Timescales of Oxygenation Following the Evolution of Oxygenic Photosynthesis.

PubMed

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.

Influence of Fluoride Ion on the Performance of Pb-Ag Anode During Long-Term Galvanostatic Electrolysis

NASA Astrophysics Data System (ADS)

Zhong, Xiaocong; Yu, Xiaoying; Jiang, Liangxing; Lv, Xiaojun; Liu, Fangyang; Lai, Yanqing; Li, Jie

2015-09-01

Anodic potential, morphology and phase composition of the anodic layer, corrosion morphology of the metallic substrate, and oxygen evolution behavior of Pb-Ag anode in H2SO4 solution without/with fluoride ion were investigated and compared. The results showed that the presence of fluoride ions contributed to a smoother anodic layer with lower PbO2 concentration, which resulted in lower double layer capacity and higher charge transfer resistance for the oxygen evolution reaction. Consequently, the Pb-Ag anode showed a higher anodic potential (about 35 mV) in the fluoride-containing electrolyte. In addition, the fluoride ions accelerated the detachment of loose flakes on the anodic layer. It was demonstrated that the anodic layer formed in the fluoride-containing H2SO4 solution was thinner. Furthermore, fluoride ions aggravated the corrosion of the metallic substrate at interdendritic boundary regions. Hence, the presence of fluoride ions is detrimental to oxygen evolution reactivity and increases the corrosion of the Pb-Ag anode, which may further increase the energy consumption and capital cost of zinc plants.

Elucidating the alkaline oxygen evolution reaction mechanism on platinum

DOE PAGES

Favaro, M.; Valero-Vidal, C.; Eichhorn, J.; ...

2017-03-07

Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistrymore » and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.« less

AC impedance study of degradation of porous nickel battery electrodes

NASA Technical Reports Server (NTRS)

Lenhart, Stephen J.; Macdonald, D. D.; Pound, B. G.

1987-01-01

AC impedance spectra of porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (nonporous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low.

The origin and evolution of oxygenic photosynthesis

NASA Technical Reports Server (NTRS)

Blankenship, R. E.; Hartman, H.

1998-01-01

The evolutionary developments that led to the ability of photosynthetic organisms to oxidize water to molecular oxygen are discussed. Two major changes from a more primitive non-oxygen-evolving reaction center are required: a charge-accumulating system and a reaction center pigment with a greater oxidizing potential. Intermediate stages are proposed in which hydrogen peroxide was oxidized by the reaction center, and an intermediate pigment, similar to chlorophyll d, was present.

Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

DOE PAGES

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira; ...

2016-11-30

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

DOE Office of Scientific and Technical Information (OSTI.GOV)

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less

Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

NASA Astrophysics Data System (ADS)

Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

2018-06-01

A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

Preparation of TiO2-Decorated Boron Particles by Wet Ball Milling and their Photoelectrochemical Hydrogen and Oxygen Evolution Reactions

PubMed Central

Jung, Hye Jin; Nam, Kyusuk; Sung, Hong-Gye; Hyun, Hyung Soo; Sohn, Youngku; Shin, Weon Gyu

2016-01-01

TiO2-coated boron particles were prepared by a wet ball milling method, with the particle size distribution and average particle size being easily controlled by varying the milling operation time. Based on the results from X-ray photoelectron spectroscopy, transmission electron microscopy, energy dispersive X-ray analysis, and Fourier transform infrared spectroscopy, it was confirmed that the initial oxide layer on the boron particles surface was removed by the wet milling process, and that a new B–O–Ti bond was formed on the boron surface. The uniform TiO2 layer on the 150 nm boron particles was estimated to be 10 nm thick. Based on linear sweep voltammetry, cyclic voltammetry, current-time amperometry, and electrochemical impedance analyses, the potential for the application of TiO2-coated boron particles as a photoelectrochemical catalyst was demonstrated. A current of 250 μA was obtained at a potential of 0.5 V for hydrogen evolution, with an onset potential near to 0.0 V. Finally, a current of 220 μA was obtained at a potential of 1.0 V for oxygen evolution. PMID:28774132

Stability of a Cu0.7Co2.3O4 electrode during the oxygen evolution reaction for alkaline anion-exchange membrane water electrolysis

NASA Astrophysics Data System (ADS)

Kang, Kyoung Eun; Kim, Chi Ho; Lee, Myung Sup; Jung, Chang Wook; Kim, Yang Do; Lee, Jae Ho

2018-01-01

The electrode materials for oxygen evolution, especially non-platinum group metal oxides, have attracted increasing attention. Among the spinel-type transition metal oxides, Cu0.7Co2.3O4 powders were evaluated as a potential replacement for expensive dimensionally stabilized anode materials. Cu0.7Co2.3O4 powder for use as an electrode material for oxygen evolution in an alkaline anion-exchange membrane water electrolyzer was prepared using a thermal decomposition method. The Cu0.7Co2.3O4 powders heat-treated at 250 °C exhibited the same X-ray diffraction patterns without any secondary phases as the Co3O4 spinel structure did. The Cu0.7Co2.3O4 powders heat-treated at 250 °C for 30 minutes showed the smallest mean particle size of approximately 376 nm with the powders having a homogeneous shape and size distribution. The fine powders with a relatively homogeneous size distribution showed a higher current density during the oxygen evolution reaction. The lifetime of the Cu0.7Co2.3O4 electrode was relatively long at a low current density, but was quickly shortened due to physical detachment of the Cu0.7Co2.3O4 powders as the current density was increased. This study showed that the efficiency and the stability of Cu0.7Co2.3O4 powders during the oxygen evolution reaction were related directly to the active electrode area.

Deconvoluting lung evolution: from phenotypes to gene regulatory networks

PubMed Central

Torday, John S.; Rehan, Virender K.; Hicks, James W.; Wang, Tobias; Maina, John; Weibel, Ewald R.; Hsia, Connie C.W.; Sommer, Ralf J.; Perry, Steven F.

2007-01-01

Speakers in this symposium presented examples of respiratory regulation that broadly illustrate principles of evolution from whole organ to genes. The swim bladder and lungs of aquatic and terrestrial organisms arose independently from a common primordial “respiratory pharynx” but not from each other. Pathways of lung evolution are similar between crocodiles and birds but a low compliance of mammalian lung may have driven the development of the diaphragm to permit lung inflation during inspiration. To meet the high oxygen demands of flight, bird lungs have evolved separate gas exchange and pump components to achieve unidirectional ventilation and minimize dead space. The process of “screening” (removal of oxygen from inspired air prior to entering the terminal units) reduces effective alveolar oxygen tension and potentially explains why nonathletic large mammals possess greater pulmonary diffusing capacities than required by their oxygen consumption. The “primitive” central admixture of oxygenated and deoxygenated blood in the incompletely divided reptilian heart is actually co-regulated with other autonomic cardiopulmonary responses to provide flexible control of arterial oxygen tension independent of ventilation as well as a unique mechanism for adjusting metabolic rate. Some of the most ancient oxygen-sensing molecules, i.e., hypoxia-inducible factor-1alpha and erythropoietin, are up-regulated during mammalian lung development and growth under apparently normoxic conditions, suggesting functional evolution. Normal alveolarization requires pleiotropic growth factors acting via highly conserved cell–cell signal transduction, e.g., parathyroid hormone-related protein transducing at least partly through the Wingless/int pathway. The latter regulates morphogenesis from nematode to mammal. If there is commonality among these diverse respiratory processes, it is that all levels of organization, from molecular signaling to structure to function, co-evolve progressively, and optimize an existing gas-exchange framework. PMID:20607138

Oxygen evolution reaction catalysis

DOEpatents

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.

Operando investigation of Au-MnO x thin films with improved activity for the oxygen evolution reaction

DOE PAGES

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

2017-01-20

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-MnO x thin films for the oxygen evolution reaction, which exhibit more than five times improvement over pure MnO x. These films are characterized withmore » operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. As a result, the magnitude of the enhancement is correlated to the size of the Au domains, where larger domains are the more beneficial.« less

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

DOE PAGES

Newhouse, Paul F.; Reyes-Lillo, Sebastian E.; Li, Guo; ...

2017-11-13

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Throughmore » the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.« less

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newhouse, Paul F.; Reyes-Lillo, Sebastian E.; Li, Guo

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Throughmore » the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.« less

Hydrothermally Driven Transformation of Oxygen Functional Groups at Multiwall Carbon Nanotubes for Improved Electrocatalytic Applications.

PubMed

Suryanto, Bryan H R; Chen, Sheng; Duan, Jingjing; Zhao, Chuan

2016-12-28

The role of carbon nanotubes in the advancement of energy conversion and storage technologies is undeniable. In particular, carbon nanotubes have attracted significant applications for electrocatalysis. However, one central issue related to the use of carbon nanotubes is the required oxidative pretreatment that often leads to significant damage of graphitic structures which deteriorates their electrochemical properties. Traditionally, the oxidized carbon nanomaterials are treated at high temperature under an inert atmosphere to repair the oxidation-induced defect sites, which simultaneously removes a significant number of oxygen functional groups. Nevertheless, recent studies have shown that oxygen functional groups on the surface of MWCNT are the essential active centers for a number of important electrocatalytic reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Herein we first show that hydrothermal treatment as a mild method to improve the electrochemical properties and activities of surface-oxidized MWCNT for OER, HER, and ORR without significantly altering the oxygen content. The results indicate that hydrothermal treatment could potentially repair the defects without significantly reducing the pre-existing oxygen content, which has never been achieved before with conventional high-temperature annealing treatment.

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE PAGES

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

2017-11-17

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used 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 –H 2O on the coordinatively unsaturated Ru sites (CUS)more » 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-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used 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 –H 2O on the coordinatively unsaturated Ru sites (CUS)more » 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-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Genomics of a phototrophic nitrite oxidizer: insights into the evolution of photosynthesis and nitrification.

PubMed

Hemp, James; Lücker, Sebastian; Schott, Joachim; Pace, Laura A; Johnson, Jena E; Schink, Bernhard; Daims, Holger; Fischer, Woodward W

2016-11-01

Oxygenic photosynthesis evolved from anoxygenic ancestors before the rise of oxygen ~2.32 billion years ago; however, little is known about this transition. A high redox potential reaction center is a prerequisite for the evolution of the water-oxidizing complex of photosystem II. Therefore, it is likely that high-potential phototrophy originally evolved to oxidize alternative electron donors that utilized simpler redox chemistry, such as nitrite or Mn. To determine whether nitrite could have had a role in the transition to high-potential phototrophy, we sequenced and analyzed the genome of Thiocapsa KS1, a Gammaproteobacteria capable of anoxygenic phototrophic nitrite oxidation. The genome revealed a high metabolic flexibility, which likely allows Thiocapsa KS1 to colonize a great variety of habitats and to persist under fluctuating environmental conditions. We demonstrate that Thiocapsa KS1 does not utilize a high-potential reaction center for phototrophic nitrite oxidation, which suggests that this type of phototrophic nitrite oxidation did not drive the evolution of high-potential phototrophy. In addition, phylogenetic and biochemical analyses of the nitrite oxidoreductase (NXR) from Thiocapsa KS1 illuminate a complex evolutionary history of nitrite oxidation. Our results indicate that the NXR in Thiocapsa originates from a different nitrate reductase clade than the NXRs in chemolithotrophic nitrite oxidizers, suggesting that multiple evolutionary trajectories led to modern nitrite-oxidizing bacteria.

Studying Biological Responses to Global Change in Atmospheric Oxygen

PubMed Central

Powell, Frank L.

2010-01-01

A popular book recently hypothesized that change in atmospheric oxygen over geological time is the most important physical factor in the evolution of many fundamental characteristics of modern terrestrial animals. This hypothesis is generated primarily using fossil data but the present paper considers how modern experimental biology can be used to test it. Comparative physiology and experimental evolution clearly show that changes in atmospheric O2 over the ages had the potential to drive evolution, assuming the physiological O2-sensitivity of animals today is similar to the past. Established methods, such as phylogenetically independent contrasts, as well new approaches, such as adding environmental history to phylogenetic analyses or modeling interactions between environmental stresses and biological responses with different rate constants, may be useful for testing (disproving) hypotheses about biological adaptations to changes in atmospheric O2. PMID:20385257

The Role of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Rao, Reshma R.; Wang, Xiao Renshaw

Rutile RuO 2 is known to exhibit high catalytic activity for the oxygen evolution reaction (OER) and large pseudocapacitance associated with redox of surface Ru, however the mechanistic link between these properties and the role of pH is yet to be understood. Here we report that the OER activities of the (101), (001) and (111) RuO 2 surfaces were found to increase while the potential of a pseudocapacitive feature just prior to OER shifted to lower potentials (“super-Nernstian” shift) with increasing pH on the reversible hydrogen electrode (RHE) scale. This behavior is in contrast to the (100) and (110) surfacesmore » that have pH-independent Ru redox and OER activity. The link in catalytic and pseudocapacitive behavior illustrates the importance of this redox feature in generating active sites, building new mechanistic understanding of the OER.« less

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

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.

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

NASA Astrophysics Data System (ADS)

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.

Nickel-based anodic electrocatalysts for fuel cells and water splitting

NASA Astrophysics Data System (ADS)

Chen, Dayi

Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel-based catalysts, methanol oxidation suffers from high overpotential and catalyst poisoning by high concentration of substrates, so current nickel-based catalysts are more suitable to be used as oxygen evolution catalysts. A photoanode design that applies nickel oxides to a semiconductor that is incorporated with surface-plasmonic metal electrodes to do solar water oxidation with visible light is proposed.

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte.

PubMed

Wang, Nan; Li, Ligui; Zhao, Dengke; Kang, Xiongwu; Tang, Zhenghua; Chen, Shaowei

2017-09-01

Nitrogen and sulfur-codoped graphene composites with Co 9 S 8 (NS/rGO-Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO 2 catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only -0.193 V to reach 10 mA cm -2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half-wave potential in ORR and the potential to reach 10 mA cm -2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm -2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S-codoped rGO, and Co 9 S 8 nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Highly Active Low Voltage Redox Mediator for Enhanced Rechargeability of Lithium-Oxygen Batteries.

