book. You'll find a quick review of introductory topics-always helpful-before the author team of experts moves you quickly into such topics as data access with ADO.NET, Language Integrated Query (LINQ), security, ASP.NET web programming with Visual Basic, Windows workflow, threading, and more. You'll explore all the new features of Visual Basic 2010 as well as all t

  5. NASA Net Zero Energy Buildings Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Pless, S.; Scheib, J.; Torcellini, P.; Hendron, B.; Slovensky, M.

    2014-10-01

    In preparation for the time-phased net zero energy requirement for new federal buildings starting in 2020, set forth in Executive Order 13514, NASA requested that the National Renewable Energy Laboratory (NREL) to develop a roadmap for NASA's compliance. NASA detailed a Statement of Work that requested information on strategic, organizational, and tactical aspects of net zero energy buildings. In response, this document presents a high-level approach to net zero energy planning, design, construction, and operations, based on NREL's first-hand experience procuring net zero energy construction, and based on NREL and other industry research on net zero energy feasibility. The strategic approach to net zero energy starts with an interpretation of the executive order language relating to net zero energy. Specifically, this roadmap defines a net zero energy acquisition process as one that sets an aggressive energy use intensity goal for the building in project planning, meets the reduced demand goal through energy efficiency strategies and technologies, then adds renewable energy in a prioritized manner, using building-associated, emission- free sources first, to offset the annual energy use required at the building; the net zero energy process extends through the life of the building, requiring a balance of energy use and production in each calendar year.

  6. Towards a Standard for Modular Petri Nets

    DEFF Research Database (Denmark)

    Kindler, Ekkart; Petrucci, Laure

    2009-01-01

    When designing complex systems, mechanisms for structuring, composing, and reusing system components are crucial. Today, there are many approaches for equipping Petri nets with such mechanisms. In the context of defining a standard interchange format for Petri nets, modular PNML was defined....... Moreover, we present and discuss some more advanced features of modular Petri nets that could be included in the standard. This way, we provide a formal foundation and a basis for a discussion of features to be included in the upcoming standard of a module concept for Petri nets in general and for high...

  7. Workshop on Oxygen in the Terrestrial Planets

    Science.gov (United States)

    2004-01-01

    Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe

  8. Experiments and simulation of a net closing mechanism for tether-net capture of space debris

    Science.gov (United States)

    Sharf, Inna; Thomsen, Benjamin; Botta, Eleonora M.; Misra, Arun K.

    2017-10-01

    This research addresses the design and testing of a debris containment system for use in a tether-net approach to space debris removal. The tether-net active debris removal involves the ejection of a net from a spacecraft by applying impulses to masses on the net, subsequent expansion of the net, the envelopment and capture of the debris target, and the de-orbiting of the debris via a tether to the chaser spacecraft. To ensure a debris removal mission's success, it is important that the debris be successfully captured and then, secured within the net. To this end, we present a concept for a net closing mechanism, which we believe will permit consistently successful debris capture via a simple and unobtrusive design. This net closing system functions by extending the main tether connecting the chaser spacecraft and the net vertex to the perimeter and around the perimeter of the net, allowing the tether to actuate closure of the net in a manner similar to a cinch cord. A particular embodiment of the design in a laboratory test-bed is described: the test-bed itself is comprised of a scaled-down tether-net, a supporting frame and a mock-up debris. Experiments conducted with the facility demonstrate the practicality of the net closing system. A model of the net closure concept has been integrated into the previously developed dynamics simulator of the chaser/tether-net/debris system. Simulations under tether tensioning conditions demonstrate the effectiveness of the closure concept for debris containment, in the gravity-free environment of space, for a realistic debris target. The on-ground experimental test-bed is also used to showcase its utility for validating the dynamics simulation of the net deployment, and a full-scale automated setup would make possible a range of validation studies of other aspects of a tether-net debris capture mission.

  9. Oxygen-enhanced combustion

    CERN Document Server

    Baukal, Charles E

    2013-01-01

    Combustion technology has traditionally been dominated by air/fuel combustion. However, two developments have increased the significance of oxygen-enhanced combustion-new technologies that produce oxygen less expensively and the increased importance of environmental regulations. Advantages of oxygen-enhanced combustion include less pollutant emissions as well as increased energy efficiency and productivity. Oxygen-Enhanced Combustion, Second Edition compiles information about using oxygen to enhance industrial heating and melting processes. It integrates fundamental principles, applications, a

  10. Catalysis of the electrochemical water oxidation to oxygen

    NARCIS (Netherlands)

    Díaz Morales, Oscar Alfonso

    2015-01-01

    This thesis discusses the parameters affecting the catalysis for the electrochemical conversion of water into oxygen. The slow kinetics for the oxygen evolution reaction (OER) is one of the major bottlenecks in the solar energy-to-fuels conversion process, which reduces the efficiency for the

  11. Functional properties of the oxygen evolving complex of photosystem 2

    NARCIS (Netherlands)

    Vliet, van P.H.

    1996-01-01


    This Thesis presents the results of a study by electron paramagnetic resonance (EPR) and measurements of oxygen evolution of the Oxygen Evolving Complex of Photosystem 11 (PS-II) in PS-II enriched membranes from spinach.

    The experimental part of this Thesis is preceded by a

  12. Cathodic oxygen consumption and electrically induced osteogenesis.

    Science.gov (United States)

    Brighton, C T; Adler, S; Black, J; Itada, N; Friedenberg, Z B

    1975-01-01

    Small amounts of electric current stimulate bone formation in the region of a cathode. The purpose of this experiment is to compare changes in oxygen and hydroxyl ion concentration that occur at the cathode at current levels known to be capable of inducing osteogenesis (10-20 muamps) with those changes that occur at current levels known to be toxic to bone (100 muamps). An oxygen consumption chamber containing an oxygen electrode is fitted with two stainless steel electrodes which are connected to a constant current source. At the cathode, with a current of 100 muamps, oxygen is consumed at nearly stoichiometric rates. At higher current (100 muamps) levels, cathodic oxygen consumption gives way to hydrogen evolution. Cathodic hydroxyl ion production is directly proportional to current. It is concluded from these in vitro experiments that at 10-20 muamps the oxygen tension in the vicinity of the cathode is lowered and the pH is moderately increased. At 100 muamps the oxygen tension is not lowered, but the pH is increased dramatically. If these same changes occur in the vicinity of a cathode in vivo, then lowering the local tissue oxygen tension and raising the local pH may be mechanisms operative in electrically induced bone formation.

  13. HANPP Collection: Human Appropriation of Net Primary Productivity as a Percentage of Net Primary Productivity

    Data.gov (United States)

    National Aeronautics and Space Administration — The Human Appropriation of Net Primary Productivity (HANPP) as a Percentage of Net Primary Product (NPP) portion of the HANPP Collection represents a map identifying...

  14. Price smarter on the Net.

    Science.gov (United States)

    Baker, W; Marn, M; Zawada, C

    2001-02-01

    Companies generally have set prices on the Internet in two ways. Many start-ups have offered untenably low prices in a rush to capture first-mover advantage. Many incumbents have simply charged the same prices on-line as they do off-line. Either way, companies are missing a big opportunity. The fundamental value of the Internet lies not in lowering prices or making them consistent but in optimizing them. After all, if it's easy for customers to compare prices on the Internet, it's also easy for companies to track customers' behavior and adjust prices accordingly. The Net lets companies optimize prices in three ways. First, it lets them set and announce prices with greater precision. Different prices can be tested easily, and customers' responses can be collected instantly. Companies can set the most profitable prices, and they can tap into previously hidden customer demand. Second, because it's so easy to change prices on the Internet, companies can adjust prices in response to even small fluctuations in market conditions, customer demand, or competitors' behavior. Third, companies can use the clickstream data and purchase histories that it collects through the Internet to segment customers quickly. Then it can offer segment-specific prices or promotions immediately. By taking full advantage of the unique possibilities afforded by the Internet to set prices with precision, adapt to changing circumstances quickly, and segment customers accurately, companies can get their pricing right. It's one of the ultimate drivers of e-business success.