PubMed

Kundu, Dipan; Black, Robert; Adams, Brian; Nazar, Linda F

2015-12-23

Owing to its high theoretical specific energy, the Li-oxygen battery is one of the fundamentally most promising energy storage systems, but also one of the most challenging. Poor rechargeability, involving the oxidation of insoluble and insulating lithium peroxide (Li2O2), has remained the "Achilles' heel" of this electrochemical energy storage system. We report here on a new redox mediator tris[4-(diethylamino)phenyl]amine (TDPA), that-at 3.1 V-exhibits the lowest and closest potential redox couple compared to the equilibrium voltage of the Li-oxygen cell of those reported to date, with a second couple also at a low potential of 3.5 V. We show it is a soluble "catalyst" capable of lowering the Li2O2 charging potential by >0.8 V without requiring direct electrical contact of the peroxide and that it also facilitates high discharge capacities. Its chemical and electrochemical stability, fast diffusion kinetics, and two dynamic redox potentials represent a significant advance in oxygen-evolution catalysis. It enables Li-O2 cells that can be recharged more than 100 cycles with average round-trip efficiencies >80%, opening a new avenue for practical Li-oxygen batteries.

Direct electrochemical reduction of metal-oxides

DOEpatents

Redey, Laszlo I.; Gourishankar, Karthick

2003-01-01

A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

Research on rechargeable oxygen electrodes

NASA Technical Reports Server (NTRS)

Giner, J.; Malachesky, P. A.; Holleck, G.

1971-01-01

Studies were carried out on a number of factors which may influence the behavior of the platinum electrocatalyst of oxygen electrodes for use in rechargeable metal-oxygen batteries or hydrogen-oxygen fuel cells. The effects of pretreatments for various potentials and added ionic species, which could be present in such systems, were studied with reguard to: (1) the state of surface oxidation, (2) platinum dissolution, (3) the kinetics of oxygen evolution and reduction (including the role of hydrogen peroxide), and (4) changes in porous electrode structure. These studies were carried out on smooth platinum, platinized platinum, and Teflon-bonded platinum black electrodes in carefully purified electrolyte solutions. The main factors which appear to affect rechargeable oxygen electrode performance and life are: (1) the buildup of a refractory anodic layer on extended cycling, and (2) the dissolution of platinum.

Oxygen evolution from olivine M n1 -xMxP O4 (M =Fe ,Ni,Al,Mg) delithiated cathode materials

NASA Astrophysics Data System (ADS)

Snydacker, David H.; Wolverton, C.

2017-01-01

Olivine LiMnP O4 is a promising cathode material for Li-ion batteries. One drawback of this material is the propensity of its delithiated phase, MnP O4 , to evolve oxygen gas above approximately 200 °C. During thermal runaway of cells, this oxygen gas can burn the electrolyte and other cell components and thereby jeopardize safety. Partial substitution of Mn with M =Fe , Ni, Al, or Mg has been used to improve the lithium intercalation kinetics of L ixMnP O4 ; however, the effect of these substitutions on oxygen evolution is not fully documented. In this paper, we calculate phase diagrams and oxygen evolution diagrams for these M n1 -xMxP O4 delithiated cathode materials. To generate the phase diagrams, we use subregular solid-solution models and fit the energetic parameters of these models to density functional theory calculations of special quasirandom structures. The resulting thermodynamic models describe the effect of mixing on the initial temperature of oxygen evolution and on the cumulative amount of oxygen evolution at elevated temperatures. We find that addition of Fe increases the initial temperature and decreases the cumulative amount of oxygen evolution. M n0.5F e0.5P O4 exhibits an initial temperature 50 °C higher than MnP O4 and releases 70% less oxygen gas at 300 °C. Al is insoluble in MnP O4 , so addition of Al has no affect on the initial temperature. However, Al addition does slightly decrease the amount of oxygen evolution due to an inactive AlP O4 component. Mg and Ni both decrease the initial temperature of oxygen evolution, and therefore may worsen the safety of MnP O4 .

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Evolution of a phase separated gravity independent bioreactor

NASA Technical Reports Server (NTRS)

Villeneuve, Peter E.; Dunlop, Eric H.

1992-01-01

The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of 4 atm with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l per hr (1000 times greater than the first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10-astronaut carbon load continuously.

Atmospheric oxygen level and the evolution of insect body size.

PubMed

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.

Hydrogen bond asymmetric local potentials in compressed ice.

PubMed

Huang, Yongli; Ma, Zengsheng; Zhang, Xi; Zhou, Guanghui; Zhou, Yichun; Sun, Chang Q

2013-10-31

A combination of the Lagrangian mechanics of oscillators vibration, molecular dynamics decomposition of volume evolution, and Raman spectroscopy of phonon relaxation has enabled us to resolve the asymmetric, local, and short-range potentials pertaining to the hydrogen bond (O:H-O) in compressed ice. Results show that both oxygen atoms in the O:H-O bond shift initially outwardly with respect to the coordination origin (H), lengthening the O-O distance by 0.0136 nm from 0.2597 to 0.2733 nm by Coulomb repulsion between electron pairs on adjacent oxygen atoms. Both oxygen atoms then move toward right along the O:H-O bond by different amounts upon being compressed, approaching identical length of 0.11 nm. The van der Waals potential VL(r) for the O:H noncovalent bond reaches a valley at -0.25 eV, and the lowest exchange VH(r) for the H-O polar-covalent bond is valued at -3.97 eV.

Oxygen and Biological Evolution.

ERIC Educational Resources Information Center

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)

Progress in Ion Transport Membranes for Gas Separation Applications

NASA Astrophysics Data System (ADS)

Bose, Arun C.; Stiegel, Gary J.; Armstrong, Phillip A.; Halper, Barry J.; (Ted) Foster, E. P.

This chapter describes the evolution and advances of ion transport membranes for gas separation applications, especially separation of oxygen from air. In partnership with the US Department of Energy (DOE), Air Products and Chemicals, Inc. (Air Products) successfully developed a novel class of mixed ion-electron conducting materials and membrane architecture. These novel materials are referred to as ion transport membranes (ITM). Generically, ITMs consist of modified perovskite and brownmillerite oxide solid electrolytes and provide high oxygen anion and electron conduction typically at high temperatures driven by an oxygen potential gradient without the need for external power. The partial pressure ratio across the ITM layer creates the driving force for oxygen separation.

The Evolution of High Temperature Gas Sensors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garzon, F. H.; Brosha, E. L.; Mukundan, R.

2001-01-01

Gas sensor technology based on high temperature solid electrolytes is maturing rapidly. Recent advances in metal oxide catalysis and thin film materials science has enabled the design of new electrochemical sensors. We have demonstrated prototype amperometric oxygen sensors, nernstian potentiometric oxygen sensors that operate in high sulfur environments, and hydrocarbon and carbon monoxide sensing mixed potentials sensors. Many of these devices exhibit part per million sensitivities, response times on the order of seconds and excellent long-term stability.

Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution.

PubMed

Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping; Zheng, Yixin; Chan, Ting-Shan; Sheu, Hwo-Shuenn; Cheng, Yuan-Chung; Chen, Hao Ming

2015-08-28

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

NASA Technical Reports Server (NTRS)

Macdonald, D. D.; Pound, B. G.; Lenhart, S. J.

1989-01-01

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

14 CFR Appendix N to Part 25 - Fuel Tank Flammability Exposure and Reliability Analysis

Code of Federal Regulations, 2012 CFR

2012-01-01

... flammability exposure time for a fuel tank. (k) Oxygen evolution occurs when oxygen dissolved in the fuel is... evolution from the fuel results in the fuel tank or compartment exceeding the inert level. The applicant must include any times when oxygen evolution from the fuel in the tank or compartment under evaluation...

14 CFR Appendix N to Part 25 - Fuel Tank Flammability Exposure and Reliability Analysis

Code of Federal Regulations, 2014 CFR

2014-01-01

... flammability exposure time for a fuel tank. (k) Oxygen evolution occurs when oxygen dissolved in the fuel is... evolution from the fuel results in the fuel tank or compartment exceeding the inert level. The applicant must include any times when oxygen evolution from the fuel in the tank or compartment under evaluation...

14 CFR Appendix N to Part 25 - Fuel Tank Flammability Exposure and Reliability Analysis

Code of Federal Regulations, 2013 CFR

2013-01-01

... flammability exposure time for a fuel tank. (k) Oxygen evolution occurs when oxygen dissolved in the fuel is... evolution from the fuel results in the fuel tank or compartment exceeding the inert level. The applicant must include any times when oxygen evolution from the fuel in the tank or compartment under evaluation...

Self-fill oxygen technology: benefits for patients, healthcare providers and the environment

PubMed Central

Hex, Nick; Setters, Jo; Little, Stuart

2016-01-01

“Non-delivery” home oxygen technologies that allow self-filling of ambulatory oxygen cylinders are emerging. They can offer a relatively unlimited supply of ambulatory oxygen in suitably assessed people who require long-term oxygen therapy (LTOT), providing they can use these systems safely and effectively. This allows users to be self-sufficient and facilitates longer periods of time away from home. The evolution and evidence base of this technology is reported with the experience of a national service review in Scotland (UK). Given that domiciliary oxygen services represent a significant cost to healthcare providers globally, these systems offer potential cost savings, are appealing to remote and rural regions due to the avoidance of cylinder delivery and have additional lower environmental impact due to reduced fossil fuel consumption and subsequently reduced carbon emissions. Evidence is emerging that self-fill/non-delivery oxygen systems can meet the ambulatory oxygen needs of many patients using LTOT and can have a positive impact on quality of life, increase time spent away from home and offer significant financial savings to healthcare providers. Educational aims Provide update for oxygen prescribers on options for home oxygen provision. Provide update on the evidence base for available self-fill oxygen technologies. Provide and update for healthcare commissioners on the potential cost-effective and environmental benefits of increased utilisation of self-fill oxygen systems. PMID:27408629

Calculation of the thermoneutral potential of NiCd and NiH2 cells

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1994-01-01

The thermoneutral potential of a nickel cadmium or nickel hydrogen cell is the potential at which the cell charge or discharge process puts out zero heat, and thus is the potential corresponding to the enthalpy change of the charge/discharge reaction, delta H. A relatively straightforward method for obtaining the thermoneutral potential E(sub tn), is based on the measured potential and temperature derivative of the cell reactions, which are related to the free energy change delta G, and entropy change delta S, respectively. Particularly in the nickel hydrogen cell, the pressure of hydrogen can often vary over an order of magnitude or more during the course of a charge or discharge. In a nickel cadmium cell, although significant changes in oxygen pressure can occur during charge or discharge, since oxygen does not enter into the charge/discharge reaction, these pressure changes are related to the heat generated from oxygen evolution and recombination. However, the entropy changes due to changes in hydrogen pressure relative to the 1 atm standard state must be included to apply this method to the nickel hydrogen cell.

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE PAGES

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

2016-12-09

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Effect of micro-oxygenation and wood type on the phenolic composition and color of an aged red wine.

PubMed

Sánchez-Iglesias, Montserrat; González-Sanjosé, Ma Luisa; Pérez-Magariño, Silvia; Ortega-Heras, Miriam; González-Huerta, Carlos

2009-12-23

Many studies have recently been published focused on the effects of micro-oxygenation on the quality of wines, its application modes, and doses, etc. However, there are still few scientific papers on how previously micro-oxygenated wines perform during storage or barrel aging. This study focused on the evolution of the phenolic composition, especially of anthocyanins, and color, together with astringency and tannins, during micro-oxygenation before barrel aging. In addition, to evaluate whether wine evolution during aging depends on barrel type, wines were aged in four different oak barrel types. Tempranillo wines, some micro-oxygenated before malolactic fermentation and others not, were aged for 12 months in American, French, Central European, and Spanish oak, following wine evolution during that period. The study was carried out for two consecutive vintages. Results showed that all wines evolved similarly; therefore, the micro-oxygenation treatment neither accelerated nor delayed the typical changes of aging. Slightly different evolutions were detected according to the barrel wood type, whether or not the wine was micro-oxygenated. The varied evolutions must therefore be associated with the differences from each oak type (structure, grain and density, composition, etc.).

Isolation Of PS II Nanoparticles And Oxygen Evolution Studies In Synechococcus Spp. PCC 7942 Under Heavy Metal Stress

NASA Astrophysics Data System (ADS)

Ahmad, Iffat Zareen; Sundaram, Shanthy; Tripathi, Ashutosh; Soumya, K. K.

2009-06-01

The effect of heavy metals was seen on the oxygen evolution pattern of a unicellular, non-heterocystous cyanobacterial strain of Synechococcus spp. PCC 7942. It was grown in a BG-11 medium supplemented with heavy metals, namely, nickel, copper, cadmium and mercury. Final concentrations of the heavy metal solution used in the culture were 0.1, 0.4 and 1 μM. All the experiments were performed in the exponential phase of the culture. Oxygen-evolving photosystem II (PS II) particles were purified from Synechococcus spp. PCC 7942 by a single-step Ni2+-affinity column chromatography after solubilization of thylakoid membranes with sucrose monolaurate. Oxygen evolution was measured with Clark type oxygen electrode fitted with a circulating water jacket. The light on the surface of the vessel was 10 w/m2. The cultures were incubated in light for 15 minutes prior to the measurement of oxygen evolution. Oxygen evolution was measured in assay mixture containing phosphate buffer (pH-7.5, 0.1 M) in the presence of potassium ferricyanide as the electron acceptor. The preparation from the control showed a high oxygen-evolving activity of 2, 300-2, 500 pmol O2 (mg Chl)-1 h-1 while the activity was decreased in the cultures grown with heavy metals. The inhibition of oxygen evolution shown by the organism in the presence of different metals was in the order Hg>Ni>Cd>Cu. Such heavy metal resistant strains will find application in the construction of PS II- based biosensors for the monitoring of pollutants.

Oxygen and Early Animal Evolution

NASA Astrophysics Data System (ADS)

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.

Singlet oxygen generator for a solar powered chemically pumped iodine laser

NASA Technical Reports Server (NTRS)

Busch, G. E.

1984-01-01

The potential of solid phase endoperoxides as a means to produce single-delta oxygen in the gas phase in concentrations useful to chemical oxygen-iodine lasers was investigated. The 1,4 - endoperoxide of ethyl 3- (4-methyl - 1-naphthyl) propanoate was deposited over an indium-oxide layer on a glass plate. Single-delta oxygen was released from the endoperoxide upon heating the organic film by means of an electrical discharge through the conductive indium oxide coating. The evolution of singlet-delta oxygen was determined by measuring the dimol emission signal at 634 nm. Comparison of the measured signal with an analytic model leads to two main conclusions: virtually all the oxygen being evolved is in the singlet-delta state and in the gas phase, and there is no significant quenching other than energy pooling on the time scale of the experiment (approximately 10 msec). The use of solid phase endoperoxide as a singlet-delta oxygen generator for an oxygen-iodine laser appears promising.

Reactive Oxygen Species on the Early Earth and Survival of Bacteria

NASA Technical Reports Server (NTRS)

Balk, Melikea; Mason, Paul; Stams, Alfons J. M.; Smidt, Hauke; Freund, Friedemann; Rothschild, Lynn

2011-01-01

An oxygen-rich atmosphere appears to have been a prerequisite for complex, multicellular life to evolve on Earth and possibly elsewhere in the Universe. However it remains unclear how free oxygen first became available on the early Earth. A potentially important, and as yet poorly constrained pathway, is the production of oxygen through the weathering of rocks and release into the near-surface environment. Reactive Oxygen Species (ROS), as precursors to molecular oxygen, are a key step in this process, and may have had a decisive impact on the evolution of life, present and past. ROS are generated from minerals in igneous rocks during hydrolysis of peroxy defects, which consist of pairs of oxygen anions oxidized to the valence state -1 and during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that, despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, organisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defences against the potentially dangerous, even lethal effects of oxygen and its derived ROS. Conversely it appears that microorganisms learned to take advantage of the enormous reactive potential and energy gain provided by nascent oxygen. We investigate how oxygen might be released through weathering. We test microorganisms in contact with rock surfaces and iron sulphides. We model bacteria such as Deionococcus radiodurans and Desulfotomaculum, Moorella and Bacillus species for their ability to grow or survive in the presence of ROS. We examine how early Life might have adapted to oxygen.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.

We report that 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. Furthermore, we report for the very first time, F doped Cu 1.5Mn 1.5O 4, identified by exploiting theoretical first principles calculations for ORR and OERmore » 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 IrO 2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO 2 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.« less

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

DOE PAGES

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; ...

2016-07-06

We report that 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. Furthermore, we report for the very first time, F doped Cu 1.5Mn 1.5O 4, identified by exploiting theoretical first principles calculations for ORR and OERmore » 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 IrO 2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO 2 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.« less

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

PubMed Central

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.

2016-01-01

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. PMID:27380719

In Situ-Grown ZnCo2O4 on Single-Walled Carbon Nanotubes as Air Electrode Materials for Rechargeable Lithium–Oxygen Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bin; Xu, Wu; Yan, Pengfei

2015-10-12

Although lithium-oxygen (Li-O2) batteries have great potential to be used as one of the next generation energy storage systems due to their ultrahigh theoretical specific energy, there are still many significant barriers before their practical applications. These barriers include electrolyte and electrode instability, poor ORR/OER efficiency and cycling capability, etc. Development of a highly efficient catalyst will not only enhance ORR/OER efficiency, it may also improve the stability of electrolyte because the reduced charge voltage. Here we report the synthesis of nano-sheet-assembled ZnCo2O4 spheres/single walled carbon nanotubes (ZCO/SWCNTs) composites as high performance air electrode materials for Li-O2 batteries. The ZCOmore » catalyzed SWCNTs electrodes delivered high discharge capacities, decreased the onset of oxygen evolution reaction by 0.9 V during charge processes, and led to more stable cycling stability. These results indicate that ZCO/SWCNTs composite can be used as highly efficient air electrode for oxygen reduction and evolution reactions. The highly enhanced catalytic activity by uniformly dispersed ZnCo2O4 catalyst on nanostructured electrodes is expected to inspire« less

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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

2016-07-06

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.

Earth’s oxygen cycle and the evolution of animal life

PubMed Central

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

Earth's oxygen cycle and the evolution of animal life.

PubMed

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

2016-08-09

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).

Peroxy defects in Rocks and H2O2 formation on the early Earth

NASA Astrophysics Data System (ADS)

Gray, A.; Balk, M.; Mason, P.; Freund, F.; Rothschild, L.

2013-12-01

An oxygen-rich atmosphere appears to have been a prerequisite for complex life to evolve on Earth and possibly elsewhere in the Universe. The question is still shrouded in uncertainty how free oxygen became available on the early Earth. Here we study processes of peroxy defects in silicate minerals which, upon weathering, generate mobilized electronic charge carriers resulting in oxygen formation in an initially anoxic subsurface environment. Reactive Oxygen Species (ROS) are precursors to molecular oxygen during this process. Due to their toxicity they may have strongly influenced the evolution of life. ROS are generated during hydrolysis of peroxy defects, which consist of pairs of oxygen anions. A second pathway for formation occurs during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, microorganisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defenses against the potentially dangerous, even lethal effects of ROS and oxygen. We have investigated how oxygen might be released through weathering and test microorganisms in contact with rock surfaces. Our results show how early Life might have adapted to oxygen. Early microorganisms must have "trained" to detoxify ROS prior to the evolution of aerobic metabolism and oxygenic photosynthesis. A possible way out of this dilemma comes from a study of igneous and high-grade metamorphic rocks, whose minerals contain a small but significant fraction of oxygen anions in the valence state 1- , forming peroxy links of the type O3Si-OO-SiO3 [1, 2]. As water hydrolyzes the peroxy links hydrogen peroxide, H2O2, forms. Continued experimental discovery of H2O2 formation at rock-water interfaces as part of stress-activated currents on the tectonically active Earth may help us better understand the oxidation of the early Earth and the evolution of early Life. [1] Balk et al. (2009) Earth and Planetary Science Letters 283, 87-92. [2] Grant, R. A. et al. (2011) Int. J. Environ. Res. Public Health 8, 1936-1956.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Daojin; Cai, Zhao; Bi, Yongmin

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE PAGES

Zhou, Daojin; Cai, Zhao; Bi, Yongmin; ...

2018-02-02

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Rational Design and Nanoscale Integration of Multi-Heterostructures as Highly Efficient Photocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, Xiangfeng

2017-11-03

The central goal of this project is to design and synthesize complex multi-hetero-nanostructures and fundamental investigation of their potential as efficient and robust photocatalysts. Specifically, the project aims to develop a nanoscale light-harvesting antenna that can efficiently convert solar photon energy into excited electrons and holes, and integrate such antenna with efficient redox nanocatalysts that can harness the photo-generated carriers for productive electrochemical processes. Focusing on this central goal, we have investigated several potential light-harvesting antennas including: silicon nanowires, nitrogen-doped TiO2 nanowires and the emerging perovskite materials. We also devoted considerable effort in developing electrocatalysts including: hydrogen evolution reaction (HER)more » catalysts, oxygen evolution reaction (OER) catalysts and oxygen reduction reaction catalysts (ORR). In previous annual reports, we have described our effort in the synthesis and photoelectrochemical properties of silicon, TiO2, perovskite-based materials and heterostructures. Here, we focus our discussion on the recent effort in investigating charge transport dynamics in organolead halide perovskites, as well as carbon nanostructure and platinum nanostructure-based electrocatalysts for energy conversion and storage.« less

Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

NASA Astrophysics Data System (ADS)

Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

2018-03-01

Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

Single crystalline Co3O4 nanocrystals exposed with different crystal planes for Li-O2 batteries.

PubMed

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-08-29

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}.

The doping effect on the catalytic activity of graphene for oxygen evolution reaction in a lithium-air battery: a first-principles study.

PubMed

Ren, Xiaodong; Wang, Beizhou; Zhu, Jinzhen; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin

2015-06-14

A lithium-air battery as an energy storage technology can be used in electric vehicles due to its large energy density. However, its poor rate capability, low power density and large overpotential problems limit its practical usage. In this paper, the first-principles thermodynamic calculations were performed to study the catalytic activity of X-doped graphene (X = B, N, Al, Si, and P) materials as potential cathodes to enhance charge reactions in a lithium-air battery. Among these materials, P-doped graphene exhibits the highest catalytic activity in reducing the charge voltage by 0.25 V, while B-doped graphene has the highest catalytic activity in decreasing the oxygen evolution barrier by 0.12 eV. By combining these two catalytic effects, B,P-codoped graphene was demonstrated to have an enhanced catalytic activity in reducing the O2 evolution barrier by 0.70 eV and the charge voltage by 0.13 V. B-doped graphene interacts with Li2O2 by Li-sited adsorption in which the electron-withdrawing center can enhance charge transfer from Li2O2 to the substrate, facilitating reduction of O2 evolution barrier. In contrast, X-doped graphene (X = N, Al, Si, and P) prefers O-sited adsorption toward Li2O2, forming a X-O2(2-)···Li(+) interface structure between X-O2(2-) and the rich Li(+) layer. The active structure of X-O2(2-) can weaken the surrounding Li-O2 bonds and significantly reduce Li(+) desorption energy at the interface. Our investigation is helpful in developing a novel catalyst to enhance oxygen evolution reaction (OER) in Li-air batteries.

Oxygen vacancy induced structural evolution of SrFeO3 -x epitaxial thin film from brownmillerite to perovskite

NASA Astrophysics Data System (ADS)

Roh, Seulki; Lee, Seokbae; Lee, Myounghoon; Seo, Yu-Seong; Khare, Amit; Yoo, Taesup; Woo, Sungmin; Choi, Woo Seok; Hwang, Jungseek; Glamazda, A.; Choi, K.-Y.

2018-02-01

We investigated SrFeO3 -x thin films on a SrTiO3 (001) substrate prepared via pulsed laser epitaxy using an optical spectroscopy technique. The oxygen vacancy level (x ) was controlled by post-annealing processes at different oxygen partial pressures. We achieved a brownmillerite (BM) structure at x =0.5 and observed the evolution of the crystal structure from BM into perovskite (PV) as the oxygen concentration increased. We observed the evolution of infrared-active phonons with respect to the oxygen concentration, which was closely related to the structural evolution observed via x-ray diffraction. We identified the phonons using the shell-model calculation. Furthermore, we studied temperature-dependent behaviors of the phonon modes of three representative samples: PV and two BMs (BMoop and BMip) with different orientations of the oxygen vacancy channel. In the BMoop sample, we observed a phonon mode, which exhibited an unusual redshift with decreasing temperature; this behavior may have been due to the apical oxygen instability in the FeO6 octahedron. Our results provide important information regarding the ionic conduction mechanism in SrFeO3 -x material systems.

Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability

NASA Technical Reports Server (NTRS)

Ross, H. Richard

2002-01-01

Recent interest in propellants with non-toxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because peroxide is sensitive to contaminants, material interactions, stability and storage issues, monitoring decomposition rates is important. Stennis Space Center (SSC) uses thermocouples to monitor bulk fluid temperature (heat evolution) to determine reaction rates. Unfortunately, large temperature rises are required to offset the heat lost into the surrounding fluid. Also, tank penetration to accomodate a thermocouple can entail modification of a tank or line and act as a source of contamination. The paper evaluates a method for monitoring oxygen evolution as a means to determine peroxide stability. Oxygen generation is not only directly related to peroxide decomposition, but occurs immediately. Measuring peroxide temperature to monitor peroxide stability has significant limitations. The bulk decomposition of 1% / week in a large volume tank can produce in excess of 30 cc / min. This oxygen flow rate corresponds to an equivalent temperature rise of approximately 14 millidegrees C, which is difficult to measure reliably. Thus, if heat transfer were included, there would be no temperature rise. Temperature changes from the surrounding environment and heat lost to the peroxide will also mask potential problems. The use of oxygen flow measurements provides an ultra sensitive technique for monitoring reaction events and will provide an earlier indication of an abnormal decomposition when compared to measuring temperature rise.

Evaluation of advanced propulsion options for the next manned transportation system: Propulsion evolution study

NASA Technical Reports Server (NTRS)

Spears, L. T.; Kramer, R. D.

1990-01-01

The objectives were to examine launch vehicle applications and propulsion requirements for potential future manned space transportation systems and to support planning toward the evolution of Space Shuttle Main Engine (SSME) and Space Transportation Main Engine (STME) engines beyond their current or initial launch vehicle applications. As a basis for examinations of potential future manned launch vehicle applications, we used three classes of manned space transportation concepts currently under study: Space Transportation System Evolution, Personal Launch System (PLS), and Advanced Manned Launch System (AMLS). Tasks included studies of launch vehicle applications and requirements for hydrogen-oxygen rocket engines; the development of suggestions for STME engine evolution beyond the mid-1990's; the development of suggestions for STME evolution beyond the Advanced Launch System (ALS) application; the study of booster propulsion options, including LOX-Hydrocarbon options; the analysis of the prospects and requirements for utilization of a single engine configuration over the full range of vehicle applications, including manned vehicles plus ALS and Shuttle C; and a brief review of on-going and planned LOX-Hydrogen propulsion technology activities.

Fire feedbacks over geological time and the evolution of atmospheric oxygen concentration

NASA Astrophysics Data System (ADS)

Mills, B.; Belcher, C.; Lenton, T. M.

2017-12-01

During the 4.5 billion year history of the Earth, the concentration of oxygen in the atmosphere has risen from trace levels to today's 21%. Yet over the last 400 million years, O2 concentration appears to have remained within a relatively narrow range (around 15% - 30%), despite dramatic changes in the nature of global biogeochemical cycling. This stability has been crucial for continued animal evolution, and is thought to have arisen through feedbacks between oxygen, wildfire and plant productivity: the strong oxygen- dependence of fire initiation and spread means that global photosynthetic primary productivity is suppressed when oxygen levels are high, and enhanced when levels are low. We present biogeochemical modelling of the long term carbon and oxygen cycles, which aims to capture the operation of the wildfire feedback alongside other key processes. We find that wildfire can effectively stabilize long term oxygen concentrations, but that the nature of this feedback has changed as plant evolution has provided different fuels. Specifically, the evolution of early angiosperms during the Cretaceous period provided new understory fuels that more easily facilitated crown and canopy fires. Adding these dynamics to our model produces a more stable system over long timescales, and the model predicts that oxygen concentration has declined towards the present day - a prediction that is supported by other independent estimates.

Low temperature alkaline pH hydrolysis of oxygen-free Titan tholins

NASA Astrophysics Data System (ADS)

Brassé, C.; Buch, A.; Raulin, F.; Coll, P.; Poch, O.; Ramirez, S.