  15. 78 FR 72393 - Net Investment Income Tax

    Science.gov (United States)

    2013-12-02

    ... Investment Income Tax; Final and Proposed Rules #0;#0;Federal Register / Vol. 78, No. 231 / Monday, December... Parts 1 and 602 RIN 1545-BK44 Net Investment Income Tax AGENCY: Internal Revenue Service (IRS), Treasury... Investment Income Tax and the computation of Net Investment Income. The regulations affect individuals...

  16. 77 FR 72611 - Net Investment Income Tax

    Science.gov (United States)

    2012-12-05

    ... December 5, 2012 Part V Department of the Treasury Internal Revenue Service 26 CFR Part 1 Net Investment... Investment Income Tax AGENCY: Internal Revenue Service (IRS), Treasury. ACTION: Notice of proposed rulemaking...) the individual's net investment income for such taxable year, or (B) the excess (if any) of (i) the...

  17. Net analyte signal based statistical quality control

    NARCIS (Netherlands)

    Skibsted, E.T.S.; Boelens, H.F.M.; Westerhuis, J.A.; Smilde, A.K.; Broad, N.W.; Rees, D.R.; Witte, D.T.

    2005-01-01

    Net analyte signal statistical quality control (NAS-SQC) is a new methodology to perform multivariate product quality monitoring based on the net analyte signal approach. The main advantage of NAS-SQC is that the systematic variation in the product due to the analyte (or property) of interest is

  18. Asynchronous stream processing with S-Net

    NARCIS (Netherlands)

    Grelck, C.; Scholz, S.-B.; Shafarenko, A.

    2010-01-01

    We present the rationale and design of S-Net, a coordination language for asynchronous stream processing. The language achieves a near-complete separation between the application code, written in any conventional programming language, and the coordination/communication code written in S-Net. Our

  19. Using the MVC architecture on . NET platform

    OpenAIRE

    Ježek, David

    2011-01-01

    This thesis deals with usage of MVC (Model View Controller) technology in web development on ASP.NET platform from Microsoft. Mainly it deals with latest version of framework ASP.NET MVC 3. First part describes MVC architecture and the second describes usage of MVC in certain parts of web application an comparing with PHP.

  20. Analysis of Petri Nets and Transition Systems

    Directory of Open Access Journals (Sweden)

    Eike Best

    2015-08-01

    Full Text Available This paper describes a stand-alone, no-frills tool supporting the analysis of (labelled place/transition Petri nets and the synthesis of labelled transition systems into Petri nets. It is implemented as a collection of independent, dedicated algorithms which have been designed to operate modularly, portably, extensibly, and efficiently.

  1. 27 CFR 7.27 - Net contents.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Net contents. 7.27 Section 7.27 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF... the net contents are displayed by having the same blown, branded, or burned in the container in...

  2. Petri nets and other models of concurrency

    DEFF Research Database (Denmark)

    Nielsen, Mogens; Sassone, Vladimiro

    1998-01-01

    This paper retraces, collects, and summarises contributions of the authors - in collaboration with others - on the theme of Petri nets and their categorical relationships to other models of concurrency.......This paper retraces, collects, and summarises contributions of the authors - in collaboration with others - on the theme of Petri nets and their categorical relationships to other models of concurrency....

  3. Delta Semantics Defined By Petri Nets

    DEFF Research Database (Denmark)

    Jensen, Kurt; Kyng, Morten; Madsen, Ole Lehrmann

    This report is identical to an earlier version of May 1978 except that Chapter 5 has been revised. A new paper: "A Petri Net Definition of a System Description Language", DAIMI, April 1979, 20 pages, extends the Petri net model to include a data state representing the program variables. Delta...

  4. Net neutrality and inflation of traffic

    NARCIS (Netherlands)

    Peitz, M.; Schütt, Florian

    Under strict net neutrality Internet service providers (ISPs) are required to carry data without any differentiation and at no cost to the content provider. We provide a simple framework with a monopoly ISP to evaluate the short-run effects of different net neutrality rules. Content differs in its

  5. Net Neutrality and Inflation of Traffic

    NARCIS (Netherlands)

    Peitz, M.; Schütt, F.