2013-09-01

Titan, the largest moon of Saturn, is known for its dense and nitrogen-rich atmosphere. The organic aerosols which are produced in Titan's atmosphere are objects of astrobiological interest. In this paper we focus on their potential chemical evolution when they reach the surface and interact with putative ammonia-water cryomagma[1]. In this context we have studied the evolution of alkaline pH hydrolysis of Titan tholins (produced by an experimental setup using a plasma DC discharge named PLASMA) at ambient and low temperature. However, we identified oxygenated molecules in non-hydrolyzed tholins meaning that oxygen gets in the PLASMA reactor during the tholins synthesis [2]. Following this preliminary study the synthesis protocol has been improved by isolating the whole device in a specially designed glove box which protect the PLASMA experiment from the laboratory atmosphere. After confirming the non-presence of oxygen in tholins produced with this new experimental setup, the study of oxygen-free tholins' evolution has been carried out. A recent study shows that the subsurface ocean may contain a lower fraction of ammonia (about 5wt% or less [3]), as previously described by other teams [2,4]. Thus new hydrolysis experiments will take this lower value into account. Additionally, a new report [5] provides upper and lower limits for the bulk content of Titan's interior for various gas species. It also shows that most of them are likely stored and dissolved in the subsurface water ocean. But considering the plausible acido-alkaline properties of the ammonia-water ocean, additional species could be dissolved in the ocean and present in the magma. They were also included in our hydrolysis experiments. Taking into account these new data, four different hydrolysis have been applied to oxygen-free tholins. For each type of hydrolysis, we also follow the influence of the hydrolysis temperature on the organic molecules production. The preliminary qualitative and quantitative results of those experiments will be presented at EPSC.

Photosystems and global effects of oxygenic photosynthesis.

PubMed

Nelson, Nathan

2011-08-01

Because life on earth is governed by the second law of thermodynamics, it is subject to increasing entropy. Oxygenic photosynthesis, the earth's major producer of both oxygen and organic matter, is a principal player in the development and maintenance of life, and thus results in increased order. The primary steps of oxygenic photosynthesis are driven by four multi-subunit membrane protein complexes: photosystem I, photosystem II, cytochrome b(6)f complex, and F-ATPase. Photosystem II generates the most positive redox potential found in nature and thus capable of extracting electrons from water. Photosystem I generates the most negative redox potential found in nature; thus, it largely determines the global amount of enthalpy in living systems. The recent structural determination of PSII and PSI complexes from cyanobacteria and plants sheds light on the evolutionary forces that shaped oxygenic photosynthesis. This newly available structural information complements knowledge gained from genomic and proteomic data, allowing for a more precise description of the scenario in which the evolution of life systems took place. This article is part of a Special Issue entitled: Regulation of Electron Transport in Chloroplasts. Copyright © 2010 Elsevier B.V. All rights reserved.

Cobalt Nanoparticle-Embedded Porous Carbon Nanofibers with Inherent N- and F-Doping as Binder-Free Bifunctional Catalysts for Oxygen Reduction and Evolution Reactions.

PubMed

Singhal, Richa; Kalra, Vibha

2017-01-18

Efficient, low-cost, non-precious metal-based, and stable bifunctional electrocatalysts are key to various energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. In this work, we report cobalt nanoparticle-embedded porous carbon nanofibers with inherent N- and F-doping as binder-free bifunctional electrocatalysts with excellent activity for both the oxygen reduction and oxygen evolution reaction (ORR/OER) in an alkaline medium. Single-step electrospinning of a solution of the polymer mixture (carbon precursor) and the cobalt precursor followed by controlled pyrolysis with an intermediate reduction step in H 2 (to reduce cobalt oxides to cobalt) was utilized to synthesize an integrated freestanding catalyst. The fabricated catalyst with effective structural and electronic interaction between the cobalt metal nanoparticles and the N- and F-doped carbon defect sites showed enhanced catalytic properties compared to the benchmark catalysts for ORR and OER (Pt, Ir, and Ru). The ORR potential at the current density of -3 mA cm -2 was 0.81 V RHE and the OER potential at a current density of 10 mA cm -2 was 1.595 V RHE , resulting in a ΔE of only 0.785 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

DOE PAGES

Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

2015-04-21

Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2/O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings revealmore » an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.« less

Multilayer Ni/Fe thin films as oxygen evolution catalysts for solar fuel production

NASA Astrophysics Data System (ADS)

Biset-Peiró, M.; Murcia-López, S.; Fàbrega, C.; Morante, J. R.; Andreu, T.

2017-03-01

The slow kinetics and high overpotential of the oxygen evolution reaction is one of the main limiting factors to achieve the minimum required performances of the so-called photoelectrochemical water splitting systems. An oxygen evolution catalyst (OEC) becomes essential in order to perform this process with higher efficiency. Herein, we report the physical, optical and electrochemical characterization of multilayer Ni/Fe thin films as earth-abundant OEC, to avoid the use of platinum group metals (PGM). Uniform films of thicknesses ranging from 1 to 10 nm were fabricated by sequential and alternate thermal evaporation of Ni and Fe. It was found that the successive deposition allows the fabrication of a Ni terminated surface that does not need activation due to the Fe underlayer. The lowest overpotential achieved for NiFe was 370 mV at 10 mA cm-2 and a Tafel slope of 37 mV dec-1 with 1 nm thickness and 95% transmittance. Finally, NiFe OEC was implemented on top of Mo:BiVO4 photoanodes which resulted in a reduction of the open circuit potential of 0.2 V and up to five fold increase of the oxidation efficiency at 0.7 VRHE. The results presented facilitate the practical implementation of BiVO4 photoanodes in tandem configuration for bias free photoassisted water splitting.

Oxidative stress, redox stress or redox success?

PubMed

Gutteridge, John M C; Halliwell, Barry

2018-05-09

The first life forms evolved in a highly reducing environment. This reduced state is still carried by cells today, which makes the concept of "reductive stress" somewhat redundant. When oxygen became abundant on the Earth, due to the evolution of photosynthesis, life forms had to adapt or become extinct. Living organisms did adapt, proliferated and an explosion of new life forms resulted, using reactive oxygen species (ROS) to drive their evolution. Adaptation to oxygen and its reduction intermediates necessitated the simultaneous evolution of select antioxidant defences, carefully regulated to allow ROS to perform their major roles. Clearly this "oxidative stress" did not cause a major problem to the evolution of complex life forms. Why not? Iron and oxygen share a close relationship in aerobic evolution. Iron is used in proteins to transport oxygen, promote electron transfers, and catalyse chemical reactions. In all of these functions, iron is carefully sequestered within proteins and restricted from reacting with ROS, this sequestration being one of our major antioxidant defences. Iron was abundant to life forms before the appearance of oxygen. However, oxygen caused its oxidative precipitation from solution and thereby decreased its bioavailability and thus the risk of iron-dependent oxidative damage. Micro-organisms had to adapt and develop strategies involving siderophores to acquire iron from the environment and eventually their host. This battle for iron between bacteria and animal hosts continues today, and is a much greater daily threat to our survival than "oxidative stress" and "redox stress". Copyright © 2018. Published by Elsevier Inc.

Oxygen evolution from BF3/MnO4-.

PubMed

Yiu, Shek-Man; Man, Wai-Lun; Wang, Xin; Lam, William W Y; Ng, Siu-Mui; Kwong, Hoi-Ki; Lau, Kai-Chung; Lau, Tai-Chu

2011-04-14

MnO(4)(-) is activated by BF(3) to undergo intramolecular coupling of two oxo ligands to generate O(2). DFT calculations suggest that there should be a spin intercrossing between the singlet and triplet potential energy surfaces on going from the active intermediate [MnO(2)(OBF(3))(2)](-) to the O···O coupling transition state.

Evolutionary significance of osmoregulatory mechanisms in cyanobacteria

NASA Technical Reports Server (NTRS)

Yopp, J. H.; Pavlicek, J. H.; Sibley, M. H.

1986-01-01

Physiological processes of all life forms on this planet are intrinsically related to their intracellular water potential. The overall goal was the elucidation of the mechanism(s) whereby the first oxygenic phtoautotrophs (the cyanobacteria) adjust their water potential to that of a changing external water potential (that is, osmoregulate). Osmoregulation is achieved by intracellular adjustment of inorganic and/or organic solutes (osmolytes) involving specific biochemical mechanisms. Structural and biochemical evolution within the cyanobacteria is believed completed (and fixed in present day forms) by the end of the Precambrain eon. Therefore, research using cyanobacteria of all three structural types (unicellular, filamentous, and branched), each grown in the photoautotrophic (PA), photoheterotrophic (PG), and chemotrophic (CH) modes of nutrition, should provide insight into the origin and evolution of the photosynthetically related osmoregulatory mechanisms of eukaryotic organisms. The chloroplasts of these organisms are phylogenetically related to the cyanobacteria.

Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts.

PubMed

Morgan Chan, Zamyla; Kitchaev, Daniil A; Nelson Weker, Johanna; Schnedermann, Christoph; Lim, Kipil; Ceder, Gerbrand; Tumas, William; Toney, Michael F; Nocera, Daniel G

2018-06-05

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn 3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn 3+ may be introduced into MnO 2 by an electrochemically induced comproportionation reaction with Mn 2+ and that Mn 3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn 3+ -activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn 3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn 3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn 3+ (T d ) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO 2 polymorph incorporating Mn 3+ ions.

Electrochemical Trapping of Metastable Mn3+ Ions for Activation of MnO2 Oxygen Evolution Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tumas, William; Chan, Zamyla Morgan; Kitchaev, Daniil A.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+. We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies showmore » that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the d-MnO2 polymorph incorporating Mn3+ ions.« less

Oxygenation of the Mesoproterozoic ocean and the evolution of complex eukaryotes

NASA Astrophysics Data System (ADS)

Zhang, Kan; Zhu, Xiangkun; Wood, Rachel A.; Shi, Yao; Gao, Zhaofu; Poulton, Simon W.

2018-05-01

The Mesoproterozoic era (1,600-1,000 million years ago (Ma)) has long been considered a period of relative environmental stasis, with persistently low levels of atmospheric oxygen. There remains much uncertainty, however, over the evolution of ocean chemistry during this period, which may have been of profound significance for the early evolution of eukaryotic life. Here we present rare earth element, iron-speciation and inorganic carbon isotope data to investigate the redox evolution of the 1,600-1,550 Ma Yanliao Basin, North China Craton. These data confirm that the ocean at the start of the Mesoproterozoic was dominantly anoxic and ferruginous. Significantly, however, we find evidence for a progressive oxygenation event starting at 1,570 Ma, immediately prior to the occurrence of complex multicellular eukaryotes in shelf areas of the Yanliao Basin. Our study thus demonstrates that oxygenation of the Mesoproterozoic environment was far more dynamic and intense than previously envisaged, and establishes an important link between rising oxygen and the emerging record of diverse, multicellular eukaryotic life in the early Mesoproterozoic.

Novel catalysts and photoelectrochemical system for solar fuel production

NASA Astrophysics Data System (ADS)

Zhang, Yan

Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption spectroscopy (XAS). The photocatalytic activities of as-made nanoparticles were investigated using a well-studied visible light driven [Ru(bpy)3]2+-persulfate system. In both Clark electrode and reactor/gas chromatography (GC) systems, Mn-substituted Co3O 4 nanoparticles exhibited the highest turnover frequency (TOF) among all the three kinds of catalysts. The data presented in this paper suggest that the photocatalytic oxygen evolution activity of Co3O 4 spinel catalyst can be further enhanced by Mn3+ substitution at the octahedral sites. The second part of this piece of work was carried out to further investigate cobalt oxide based photocatalytic oxygen evolution catalyst. A new strategy was developed to synthesize nonsupported cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO 3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.0023 per second per cobalt in photocatalytic oxygen evolution reaction. X-ray absorption results suggested that a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen atoms and hydroxide groups in an octahedral arrangement to form 8 Co4O4 cubanes, may be responsible for the exceptionally high oxygen evolution catalysis activity. This thesis work is completed with the development of a photoanode-driven photoelectrochemical cell for CO2 reduction. A NiOx decorated Si photoanode and nanoporous Ag cathode were employed. With an external bias of 2.0 V, a current density at cathode of 10 mA/cm2 and Faradaic efficiency of 70% for CO2 to CO was achieved. Compared to a normal electrochemical cell, the photoelectrochemical cell saves 0.4 V electrical energy by absorbing photo-energy. In addition, post-test photoanodes were carefully characterized by SEM, XAS, and XPS analysis.

Controls on O2 Production in Cyanobacterial Mats and Implications for Earth's Oxygenation

NASA Astrophysics Data System (ADS)

Dick, Gregory J.; Grim, Sharon L.; Klatt, Judith M.

2018-05-01

Cyanobacterial mats are widely assumed to have been globally significant hot spots of biogeochemistry and evolution during the Archean and Proterozoic, but little is known about their quantitative contributions to global primary productivity or Earth's oxygenation. Modern systems show that mat biogeochemistry is the outcome of concerted activities and intimate interactions between various microbial metabolisms. Emerging knowledge of the regulation of oxygenic and sulfide-driven anoxygenic photosynthesis by versatile cyanobacteria, and their interactions with sulfur-oxidizing bacteria and sulfate-reducing bacteria, highlights how ecological and geochemical processes can control O2 production in cyanobacterial mats in unexpected ways. This review explores such biological controls on O2 production. We argue that the intertwined effects of light availability, redox geochemistry, regulation and competition of microbial metabolisms, and biogeochemical feedbacks result in emergent properties of cyanobacterial mat communities that are all critical yet largely overlooked mechanisms to potentially explain the protracted nature of Earth's oxygenation.

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

PubMed

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

2016-03-09

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

Rechargeable aqueous lithium-air batteries with an auxiliary electrode for the oxygen evolution

NASA Astrophysics Data System (ADS)

Sunahiro, S.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

2014-09-01

A rechargeable aqueous lithium-air cell with a third auxiliary electrode for the oxygen evolution reaction was developed. The cell consists of a lithium metal anode, a lithium conducting solid electrolyte of Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12, a carbon black oxygen reduction air electrode, a RuO2 oxygen evolution electrode, and a saturated aqueous solution of LiOH with 10 M LiCl. The cell was successfully operated for several cycles at 0.64 mA cm-2 and 25 °C under air, where the capacity of air electrode was 2000 mAh gcathod-1. The cell performance was degraded gradually by cycling under open air. The degradation was reduced under CO2-free air and pure oxygen. The specific energy density was calculated to be 810 Wh kg-1 from the weight of water, lithium, oxygen, and carbon in the air electrode.

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

EPA Science Inventory

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...

Single Crystalline Co3O4 Nanocrystals Exposed with Different Crystal Planes for Li-O2 Batteries

PubMed Central

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-01-01

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}. PMID:25169737

Hydrogen peroxide and the evolution of oxygenic photosynthesis

NASA Technical Reports Server (NTRS)

Mckay, C. P.; Hartman, H.

1991-01-01

Possible pathways for the evolution of oxygenic photosynthesis in the early reducing atmosphere of the earth are discussed. It is suggested that 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 (rather than ferrous or sulfide ions) as the electron donor. It is argued that atmospheric H2O2 played the key role in inducing oxygenic photosynthesis, because, as peroxide concentrations local environments increased, primitive organisms would not only be faced with a loss of a reductant, but would be also forced to develop a biochemical apparatus (such as catalase) that would protect them against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis at the time when global conditions were still anaerobic.

Dual organism design cycle reveals small subunit substitutions that improve [NiFe] hydrogenase hydrogen evolution.

PubMed

Yonemoto, Isaac T; Matteri, Christopher W; Nguyen, Thao Amy; Smith, Hamilton O; Weyman, Philip D

2013-07-02

Photosynthetic microorganisms that directly channel solar energy to the production of molecular hydrogen are a potential future biofuel system. Building such a system requires installation of a hydrogenase in the photosynthetic organism that is both tolerant to oxygen and capable of hydrogen production. Toward this end, we have identified the [NiFe] hydrogenase from the marine bacterium Alteromonas macleodii "Deep ecotype" that is able to be heterologously expressed in cyanobacteria and has tolerance to partial oxygen. The A. macleodii enzyme shares sequence similarity with the uptake hydrogenases that favor hydrogen uptake activity over hydrogen evolution. To improve hydrogen evolution from the A. macleodii hydrogenase, we examined the three Fe-S clusters found in the small subunit of many [NiFe] uptake hydrogenases that presumably act as a molecular wire to guide electrons to or from the active site of the enzyme. Studies by others altering the medial cluster of a Desulfovibrio fructosovorans hydrogenase from 3Fe-4S to 4Fe-4S resulted in two-fold improved hydrogen evolution activity. We adopted a strategy of screening for improved hydrogenase constructs using an Escherichia coli expression system before testing in slower growing cyanobacteria. From the A. macleodii enzyme, we created a mutation in the gene encoding the hydrogenase small subunit that in other systems is known to convert the 3Fe-4S medial cluster to 4Fe-4S. The medial cluster substitution did not improve the hydrogen evolution activity of our hydrogenase. However, modifying both the medial cluster and the ligation of the distal Fe-S cluster improved in vitro hydrogen evolution activity relative to the wild type hydrogenase by three- to four-fold. Other properties of the enzyme including thermostability and tolerance to partial oxygen did not appear to be affected by the substitutions. Our results show that substitution of amino acids altering the ligation of Fe-S clusters in the A. macleodii [NiFe] uptake hydrogenase resulted in increased hydrogen evolution activity. This activity can be recapitulated in multiple host systems and with purified protein. These results validate the approach of using an E. coli-cyanobacteria shuttle system for enzyme expression and improvement.

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

PubMed

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/MnO 2 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.

Decorating unoxidized-carbon nanotubes with homogeneous Ni-Co spinel nanocrystals show superior performance for oxygen evolution/reduction reactions

NASA Astrophysics Data System (ADS)

Yang, Jun; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2017-03-01

We present a new concept for homogeneous spinel nanocrystal-coating on high crystalline pristine-carbon nanotubes (CNTs) for efficient and durable oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Oxidized CNTs have widely been used to functionalize with metal or metal oxides since the defect sites act as anchoring for metal oxide binding. However, such defects on the tubes cause the decrease in electrical conductivity and stability, leading to lower catalyst performance. In the present study, at first, pristine multi-walled carbon nanotubes (MWNTs) were wrapped by pyridine-based polybenzimidazole (PyPBI) to which uniform NixCo3-xO4 nanocrystals were homogeneously deposited by the solvothermal method without damaging the MWNTs, in which PyPBI acted as efficient anchoring sites for the deposition of spinel oxide nanocrystals with ~5 nm size. The obtained catalyst (MWNT-PyPBI-NixCo3-xO4) outperformed most state-of-the-art non-precious metal-based bifunctional catalysts; namely, for OER, the potential at 10 mA cm-2 and Tafel slope in 1 M KOH solution were 1.54 V vs. RHE and 42 mV dec-1, respectively. For ORR, the onset and half-wave potentials are 0.918 V and 0.811 V vs. RHE, respectively. Moreover, the MWNT-PyPBI-NixCo3-xO4 demonstrates an excellent durability for both ORR and OER.

Chasing Neoproterozoic Atmospheric Oxygen Ghosts

NASA Astrophysics Data System (ADS)

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.

The biosphere as a driver of global atmospheric change

NASA Technical Reports Server (NTRS)

Levine, Joel S.

1991-01-01

The effects of the biosphere on the evolution of atmospheric oxygen and ozone, and the consequences of that development for global atmospheric change, are discussed. Attention is given to the impact of oxygen and ozone on atmospheric photolysis rates, the effect of oxygen on the biogenic production of nitrous oxide and nitric oxide, and the effects of the evolution of atmospheric oxygen on fires and biomass burning. The influence of the latter on atmospheric processes, particularly the production of methane, carbon dioxide, and carbon monoxide, is considered.

The structural and electrical evolution of graphene by oxygen plasma-induced disorder.

PubMed

Kim, Dong Chul; Jeon, Dae-Young; Chung, Hyun-Jong; Woo, YunSung; Shin, Jai Kwang; Seo, Sunae

2009-09-16

Evolution of a single graphene layer with disorder generated by remote oxygen plasma irradiation is investigated using atomic force microscopy, Raman spectroscopy and electrical measurement. Gradual changes of surface morphology from planar graphene to isolated granular structure associated with a decrease of transconductance are accounted for by two-dimensional percolative conduction by disorder and the oxygen plasma-induced doping effect. The corresponding evolution of Raman spectra of graphene shows several peculiarities such as a sudden appearance of a saturated D peak followed by a linear decrease in its intensity, a relatively inert characteristic of a D' peak and a monotonic increase of a G peak position as the exposure time to oxygen plasma increases. These are discussed in terms of a disorder-induced change of Raman spectra in the graphite system.

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction.

PubMed

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M; Elzatahry, Ahmed A; Zheng, Gengfeng

2015-09-14

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g(-1), with excellent capacitance retention (>90%) at 10 A g(-1) for over 10,000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm(-2) at 1.65 V vs. the RHE.

Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

PubMed Central

T. Weller, Mark

2018-01-01

Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

The surface sulfur doping induced enhanced performance of cobalt catalysts in oxygen evolution reactions.

PubMed

Al-Mamun, Mohammad; Zhu, Zhengju; Yin, Huajie; Su, Xintai; Zhang, Haimin; Liu, Porun; Yang, Huagui; Wang, Dan; Tang, Zhiyong; Wang, Yun; Zhao, Huijun

2016-08-04

A novel surface sulfur (S) doped cobalt (Co) catalyst for the oxygen evolution reaction (OER) is theoretically designed through the optimisation of the electronic structure of highly reactive surface atoms which is also validated by electrocatalytic OER experiments.

Defect engineering in atomically-thin bismuth oxychloride towards photocatalytic oxygen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di, Jun; Chen, Chao; Yang, Shi -Ze

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

Defect engineering in atomically-thin bismuth oxychloride towards photocatalytic oxygen evolution

DOE PAGES

Di, Jun; Chen, Chao; Yang, Shi -Ze; ...

2017-06-26

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

Proceedings of the Astrobiology Science Conference 2010. Evolution and Life: Surviving Catastrophes and Extremes on Earth and Beyond

NASA Technical Reports Server (NTRS)

2010-01-01

The Program of the 2010 Astrobiology Science Conference: Evolution and Life: Surviving Catastrophes and Extremes on Earth and Beyond, included sessions on: 50 Years of Exobiology and Astrobiology: Greatest Hits; Extraterrestrial Molecular Evolution and Pre-Biological Chemistry: From the Interstellar Medium to the Solar System I; Human Exploration, Astronaut Health; Diversity in Astrobiology Research and Education; Titan: Past, Present, and Future; Energy Flow in Microbial Ecosystems; Extraterrestrial Molecular Evolution and Prebiological Chemistry: From the Interstellar Medium to the Solar System II; Astrobiology in Orbit; Astrobiology and Interdisciplinary Communication; Science from Rio Tinto: An Acidic Environment; Can We Rule Out Spontaneous Generation of RNA as the Key Step in the Origin of Life?; How Hellish Was the Hadean Earth?; Results from ASTEP and Other Astrobiology Field Campaigns I; Prebiotic Evolution: From Chemistry to Life I; Adaptation of Life in Hostile Space Environments; Extrasolar Terrestrial Planets I: Formation and Composition; Collaborative Tools and Technology for Astrobiology; Results from ASTEP and Other Astrobiology Field Campaigns II; Prebiotic Evolution: From Chemistry to Life II; Survival, Growth, and Evolution of Microrganisms in Model Extraterrestrial Environments; Extrasolar Terrestrial Planets II: Habitability and Life; Planetary Science Decadal Survey Update; Astrobiology Research Funding; Bioessential Elements Through Space and Time I; State of the Art in Life Detection; Terrestrial Evolution: Implications for the Past, Present, and Future of Life on Earth; Psychrophiles and Polar Environments; Life in Volcanic Environments: On Earth and Beyond; Geochronology and Astrobiology On and Off the Earth; Bioessential Elements Through Space and Time II; Origins and Evolution of Genetic Systems; Evolution of Advanced Life; Water-rich Asteroids and Moons: Composition and Astrobiological Potential; Impact Events and Evolution; A Warm, Wet Mars?; Titan Versus Europa - Potential for Astrobiology; Habitability Potential of Mars; Biosignatures: Tools and Development I; Origins of Molecular Asymmetry, Homochirality, and Life Detection; Deserts and Evaporite Basins and Associated Microbialite Systems; Ancient Life and Synthetic Biology: Crossroad of the Past and Future; Biosignatures: Tools and Development II; Free Oxygen: Proxies, Causes, and Consequences; Life in Modern Microbialite Systems - Function and Adaptation; Hydrothermal Systems and Organosynthesis Processes: Origin and Evolution of Life; Where Should We Go on Mars to Seek Signs of Life?; Search for Intelligent Life I. Innovative SETI Observing Programs and Future Directions; Integrating Astrobiology Research Across and Beyond the Community; Education in Astrobiology in K-12; Search for Intelligent Life II. Global Engagement and Interstellar Message Construction; Poster sessions included: Extraterrestrial Molecular Evolution and Pre-Biological Chemistry; Prebiotic Evolution: From Chemistry to Life; RNA World; Terrestrial Evolution: Implications for the Past, Present, and Future of Life on Earth; Hydrothermal Systems and Organosynthesis Processes: Origin and Evolution of Life; Virology and Astrobiology; Horizontal Genetic Transfer and Properties of Ancestral Organisms; Life in Volcanic Environments: On Earth and Beyond; Impact Events and Evolution; Evolution of Advanced Life; Evolution of Intelligent Life; Education in Astrobiology in K-12; Origins of Molecular Asymmetry, Homochirality, and Life Detection; Astrobiology and Interdisciplinary Communication; Diversity in Astrobiology Research and Education; Integrating Astrobiology Research Across and Beyond the Community; Policy and Societal Issues: Dealing with Potential Bumps in the Astrobiology Road Ahead; Results from ASTEP and Other Astrobiology Field Campaigns; Energy Flow in Microbial Ecosystems; Psychrophiles and Polar Environments; Deserts and Evaporite Basins and Associated Microbialite stems; Life in Modern Microbialite Systems - Function and Adaptation; Free Oxygen: Proxies, Causes, and Consequences; Bioessential Elements Through Space and Time; Water-rich Asteroids and Moons: Composition and Astrobiological Potential; Biosignatures: Tools and Developments; Robotics and Instrumentation for Astrobiology; State of the Art in Life Detection; Astrobiology in Orbit; Survival, Growth, and Evolution of Microrganisms in Model Extraterrestrial Evolution; Search for Intelligent Life; Habitability Potential of Mars; How and Where Should We Seek Signs of Life on Mars?; Titan: Past, Present, and Future; Extrasolar Terrestrial Planets: Formation, Composition, Diversity, Habitability and Life; Human Exploration, Astronaut Health; Science from Rio Tinto: An Acidic Environment and Adaptation of Life in Hostile Space Environments;

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

NASA Astrophysics Data System (ADS)

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.

Reduced Moment-Based Models for Oxygen Precipitates and Dislocation Loops in Silicon

NASA Astrophysics Data System (ADS)

Trzynadlowski, Bart

The demand for ever smaller, higher-performance integrated circuits and more efficient, cost-effective solar cells continues to push the frontiers of process technology. Fabrication of silicon devices requires extremely precise control of impurities and crystallographic defects. Failure to do so not only reduces performance, efficiency, and yield, it threatens the very survival of commercial enterprises in today's fiercely competitive and price-sensitive global market. The presence of oxygen in silicon is an unavoidable consequence of the Czochralski process, which remains the most popular method for large-scale production of single-crystal silicon. Oxygen precipitates that form during thermal processing cause distortion of the surrounding silicon lattice and can lead to the formation of dislocation loops. Localized deformation caused by both of these defects introduces potential wells that trap diffusing impurities such as metal atoms, which is highly desirable if done far away from sensitive device regions. Unfortunately, dislocations also reduce the mechanical strength of silicon, which can cause wafer warpage and breakage. Engineers must negotiate this and other complex tradeoffs when designing fabrication processes. Accomplishing this in a complex, modern process involving a large number of thermal steps is impossible without the aid of computational models. In this dissertation, new models for oxygen precipitation and dislocation loop evolution are described. An oxygen model using kinetic rate equations to evolve the complete precipitate size distribution was developed first. This was then used to create a reduced model tracking only the moments of the size distribution. The moment-based model was found to run significantly faster than its full counterpart while accurately capturing the evolution of oxygen precipitates. The reduced model was fitted to experimental data and a sensitivity analysis was performed to assess the robustness of the results. Source code for both models is included. A moment-based model for dislocation loop formation from {311} defects in ion-implanted silicon was also developed and validated against experimental data. Ab initio density functional theory calculations of stacking faults and edge dislocations were performed to extract energies and elastic properties. This allowed the effect of applied stress on the evolution of {311} defects and dislocation loops to be investigated.