    2015-01-01

    Under strict net neutrality Internet service providers (ISPs) are required to carry data without any differentiation and at no cost to the content provider. We provide a simple framework with a monopoly ISP to evaluate different net neutrality rules. Content differs in its sensitivity to delay.

  6. The Net Neutrality Debate: The Basics

    Science.gov (United States)

    Greenfield, Rich

    2006-01-01

    Rich Greenfield examines the basics of today's net neutrality debate that is likely to be an ongoing issue for society. Greenfield states the problems inherent in the definition of "net neutrality" used by Common Cause: "Network neutrality is the principle that Internet users should be able to access any web content they choose and…

  7. Dynamic response of the thermometric net radiometer

    Science.gov (United States)

    J. D. Wilson; W. J. Massman; G. E. Swaters

    2009-01-01

    We computed the dynamic response of an idealized thermometric net radiometer, when driven by an oscillating net longwave radiation intended roughly to simulate rapid fluctuations of the radiative environment such as might be expected during field use of such devices. The study was motivated by curiosity as to whether non-linearity of the surface boundary conditions...

  8. Teaching and Learning with the Net Generation

    Science.gov (United States)

    Barnes, Kassandra; Marateo, Raymond C.; Ferris, S. Pixy

    2007-01-01

    As the Net Generation places increasingly greater demands on educators, students and teachers must jointly consider innovative ways of teaching and learning. In this, educators are supported by the fact that the Net Generation wants to learn. However, these same educators should not fail to realize that this generation learns differently from…

  9. Verification of Timed-Arc Petri Nets

    DEFF Research Database (Denmark)

    Jacobsen, Lasse; Jacobsen, Morten; Møller, Mikael Harkjær

    2011-01-01

    Timed-Arc Petri Nets (TAPN) are an extension of the classical P/T nets with continuous time. Tokens in TAPN carry an age and arcs between places and transitions are labelled with time intervals restricting the age of tokens available for transition firing. The TAPN model posses a number...

  10. A Brief Introduction to Coloured Petri Nets

    DEFF Research Database (Denmark)

    Jensen, Kurt

    1997-01-01

    Coloured Petri Nets (CP-nets or CPN) is a graphical oriented language for design, specification, simulation and verification of systems. It is in particular well- suited for systems in which communication, synchronisation and resource sharing are important. Typical examples of application areas a...

  11. Gill net and trammel net selectivity in the northern Aegean Sea, Turkey

    Directory of Open Access Journals (Sweden)

    F. Saadet Karakulak

    2008-09-01

    Full Text Available Fishing trials were carried out with gill nets and trammel nets in the northern Aegean Sea from March 2004 to February 2005. Four different mesh sizes for the gill nets and the inner panel of trammel nets (16, 18, 20 and 22 mm bar length were used. Selectivity parameters for the five most economically important species, bogue (Boops boops, annular sea bream (Diplodus annularis, striped red mullet (Mullus surmuletus, axillary sea bream (Pagellus acarne and blotched picarel (Spicara maena, caught by the two gears were estimated. The SELECT method was used to estimate the selectivity parameters of a variety of models. Catch composition and catch proportion of several species were different in gill and trammel nets. The length frequency distributions of the species caught by the two gears were significantly different. The bi-modal model selectivity curve gave the best fit for gill net and trammel net data, and there was little difference between the modal lengths of these nets. However, a clear difference was found in catching efficiency. The highest catch rates were obtained with the trammel net. Given that many discard species and small fish are caught by gill nets and trammel nets with a mesh size of 16 mm, it is clear that these nets are not appropriate for fisheries. Consequently, the best mesh size for multispecies fisheries is 18 mm. This mesh size will considerably reduce the numbers of small sized individuals and discard species in the catch.

  12. Discrete, continuous, and hybrid petri nets

    CERN Document Server

    David, René

    2004-01-01

    Petri nets do not designate a single modeling formalism. In fact, newcomers to the field confess sometimes to be a little puzzled by the diversity of formalisms that are recognized under this "umbrella". Disregarding some extensions to the theoretical modeling capabilities, and looking at the level of abstraction of the formalisms, Condition/Event, Elementary, Place/Transition, Predicate/Transition, Colored, Object Oriented... net systems are frequently encountered in the literature. On the other side, provided with appropriate interpretative extensions, Controled Net Systems, Marking Diagrams (the Petri net generalization of State Diagrams), or the many-many variants in which time can be explicitly incorporated -Time(d), Deterministic, (Generalized) Stochastic, Fuzzy...- are defined. This represents another way to define practical formalisms that can be obtained by the "cro- product" of the two mentioned dimensions. Thus Petri nets constitute a modeling paradigm, understandable in a broad sense as "the total...

  13. Oxygen and sulfur isotopes in sulfate in modern euxinic systems with implications for evaluating the extent of euxinia in ancient oceans

    Science.gov (United States)

    Gomes, Maya L.; Johnston, David T.

    2017-05-01

    Euxinic conditions, which are defined by the presence of sulfide in the water column, were common in ancient oceans. However, it is not clear how the presence of sulfide in the water column affects the balance between rates of sulfide oxidation and sulfate reduction, which plays a major role in regulating the net redox state of the ocean-atmosphere system. Euxinia could lead to higher rates of sulfide oxidation because sulfide may diffuse more rapidly into the oxic zone in solution than in sediment. Alternatively, sulfide oxidation could be inhibited by low overall availability of suitable oxidants in euxinic settings. Here, we constrain rates of sulfide oxidation versus sulfate reduction in four euxinic water columns in coastal ponds by modeling the evolution of the concentration and sulfur and oxygen isotope compositions of sulfate from post-hurricane, well-oxygenated conditions to modern, euxinic conditions. The results of the one-dimensional, depth-dependent models of water column sulfate geochemistry indicate that the fraction of sulfate reduced that is subsequently reoxidized is low (0.11-0.42) in euxinic systems relative to the modern well-oxygenated ocean (0.75-0.90). This implies that sulfide reoxidation rates are low in euxinic systems because of oxidant limitation and physical transport. Low fractional sulfide reoxidation in euxinic systems has important implications for exploring how oxygen levels in the ocean and atmosphere have changed through Earth history. We use a marine sulfate isotope box model to explore how low reoxidation rates in euxinic systems affect marine sulfate sulfur and oxygen isotope records. Model results indicate that marine sulfate sulfur and oxygen isotope compositions increase during the expansion of euxinia with patterns that are distinct from other isotopic changes to the marine sulfate reservoir. Thus, marine sulfate sulfur and oxygen isotope box models can be applied to ancient isotope records in order to evaluate the

  14. Pro visual C++/CLI and the net 35 platform

    CERN Document Server

    Fraser, Stephen

    2008-01-01

    Pro Visual C++/CLI and the .NET 3.5 Platform is about writing .NET applications using C++/CLI. While readers are learning the ins and outs of .NET application development, they will also be learning the syntax of C++, both old and new to .NET. Readers will also gain a good understanding of the .NET architecture. This is truly a .NET book applying C++ as its development language not another C++ syntax book that happens to cover .NET.

  15. Control of proton exchange membrane fuel cell system breathing based on maximum net power control strategy

    Science.gov (United States)

    Li, Qi; Chen, Weirong; Liu, Zhixiang; Guo, Ai; Liu, Shukui

    2013-11-01

    In order to achieve the maximum net power, the analysis for the maximum net power characterization of a proton exchange membrane fuel cell (PEMFC) system is carried out. A maximum net power control (MNPC) strategy based on an implicit generalized predictive control (IGPC) and a reference governor is proposed to keep optimal oxygen excess ratio (OER) trajectory. The IGPC based on an effective informed adaptive particle swarm optimization (EIA-PSO) algorithm is developed to solve the predictive control law and reduce the computational complexity in the rolling optimization process. The simulations of three conditional tests are implemented and the results demonstrate that the proposed strategy can track the optimal OER trajectory, reduce the parasitic power and maximize the output net power. The comprehensive comparisons based on three conditional tests verify that the MNPC-IGPC has better robust performance in the presence of large disturbances, time delay and various noises. The experimental comparison with internal control system of Ballard 1.2 kW Nexa Power Module testifies the validity of the MNPC-IGPC for increasing the net power. Hence, this proposed strategy can provide better behavior to guarantee optimal OER trajectory and the maximum net power even though the disturbances and uncertainties occur.