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei

2017-01-18

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkalinemore » solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.« less

Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

PubMed

Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

2013-04-07

Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

Electrochemical approach for passivating steel and other metals and for the simultaneous production of a biocide to render water potable

NASA Technical Reports Server (NTRS)

1972-01-01

Potentiostatic polarization curves indicated that the cathodic reactions in deaerated KI-I2 water solutions were due to iodine reduction and hydrogen evolution. In the presence of oxygen an additional reduction wave appeared. Anodic polarization curves revealed that iodine could be produced in the region of potential from +600 to +1000 nv vs. SCE.

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

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

PubMed

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 TiO 2 ) 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 TiO 2 . The TiO 2 /FeMnP core/shell photoanode reaches the theoretical photocurrent density for rutile TiO 2 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 TiO 2 /FeMnP core/shell nanorod array photoanode offers a compelling strategy for preparing highly efficient photoelectrochemical solar energy conversion devices.

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

NASA Astrophysics Data System (ADS)

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.

2014-06-01

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)>(110)>(111), is inversely proportional to the activity. Both stability and reactivity are governed by the potential-induced transformation of stable Ru4+ to unstable Run>4+. This ordered(Ru4+)-to-disordered(Run>4+) transition and the development of active sites for the reaction are determined by a synergy between electronic and morphological effects.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan

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 templatesmore » 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.« less

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

DOE PAGES

Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan; ...

2018-01-22

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 templatesmore » 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.« less

Sufficient oxygen for animal respiration 1,400 million years ago

PubMed Central

Zhang, Shuichang; Wang, Xiaomei; Wang, Huajian; Bjerrum, Christian J.; Hammarlund, Emma U.; Costa, M. Mafalda; Connelly, James N.; Zhang, Baomin; Su, Jin; Canfield, Donald E.

2016-01-01

The Mesoproterozoic Eon [1,600–1,000 million years ago (Ma)] is emerging as a key interval in Earth history, with a unique geochemical history that might have influenced the course of biological evolution on Earth. Indeed, although this time interval is rather poorly understood, recent chromium isotope results suggest that atmospheric oxygen levels were <0.1% of present levels, sufficiently low to have inhibited the evolution of animal life. In contrast, using a different approach, we explore the distribution and enrichments of redox-sensitive trace metals in the 1,400 Ma sediments of Unit 3 of the Xiamaling Formation, North China Block. Patterns of trace metal enrichments reveal oxygenated bottom waters during deposition of the sediments, and biomarker results demonstrate the presence of green sulfur bacteria in the water column. Thus, we document an ancient oxygen minimum zone. We develop a simple, yet comprehensive, model of marine carbon−oxygen cycle dynamics to show that our geochemical results are consistent with atmospheric oxygen levels >4% of present-day levels. Therefore, in contrast to previous suggestions, we show that there was sufficient oxygen to fuel animal respiration long before the evolution of animals themselves. PMID:26729865

Atmospheric oxygenation driven by unsteady growth of the continental sedimentary reservoir

NASA Astrophysics Data System (ADS)

Husson, Jon M.; Peters, Shanan E.

2017-02-01

Atmospheric oxygen concentration has increased over Earth history, from ∼0 before 2.5 billion years ago to its present-day concentration of 21%. The initial rise in pO2 approximately 2.3 billion years ago required oxygenic photosynthesis, but the evolution of this key metabolic pathway was not sufficient to propel atmospheric oxygen to modern levels, which were not sustained until approximately two billion years later. The protracted lag between the origin of oxygenic photosynthesis and abundant O2 in the surface environment has many implications for the evolution of animals, but the reasons for the delay remain unknown. Here we show that the history of sediment accumulation on continental crust covaries with the history of atmospheric oxygen concentration. A forward model based on the empirical record of net organic carbon burial and oxidative weathering of the crust predicts two significant rises in pO2 separated by three comparatively stable plateaus, a pattern that reproduces major biological transitions and proxy-based pO2 records. These results suggest that the two-phased oxygenation of Earth's surface environment, and the long delays between the origin of life, the evolution of metazoans, and their subsequent diversification during the Cambrian Explosion, was caused by step-wise shifts in the ability of the continents to accumulate and store sedimentary organic carbon. The geodynamic mechanisms that promote and inhibit sediment accumulation on continental crust have, therefore, exerted a first-order control on the evolution of Earth's life and environment.

Structure and function of isozymes: Evolutionary aspects and role of oxygen in eucaryotic organisms

NASA Technical Reports Server (NTRS)

Satyanarayana, T.

1985-01-01

Oxygen is not only one of the most abundant elements on the Earth, but it is also one of the most important elements for life. In terms of composition, the feature of the atmosphere that most distinguishes Earth from other planets is the presence of abundant amounts of oxygen. The first forms of life may have been similar to present day anaerobic bacteria such as clostridium. The relationship between prokaryotes and eukaryotes, if any, has been a topic of much speculation. With only a few exceptions eukaryotes are oxygen-utilizing organisms. This research eukaryotes or eukaryotic biochemical processes requiring oxygen, could have arisen quite early in evolution and utilized the small quantities of photocatalytically produced oxygen which are thought to have been present on the Earth prior to the evolution of massive amounts of photosynthetically-produced oxygen.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Comment on Egami's concept of the evolution of nitrate respiration

NASA Technical Reports Server (NTRS)

Rambler, M.; Margulis, L.

1976-01-01

Recent results suggest that the presence of common nitrogen salts (sodium nitrite and nitrate) in the irradiation medium can markedly protect filamentous blue-green algae from potentially lethal ultraviolet irradiation. The present results as well as general biological arguments of Egami support and extend Egami's original view that anaerobic respiratory pathways using nitrite and nitrate as terminal electron acceptors evolved prior to oxygen requiring aerobic respiratory pathways.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Ying-Ying; Kong, De-Xin; Qin, Tao

2010-01-08

It is well known that oxygen rise greatly facilitated biological evolution. However, the underlying mechanisms remain elusive. Recently, Raymond and Segre 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 producedmore » 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.« less

Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis.

PubMed

Liu, Yang; Yin, Shibin; Shen, Pei Kang

2018-06-27

The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni 3 S 2 , Fe 5 Ni 4 S 8 , and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe 5 Ni 4 S 8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. This journal is © The Royal Society of Chemistry 2012

A large oxygen-dominated core from the seismic cartography of a pulsating white dwarf

NASA Astrophysics Data System (ADS)

Giammichele, N.; Charpinet, S.; Fontaine, G.; Brassard, P.; Green, E. M.; Van Grootel, V.; Bergeron, P.; Zong, W.; Dupret, M.-A.

2018-02-01

White-dwarf stars are the end product of stellar evolution for most stars in the Universe. Their interiors bear the imprint of fundamental mechanisms that occur during stellar evolution. Moreover, they are important chronometers for dating galactic stellar populations, and their mergers with other white dwarfs now appear to be responsible for producing the type Ia supernovae that are used as standard cosmological candles. However, the internal structure of white-dwarf stars—in particular their oxygen content and the stratification of their cores—is still poorly known, because of remaining uncertainties in the physics involved in stellar modelling codes. Here we report a measurement of the radial chemical stratification (of oxygen, carbon and helium) in the hydrogen-deficient white-dwarf star KIC08626021 (J192904.6+444708), independently of stellar-evolution calculations. We use archival data coupled with asteroseismic sounding techniques to determine the internal constitution of this star. We find that the oxygen content and extent of its core exceed the predictions of existing models of stellar evolution. The central homogeneous core has a mass of 0.45 solar masses, and is composed of about 86 per cent oxygen by mass. These values are respectively 40 per cent and 15 per cent greater than those expected from typical white-dwarf models. These findings challenge present theories of stellar evolution and their constitutive physics, and open up an avenue for calibrating white-dwarf cosmochronology.

A large oxygen-dominated core from the seismic cartography of a pulsating white dwarf.

PubMed

Giammichele, N; Charpinet, S; Fontaine, G; Brassard, P; Green, E M; Van Grootel, V; Bergeron, P; Zong, W; Dupret, M-A

2018-02-01

White-dwarf stars are the end product of stellar evolution for most stars in the Universe. Their interiors bear the imprint of fundamental mechanisms that occur during stellar evolution. Moreover, they are important chronometers for dating galactic stellar populations, and their mergers with other white dwarfs now appear to be responsible for producing the type Ia supernovae that are used as standard cosmological candles. However, the internal structure of white-dwarf stars-in particular their oxygen content and the stratification of their cores-is still poorly known, because of remaining uncertainties in the physics involved in stellar modelling codes. Here we report a measurement of the radial chemical stratification (of oxygen, carbon and helium) in the hydrogen-deficient white-dwarf star KIC08626021 (J192904.6+444708), independently of stellar-evolution calculations. We use archival data coupled with asteroseismic sounding techniques to determine the internal constitution of this star. We find that the oxygen content and extent of its core exceed the predictions of existing models of stellar evolution. The central homogeneous core has a mass of 0.45 solar masses, and is composed of about 86 per cent oxygen by mass. These values are respectively 40 per cent and 15 per cent greater than those expected from typical white-dwarf models. These findings challenge present theories of stellar evolution and their constitutive physics, and open up an avenue for calibrating white-dwarf cosmochronology.

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

PubMed Central

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

Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO 3 Perovskites

DOE PAGES

Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; ...

2016-02-11

Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO 3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting ofmore » the e g orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.« less

Observations of CO2 in Comets C/2012 S1 ISON and C/2012 K1 PANSTARRS

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Lisse, Carey; Chanover, Nancy

2013-10-01

Comets have undergone very little thermal evolution in their lifetimes, resulting in a primitive composition. This primitive composition makes observations of comets very important tools for understanding the origin of the Solar System. The ices H2O, CO2, and CO are the primary ices present in cometary nuclei, and constraining their abundances has tremendous implications for the formation and evolutionary history of comets. Of these ices, H2O and CO can be observed from the ground, while CO2 cannot. A potentially effective tracer for CO2 in comets that is accessible from the ground is atomic oxygen. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comets C/2012 S1 ISON and C/2012 K1 PANSTARRS. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and McDonald Observatory and observations of H2O and CO at Keck and IRTF. These observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of CO2. In addition, ISON is the target of an extensive observing campaign led by NASA, and the proposed Spitzer observations fill a vital niche as the only observatory that can observe CO2 during both the near-perihelion time frame and significantly (months) after perihelion. Understanding the evolution of the CO2 abundance over the apparition is a key piece to understanding how the volatile compostion of the comet changes over the apparition.

Observation of CO2 in Comet C/2012 K5 LINEAR

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Chanover, Nancy

2012-12-01

The study of cometary composition is important to understanding the formation and evolution of our solar system. Comets have undergone very little thermal evolution in their lifetimes, which results in their near pristine composition. The nucleus of a comet is very rarely detected directly. Instead, we observe the coma that surrounds the nucleus. Physical and chemical processes in the coma affect its composition, and therefore coma composition is not a direct representation of nuclear composition. An important trend is the observed variation of coma composition with heliocentric distance, most likely influenced by the volatility of the main surface ices, H2O, CO2, and CO. Infrared studies of these molecules are complicated by telluric features, so often daughter molecules of these species such as OH are observed instead. A potentially effective tracer for these primary ices is atomic oxygen in the coma. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comet C/2012 K5 LINEAR. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and observations of H2O at Keck. These near simultaneous observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of these primary volatiles and aid our understanding of the variation in coma composition as a function of heliocentric distance, and therefore the composition of the nucleus and how our solar system was formed.

Health effects of metals: a role for evolution?

PubMed Central

Clarkson, T

1995-01-01

Metals have been mined and used since ancient times. The industrial era has seen a sharp increase in both the amounts and variety of metals that find applications in industry. The inadvertent release of metals, such as from fossil fuel consumption, also adds to the global burden. A number of catastrophic outbreaks have alerted us to the occupational and environmental health risks. Life on this planet has evolved in the presence of metals. Cells learned to make use of the more abundant metals in the Archean oceans as an integral component in their structure and function. Today, we inherit these as the essential metals. At the same time, evolving life must have developed means of coping with the potentially toxic actions of metals. The appearance of oxygen in the atmosphere in the Precambrian period also resulted in cells both using and developing protective mechanisms against what must have been a highly toxic, reactive gas. Atmospheric oxygen must have increased the solubility of many metals as insoluble metal sulfides were oxidized to the more soluble sulfates. It may be no coincidence that the protective mechanisms for oxygen are also used to protect against a number of toxic metals. Selected examples are given on the role of evolution in metal toxicology, specifically, examples where the normal function of essential metals is deranged by competition with nonessential metals. Examples are also given of protective mechanisms that involve enzymes or cofactors involved in the oxygen defense system. PMID:7621810

Enhancing Electrocatalytic Performance of Bifunctional Cobalt–Manganese-Oxynitride Nanocatalysts on Graphene

DOE PAGES

Li, Yang; Kuttiyiel, Kurian A.; Wu, Lijun; ...

2016-11-21

In this paper, we report the synthesis and characterization of graphenesupported cobalt–manganese-oxynitride nanocatalysts (CoMnON/G) as bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A nitriding treatment of spinel compound CoMnO increased the ORR activity considerably, and the most active material catalyzed the ORR with only a 30 mV half-wave potential difference from the commercial carbon-supported platinum (Pt/C) in alkaline media. In addition to high activity, the catalyst also exhibited an intrinsic stability that outperformed Pt/C. Finally, an appropriately designed nitridation thus facilitates new directions for developing active and durable non-precious-metal oxynitride electocatalysts.

"The Evolution of Photosynthesis and the Transition from an Anaerobic to an Aerobic World"

NASA Technical Reports Server (NTRS)

Blankenship, Robert E.