  16. Oxygen transport membrane

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a novel composite oxygen transport membrane as well as its preparation and uses thereof.......The present invention relates to a novel composite oxygen transport membrane as well as its preparation and uses thereof....

  17. Using oxygen at home

    Science.gov (United States)

    ... a gas stove) or any other heating source. Travel and Oxygen Most sure oxygen will be available ... Duplication for commercial use must be authorized in writing by ADAM Health Solutions. About MedlinePlus Site Map ...

  18. Miniature oxygen resuscitator

    Science.gov (United States)

    Johnson, G.; Teegen, J. T.; Waddell, H.

    1969-01-01

    Miniature, portable resuscitation system is used during evacuation of patients to medical facilities. A carrying case contains a modified resuscitator head, cylinder of oxygen, two-stage oxygen regulator, low pressure tube, and a mask for mouth and nose.

  19. KONVERGENSI DALAM PROGRAM NET CITIZEN JOURNALISM

    Directory of Open Access Journals (Sweden)

    Rhafidilla Vebrynda

    2017-06-01

    Full Text Available Di dalam artikel ini, peneliti ingin melihat perkembangan teknologi di Indonesia sebagai sebuah peluang untuk menjalankan sebuah program berita berbasis video kiriman masyarakat. Perkembangan teknologi tersebut adalah teknologi penyiaran, teknologi sosial media dan teknologi dalam proses produksi sebuah video. Di Indonesia, jumlah televisi semakin banyak. Setiap stasiun televisi harus bersaing untuk dapat bertahan hidup. Net TV merupakan sebuah stasiun televisi baru di Indonesia yang harus memiliki berbagai program unggulan baru agar dapat bersaing dengan televisi lainnya yang sudah ada. Net TV menggunakan berbagai platform media untuk menjalankan program Net Citizen Journalism (Net CJ. Penggunaan berbagai platform media dikenal dengan istilah multiplatform dan secara teoritis dikenal dengan istilah konvergensi. Konvergensi yaitu saat meleburnya domain-domain dalam berbagai media komunikasi. Artikel ini menggunakan metode studi kasus untuk melihat bagaimana konvergensi terjadi dalam proses pengelolaan program Net CJ. Teknik pengumpulan data adalah dengan wawancara mendalam, observasi dan studi dokumen. Wawancara mendalam dilakukan dari tiga sudut pandang yaitu dari pengelola program, pengguna/audience dan pengamat media. Penelitian ini menemukan bahwa dengan menggunakan berbagai platform media yang fungsinya berbeda, memiliki satu tujuan yang sama yaitu untuk menjalankan program Net CJ. Adapun berbagai platform dalam proses produksi program yaitu tayangan TV konvensional, streaming TV, website, aplikasi Net CJ, facebook, twitter, instagram dan path. Konvergensi media dijalankan dalam dua proses, yaitu proses produksi dan proses promosi program berita.

  20. Net Neutrality: Media Discourses and Public Perception

    Directory of Open Access Journals (Sweden)

    Christine Quail

    2010-01-01

    Full Text Available This paper analyzes media and public discourses surrounding net neutrality, with particular attention to public utility philosophy, from a critical perspective. The article suggests that further public education about net neutrality would be beneficial. The first portion of this paper provides a survey of the existing literature surrounding net neutrality, highlighting the contentious debate between market-based and public interest perspectives. In order to contextualize the debate, an overview of public utility philosophy is provided, shedding light on how the Internet can be conceptualized as a public good. Following this discussion, an analysis of mainstream media is presented, exploring how the media represents the issue of net neutrality and whether or not the Internet is discussed through the lens of public utility. To further examine how the net neutrality debate is being addressed, and to see the potential impacts of media discourses on the general public, the results of a focus group are reported and analyzed. Finally, a discussion assesses the implications of the net neutrality debate as presented through media discourses, highlighting the future of net neutrality as an important policy issue.