2005-01-01

This project was focused on elucidating the evolution of photosynthesis, in particular the evolutionary developments that preceded and accompanied the transition from anoxygenic to oxygenic photosynthesis. Development of this process has clearly been of central importance to evolution of life on Earth. Photosynthesis is the mechanism that ultimately provides for the energy needs of most surface-dwelling organisms. Eukaryotic organisms are absolutely dependent on the molecular oxygen that has been produced by oxygenic photosynthesis. In this project we have employed a multidisciplinary approach to understand some of the processes that took place during the evolution of photosynthesis. In this project, we made excellent progress in the overall area of understanding the origin and evolution of photosynthesis. Particular progress has been made on several more specific research questions, including the molecular evolutionary analysis of photosynthetic components and biosynthetic pathways (2,3, 5, 7, 10), as well as biochemical characterization of electron transfer proteins related to photosynthesis and active oxygen protection (4,6,9). Finally, several review and commentary papers have been published (1, 8, 1 1). A total of twelve publications arose out of this grant, references to which are given below. Some specific areas of progress are highlighted and discussed in more detail.

Molecular evolution and expression of oxygen transport genes in livebearing fishes (Poeciliidae) from hydrogen sulfide rich springs.

PubMed

Barts, Nicholas; Greenway, Ryan; Passow, Courtney N; Arias-Rodriguez, Lenin; Kelley, Joanna L; Tobler, Michael

2018-04-01

Hydrogen sulfide (H 2 S) is a natural toxicant in some aquatic environments that has diverse molecular targets. It binds to oxygen transport proteins, rendering them non-functional by reducing oxygen-binding affinity. Hence, organisms permanently inhabiting H 2 S-rich environments are predicted to exhibit adaptive modifications to compensate for the reduced capacity to transport oxygen. We investigated 10 lineages of fish of the family Poeciliidae that have colonized freshwater springs rich in H 2 S-along with related lineages from non-sulfidic environments-to test hypotheses about the expression and evolution of oxygen transport genes in a phylogenetic context. We predicted shifts in the expression of and signatures of positive selection on oxygen transport genes upon colonization of H 2 S-rich habitats. Our analyses indicated significant shifts in gene expression for multiple hemoglobin genes in lineages that have colonized H 2 S-rich environments, and three hemoglobin genes exhibited relaxed selection in sulfidic compared to non-sulfidic lineages. However, neither changes in gene expression nor signatures of selection were consistent among all lineages in H 2 S-rich environments. Oxygen transport genes may consequently be predictable targets of selection during adaptation to sulfidic environments, but changes in gene expression and molecular evolution of oxygen transport genes in H 2 S-rich environments are not necessarily repeatable across replicated lineages.

Dual organism design cycle reveals small subunit substitutions that improve [NiFe] hydrogenase hydrogen evolution

PubMed Central

2013-01-01

Background Photosynthetic microorganisms that directly channel solar energy to the production of molecular hydrogen are a potential future biofuel system. Building such a system requires installation of a hydrogenase in the photosynthetic organism that is both tolerant to oxygen and capable of hydrogen production. Toward this end, we have identified the [NiFe] hydrogenase from the marine bacterium Alteromonas macleodii “Deep ecotype” that is able to be heterologously expressed in cyanobacteria and has tolerance to partial oxygen. The A. macleodii enzyme shares sequence similarity with the uptake hydrogenases that favor hydrogen uptake activity over hydrogen evolution. To improve hydrogen evolution from the A. macleodii hydrogenase, we examined the three Fe-S clusters found in the small subunit of many [NiFe] uptake hydrogenases that presumably act as a molecular wire to guide electrons to or from the active site of the enzyme. Studies by others altering the medial cluster of a Desulfovibrio fructosovorans hydrogenase from 3Fe-4S to 4Fe-4S resulted in two-fold improved hydrogen evolution activity. Results We adopted a strategy of screening for improved hydrogenase constructs using an Escherichia coli expression system before testing in slower growing cyanobacteria. From the A. macleodii enzyme, we created a mutation in the gene encoding the hydrogenase small subunit that in other systems is known to convert the 3Fe-4S medial cluster to 4Fe-4S. The medial cluster substitution did not improve the hydrogen evolution activity of our hydrogenase. However, modifying both the medial cluster and the ligation of the distal Fe-S cluster improved in vitro hydrogen evolution activity relative to the wild type hydrogenase by three- to four-fold. Other properties of the enzyme including thermostability and tolerance to partial oxygen did not appear to be affected by the substitutions. Conclusions Our results show that substitution of amino acids altering the ligation of Fe-S clusters in the A. macleodii [NiFe] uptake hydrogenase resulted in increased hydrogen evolution activity. This activity can be recapitulated in multiple host systems and with purified protein. These results validate the approach of using an E. coli-cyanobacteria shuttle system for enzyme expression and improvement. PMID:23819621

Promiscuous anaerobes: new and unconventional metabolism in methanogenic archaea.

PubMed

Grochowski, Laura L; White, Robert H

2008-03-01

The development of an oxygenated atmosphere on earth resulted in the polarization of life into two major groups, those that could live in the presence of oxygen and those that could not-the aerobes and the anaerobes. The evolution of aerobes from the earliest anaerobic prokaryotes resulted in a variety of metabolic adaptations. Many of these adaptations center on the need to sustain oxygen-sensitive reactions and cofactors to function in the new oxygen-containing atmosphere. Still other metabolic pathways that were not sensitive to oxygen also diverged. This is likely due to the physical separation of the organisms, based on their ability to live in the presence of oxygen, which allowed for the independent evolution of the pathways. Through the study of metabolic pathways in anaerobes and comparison to the more established pathways from aerobes, insight into metabolic evolution can be gained. This, in turn, can allow for extra- polation to those metabolic pathways occurring in the Last Universal Common Ancestor (LUCA). Some of the unique and uncanonical metabolic pathways that have been identified in the archaea with emphasis on the biochemistry of an obligate anaerobic methanogen, Methanocaldococcus jannaschii are reviewed.

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

NASA Astrophysics Data System (ADS)

Joya, Khurram S.; Sinatra, Lutfan; Abdulhalim, Lina G.; Joshi, Chakra P.; Hedhili, M. N.; Bakr, Osman M.; Hussain, Irshad

2016-05-01

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation. Electronic supplementary information (ESI) available: CCDC 1419754 and 1419731. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6nr00709k

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

PubMed Central

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 photosynthesis, including the activity of metabolically versatile cyanobacteria, played an important role in delaying the oxygenation of Earth's surface ocean during the Proterozoic Eon. PMID:26549614

Ultrafine and highly disordered Ni 2 Fe 1 nanofoams enabled highly efficient oxygen evolution reaction in alkaline electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Song, Junhua; Zhu, Chengzhou

Nickel iron hydroxides are the most promising non-noble electrocatalysts for oxygen evolution reaction (OER) in alkaline media. By in situ reduction of metal precursors, compositionally controlled three-dimensional (3D) NixFeyB nanofoams (NFs) are synthesized with high surface area and uniformly distributed bimetallic networks. The resultant ultrafine amorphous Ni2Fe1B NFs exhibit extraordinary electrocatalytic performance toward OER and overall water splitting in alkaline media. At a potential as low as 1.42 V (vs. RHE), Ni2Fe1B NFs can deliver a current density of 10 mA/cm2 and show negligible activity loss after 12 hours’ stability test. Even at large current flux of 100 mA/cm2, anmore » ultralow overpotential of 0.27 V is achieved, which is about 0.18 V more negative than benchmark RuO2. Both ex-situ Mӧssbauer spectroscopy and X-ray Absorption Spectroscopy (XAS) reveal a phase separation and transformation for the Ni2Fe1B catalyst during OER process. The evolution of oxidation state and disordered structure of Ni2Fe1B might be a key to the high catalytic performance for OER.« less

Biogeochemical Modeling of the Second Rise of Oxygen

NASA Astrophysics Data System (ADS)

Smith, M. L.; Catling, D.; Claire, M.; Zahnle, K.

2014-03-01

The rise of atmospheric oxygen set the tempo for the evolution of complex life on Earth. Oxygen levels are thought to have increased in two broad steps: one step occurred in the Archean ~ 2.45 Ga (the Great Oxidation Event or GOE), and another step occured in the Neoproterozoic ~750-580 Ma (the Neoprotoerozoic Oxygenation Event or NOE). During the NOE, oxygen levels increased from ~1-10% of the present atmospheric level (PAL) (Holland, 2006), to ~15% PAL in the late Neoproterozoic, to ~100% PAL later in the Phanerozoic. Complex life requires O2, so this transition allowed complex life to evolve. We seek to understand what caused the NOE. To explore causes for the NOE, we build upon the biogeochemical model of Claire et al. (2006), which calculates the redox evolution of the atmosphere, ocean, biosphere, and crust in the Archean through to the early Proterozoic. In this model, the balance between oxygenconsuming and oyxgen-producing fluxes evolves over time such that at ~2.4 Ga, the rapidly acting sources of oxygen outweigh the rapidly-acting sinks. Or, in other words, at ~2.4 Ga, the flux of oxygen from organic carbon burial exceeds the sinks of oxygen from reaction with reduced volcanic and metamoprphic gases. The model is able to drive oxygen levels to 1-10% PAL in the Proterozoic; however, the evolving redox fluxes in the model cannot explain how oxygen levels pushed above 1-10% in the late Proterozoic. The authors suggest that perhaps another buffer, such as sulfur, is needed to describe Proterozoic and Phanerozoic redox evolution. Geologic proxies show that in the Proterozoic, up to 10% of the deep ocean may have been sulfidic. With this ocean chemistry, the global sulfur cycle would have worked differently than it does today. Because the sulfur and oxygen cycles interact, the oxygen concentration could have permanently changed due to an evolving sulfur cycle (in combination with evolving redox fluxes associated with other parts of the oxygen cycle and carbon cycles). To determine how fluxes of sulfur, carbon, and oxygen define oxygen levels before, during, and after the NOE, we add a sulfur cycle to the biogeochemical model of Claire et al. (2006). Understanding processes that impact the evolution of atmospheric oxygen on Earth is key to diagnosing the habitability of other planets because it is possible that other planets undergo a similar evolution. If a sulfidic deep ocean was instrumental in driving oxygen levels to modern values, then it would be valuable to remotely detect a sulfide-rich ocean on another planet. One such remotely-detectable signature could be the color of a sulfide-rich ocean. For example, Gallardo and Espinoza (2008) have hypothesized that a sulfidic ocean may be have been blacker in color. Even if a sulfidic ocean is not key to oxygenation, detecting a planet in transition--that is, a planet with intermediate levels of oxygen co-existing with higher levels of reduced gases - would be important for diagnosing habitability.

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE PAGES

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros; ...

2017-12-06

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Oxygen and Carbon Dioxide Fluxes from Barley Shoots Depend on Nitrate Assimilation 1

PubMed Central

Bloom, Arnold J.; Caldwell, Richard M.; Finazzo, John; Warner, Robert L.; Weissbart, Joseph

1989-01-01

A custom oxygen analyzer in conjunction with an infrared carbon dioxide analyzer and humidity sensors permitted simultaneous measurements of oxygen, carbon dioxide, and water vapor fluxes from the shoots of intact barley plants (Hordeum vulgare L. cv Steptoe). The oxygen analyzer is based on a calciazirconium sensor and can resolve concentration differences to within 2 microliters per liter against the normal background of 210,000 microliters per liter. In wild-type plants receiving ammonium as their sole nitrogen source or in nitrate reductase-deficient mutants, photosynthetic and respiratory fluxes of oxygen equaled those of carbon dioxide. By contrast, wild-type plants exposed to nitrate had unequal oxygen and carbon dioxide fluxes: oxygen evolution at high light exceeded carbon dioxide consumption by 26% and carbon dioxide evolution in the dark exceeded oxygen consumption by 25%. These results indicate that a substantial portion of photosynthetic electron transport or respiration generates reductant for nitrate assimilation rather than for carbon fixation or mitochondrial electron transport. PMID:16667024

Coping with cyclic oxygen availability: evolutionary aspects.

PubMed

Flück, Martin; Webster, Keith A; Graham, Jeffrey; Giomi, Folco; Gerlach, Frank; Schmitz, Anke

2007-10-01

Both the gradual rise in atmospheric oxygen over the Proterozoic Eon as well as episodic fluctuations in oxygen over several million-year time spans during the Phanerozoic Era, have arguably exerted strong selective forces on cellular and organismic respiratory specialization and evolution. The rise in atmospheric oxygen, some 2 billion years after the origin of life, dramatically altered cell biology and set the stage for the appearance of multicelluar life forms in the Vendian (Ediacaran) Period of the Neoproterozoic Era. Over much of the Paleozoic, the level of oxygen in the atmosphere was near the present atmospheric level (21%). In the Late Paleozoic, however, there were extended times during which the level of atmospheric oxygen was either markedly lower or markedly higher than 21%. That these Paleozoic shifts in atmospheric oxygen affected the biota is suggested by the correlations between: (1) Reduced oxygen and the occurrences of extinctions, a lowered biodiversity and shifts in phyletic succession, and (2) During hyperoxia, the corresponding occurrence of phenomena such as arthropod gigantism, the origin of insect flight, and the evolution of vertebrate terrestriality. Basic similarities in features of adaptation to hyopoxia, manifest in living organisms at levels ranging from genetic and cellular to physiological and behavioral, suggest the common and early origin of a suite of adaptive mechanisms responsive to fluctuations in ambient oxygen. Comparative integrative approaches addressing the molecular bases of phenotypic adjustments to cyclic oxygen fluctuation provide broad insight into the incremental steps leading to the early evolution of homeostatic respiratory mechanisms and to the specialization of organismic respiratory function.

Molecular Evolution of the Oxygen-Binding Hemerythrin Domain

PubMed Central

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

2016-01-01

Background 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. Results 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. Conclusions 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-binding hemerythrin domain in both prokaryotes and eukaryotes led to a wide variety of functions, ranging from protection against oxidative damage in anaerobic and microaerophilic organisms, to oxygen supplying to particular enzymes and pathways in aerobic and facultative species. PMID:27336621

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

PubMed

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

2013-10-09

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

Correlation between pH dependence of O2 evolution and sensitivity of Mn cations in the oxygen-evolving complex to exogenous reductants.

PubMed

Semin, Boris K; Davletshina, Lira N; Rubin, Andrei B

2015-08-01

Effects of pH, Ca(2+), and Cl(-) ions on the extraction of Mn cations from oxygen-evolving complex (OEC) in Ca-depleted photosystem II (PSII(-Ca)) by exogenous reductants hydroquinone (H2Q) and H2O2 were studied. Two of 4 Mn cations are released by H2Q and H2O2 at pHs 5.7, 6.5, and 7.5, and their extraction does not depend on the presence of Ca(2+) and Cl(-) ions. One of Mn cations ("resistant" Mn cation) cannot be extracted by H2Q and H2O2 at any pH. Extraction of 4th Mn ion ("flexible" Mn cation) is sensitive to pH, Ca(2+), and Cl(-). This Mn cation is released by reductants at pH 6.5 but not at pHs 5.7 and 7.5. A pH dependence curve of the oxygen-evolving activity in PSII(-Ca) membranes (in the presence of exogenous Ca(2+)) has a bell-shaped form with the maximum at pH 6.5. Thus, the increase in the resistance of flexible Mn cation in OEC to the action of reductants at acidic and alkaline pHs coincides with the decrease in oxygen evolution activity at these pHs. Exogenous Ca(2+) protects the extraction of flexible Mn cation at pH 6.5. High concentration of Cl(-) anions (100 mM) shifts the pH optimum of oxygen evolution to alkaline region (around pH 7.5), while the pH of flexible Mn extraction is also shifted to alkaline pH. This result suggests that flexible Mn cation plays a key role in the water-splitting reaction. The obtained results also demonstrate that only one Mn cation in Mn4 cluster is under strong control of calcium. The change in the flexible Mn cation resistance to exogenous reductants in the presence of Ca(2+) suggests that Ca(2+) can control the redox potential of this cation.

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Zheng, Gengfeng

2015-08-01

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE.A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE. Electronic supplementary information (ESI) available: Supporting figures, with additional SEM images, EDS spectra, N2 sorption isotherms, charge-discharge curves, cycling performance, Ragone plot, Nyquist plots and linear scan voltammogram plots. See DOI: 10.1039/c5nr04603c

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

PubMed

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.

Aerobic metabolism underlies complexity and capacity

PubMed Central

Koch, Lauren G; Britton, Steven L

2008-01-01

The evolution of biological complexity beyond single-celled organisms was linked temporally with the development of an oxygen atmosphere. Functionally, this linkage can be attributed to oxygen ranking high in both abundance and electronegativity amongst the stable elements of the universe. That is, reduction of oxygen provides for close to the largest possible transfer of energy for each electron transfer reaction. This suggests the general hypothesis that the steep thermodynamic gradient of an oxygen environment was permissive for the development of multicellular complexity. A corollary of this hypothesis is that aerobic metabolism underwrites complex biological function mechanistically at all levels of organization. The strong contemporary functional association of aerobic metabolism with both physical capacity and health is presumably a product of the integral role of oxygen in our evolutionary history. Here we provide arguments from thermodynamics, evolution, metabolic network analysis, clinical observations and animal models that are in accord with the centrality of oxygen in biology. PMID:17947307

Raman spectra of Hg-based superconductors: Effect of oxygen defects

NASA Astrophysics Data System (ADS)

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

1996-09-01

Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa2Can-1CunO2n+2+δ (n=1, 2, 3, 4, and 5) high-Tc superconductor family. A systematic evolution of the spectrum, which mainly involves oxygen-related phonons around 590, 570, 540, and 470 cm-1, with an increasing number of CuO2 layers, has been observed. Local laser annealing measurements clearly demonstrate that all these phonons are closely related to interstitial oxygen in the HgOδ planes. The origin of the spectrum evolution with the number of CuO2 layers lies in the variation of interstitial oxygen content.

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-09-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm-2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER.

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

PubMed Central

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-01-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm−2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER. PMID:27658968

Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Lei; Zhang, Yan; Hudak, Bethany M.

This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxidemore » nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

The Paleoproterozoic snowball Earth: a climate disaster triggered by the evolution of oxygenic photosynthesis.

PubMed

Kopp, Robert E; Kirschvink, Joseph L; Hilburn, Isaac A; Nash, Cody Z

2005-08-09

Although biomarker, trace element, and isotopic evidence have been used to claim that oxygenic photosynthesis evolved by 2.8 giga-annum before present (Ga) and perhaps as early as 3.7 Ga, a skeptical examination raises considerable doubt about the presence of oxygen producers at these times. Geological features suggestive of oxygen, such as red beds, lateritic paleosols, and the return of sedimentary sulfate deposits after a approximately 900-million year hiatus, occur shortly before the approximately 2.3-2.2 Ga Makganyene "snowball Earth" (global glaciation). The massive deposition of Mn, which has a high redox potential, practically requires the presence of environmental oxygen after the snowball. New age constraints from the Transvaal Supergroup of South Africa suggest that all three glaciations in the Huronian Supergroup of Canada predate the Snowball event. A simple cyanobacterial growth model incorporating the range of C, Fe, and P fluxes expected during a partial glaciation in an anoxic world with high-Fe oceans indicates that oxygenic photosynthesis could have destroyed a methane greenhouse and triggered a snowball event on time-scales as short as 1 million years. As the geological evidence requiring oxygen does not appear during the Pongola glaciation at 2.9 Ga or during the Huronian glaciations, we argue that oxygenic cyanobacteria evolved and radiated shortly before the Makganyene snowball.

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

Occurrence and formation kinetics of pyranomalvidin-procyanidin dimer pigment in Merlot red wine: impact of acidity and oxygen concentrations.

PubMed

Pechamat, Laurent; Zeng, Liming; Jourdes, Michael; Ghidossi, Rémy; Teissedre, Pierre-Louis

2014-02-19

Once released from red grape skins, anthocyanins undergo various chemical reactions leading to the formation of more stable pigments such as pyranoanthocyanin, as well as other derivatives. Among these pigments, pyranoanthocyanins linked directly to flavanol dimers have been detected and identified in aged Port wine but not in dry red wine. These pigments are very important with regard to the wine color evolution since they are involved in wine color evolution and stabilization. During this investigation, the occurrence in dry red wine of two pyranomalvidin-procyanidin dimer has been established by low and high resolution HPLC-UV-MS analysis. Moreover, the impact of acidity and oxygen levels on their formation in red wine has been estimated. After four months of evolution, the results showed that, for the same pH, the quantity of this pigment was correlated with oxygen concentrations. Moreover, for the same quantity of oxygen, the concentration of this pigment was related to the acidity level.

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

PubMed

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

2017-09-08

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.

Structure Evolution of Graphene Oxide during Thermally Driven Phase Transformation: Is the Oxygen Content Really Preserved?

PubMed Central

Sun, Pengzhan; Wang, Yanlei; Liu, He; Wang, Kunlin; Wu, Dehai; Xu, Zhiping; Zhu, Hongwei

2014-01-01

A mild annealing procedure was recently proposed for the scalable enhancement of graphene oxide (GO) properties with the oxygen content preserved, which was demonstrated to be attributed to the thermally driven phase separation. In this work, the structure evolution of GO with mild annealing is closely investigated. It reveals that in addition to phase separation, the transformation of oxygen functionalities also occurs, which leads to the slight reduction of GO membranes and furthers the enhancement of GO properties. These results are further supported by the density functional theory based calculations. The results also show that the amount of chemically bonded oxygen atoms on graphene decreases gradually and we propose that the strongly physisorbed oxygen species constrained in the holes and vacancies on GO lattice might be responsible for the preserved oxygen content during the mild annealing procedure. The present experimental results and calculations indicate that both the diffusion and transformation of oxygen functional groups might play important roles in the scalable enhancement of GO properties. PMID:25372142

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

NASA Astrophysics Data System (ADS)

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.

Early oxygenation of the terrestrial environment during the Mesoproterozoic.

PubMed

Parnell, John; Boyce, Adrian J; Mark, Darren; Bowden, Stephen; Spinks, Sam

2010-11-11

Geochemical data from ancient sedimentary successions provide evidence for the progressive evolution of Earth's atmosphere and oceans. Key stages in increasing oxygenation are postulated for the Palaeoproterozoic era (∼2.3 billion years ago, Gyr ago) and the late Proterozoic eon (about 0.8 Gyr ago), with the latter implicated in the subsequent metazoan evolutionary expansion. In support of this rise in oxygen concentrations, a large database shows a marked change in the bacterially mediated fractionation of seawater sulphate to sulphide of Δ(34)S < 25‰ before 1 Gyr to ≥50‰ after 0.64 Gyr. This change in Δ(34)S has been interpreted to represent the evolution from single-step bacterial sulphate reduction to a combination of bacterial sulphate reduction and sulphide oxidation, largely bacterially mediated. This evolution is seen as marking the rise in atmospheric oxygen concentrations and the evolution of non-photosynthetic sulphide-oxidizing bacteria. Here we report Δ(34)S values exceeding 50‰ from a terrestrial Mesoproterozoic (1.18 Gyr old) succession in Scotland, a time period that is at present poorly characterized. This level of fractionation implies disproportionation in the sulphur cycle, probably involving sulphide-oxidizing bacteria, that is not evident from Δ(34)S data in the marine record. Disproportionation in both red beds and lacustrine black shales at our study site suggests that the Mesoproterozoic terrestrial environment was sufficiently oxygenated to support a biota that was adapted to an oxygen-rich atmosphere, but had also penetrated into subsurface sediment.

One-pot Synthesis of CdS Irregular Nanospheres Hybridized with Oxygen-Incorporated Defect-Rich MoS2 Ultrathin Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

PubMed

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.

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favaro, Marco; Yang, Jinhui; Nappini, Silvia

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Favaro, Marco; Yang, Jinhui; Nappini, Silvia; ...

2017-06-09

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst

PubMed Central

Yang, Hong Bin; Miao, Jianwei; Hung, Sung-Fu; Chen, Jiazang; Tao, Hua Bing; Wang, Xizu; Zhang, Liping; Chen, Rong; Gao, Jiajian; Chen, Hao Ming; Dai, Liming; Liu, Bin

2016-01-01

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g−1, and a peak power density of 65 mW cm−2, which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance. PMID:27152333

The Remarkable Deaths of 9-11 Solar Mass Stars

NASA Astrophysics Data System (ADS)

Woosley, S. E.; Heger, Alexander

2015-09-01

The post-helium-burning evolution of stars from 7 {M}⊙ to 11 {M}⊙ is complicated by the lingering effects of degeneracy and off-center ignition. Here, stars in this mass range are studied using a standard set of stellar physics. Two important aspects of the study are the direct coupling of a reaction network of roughly 220 nuclei to the structure calculation at all stages and the use of a subgrid model to describe the convective bounded flame that develops during neon and oxygen burning. Below 9.0 {M}⊙ degenerate oxygen-neon cores form that may become either white dwarfs or electron-capture supernovae. Above 10.3 {M}⊙ the evolution proceeds “normally” to iron-core collapse, without composition inversions or degenerate flashes. Emphasis here is upon the stars in between, which typically ignite oxygen burning off-center. After oxygen burns in a convectively bounded flame, silicon burning ignites in a degenerate flash that commences closer to the stellar center and with increasing violence for stars of larger mass. In some cases the silicon flash is so violent that it could lead to the early ejection of the hydrogen envelope. This might have interesting observable consequences. For example, the death of a 10.0 {M}⊙ star could produce two supernova-like displays, a faint low-energy event due to the silicon flash, and an unusually bright supernova many months later as the low-energy ejecta from core collapse collides with the previously ejected envelope. The potential relation to the Crab supernova is discussed.

Three reversible states controlled on a gold monoatomic contact by the electrochemical potential

NASA Astrophysics Data System (ADS)

Kiguchi, Manabu; Konishi, Tatsuya; Hasegawa, Kouta; Shidara, Satoshi; Murakoshi, Kei

2008-06-01

Conductance of a Au monoatomic contact was investigated under the electrochemical potential control. The Au contact showed three different behaviors depending on the potential: 1G0 (G0=2e2/h) , 0.5G0 , and not-well-defined values below 1G0 were shown when the potential of the contact was kept at -0.6V (double layer potential), -1.0V (hydrogen evolution potential), and 0.8 V (oxide formation potential) versus Ag/AgCl in 0.1M Na2SO4 solution, respectively. These three reversible states and their respective conductances could be fully controlled by the electrochemical potential. These changes in the conductance values are discussed based on the proposed structure models of hydrogen adsorbed and oxygen incorporated on a Au monoatomic contact.

Activity–stability relationship in the surface electrochemistry of the oxygen evolution reaction

DOE PAGES

Chang, Seo Hyoung; Connell, Justin G.; Danilovic, Nemanja; ...

2014-07-25

Understanding the functional links between the stability and reactivity of oxide materials during the oxygen evolution reaction (OER) is one key to enabling a vibrant hydrogen economy capable of competing with fossil fuel-based technologies. In this work, by focusing on the surface chemistry of monometallic Ru oxide in acidic and alkaline environments, we found that the kinetics of the OER are almost entirely controlled by the stability of the Ru surface atoms. The same activity–stability relationship was found for more complex, polycrystalline and single-crystalline SrRuO 3 thin films in alkaline solutions. We propose that the electrochemical transformation of either watermore » (acidic solutions) or hydroxyl ions (alkaline solutions) to di-oxygen molecules takes place at defect sites that are inherently present on every electrode surface. During the OER, surface defects are also created by the corrosion of the Ru ions. The dissolution is triggered by the potential-dependent change in the valence state ( n) of Ru: from stable but inactive Ru 4+ to unstable but active Ru n>4+. We conclude that if the oxide is stable then it is completely inactive for the OER. As a result, a practical consequence is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate of the oxide is neither too fast nor too slow.« less

The effects of parametric changes in electropolishing process on surface properties of 316L stainless steel

NASA Astrophysics Data System (ADS)

ur Rahman, Zia; Deen, K. M.; Cano, Lawrence; Haider, Waseem

2017-07-01

Corrosion resistance and biocompatibility of 316L stainless steel implants depend on the surface features and the nature of the passive film. The influence of electropolishing on the surface topography, surface free energy and surface chemistry was determined by atomic force microscopy, contact angle meter and X-ray photoelectron spectroscopy, respectively. The electropolishing of 316L stainless steel was conducted at the oxygen evolution potential (EPO) and below the oxygen evolution potential (EPBO). Compared to mechanically polished (MP) and EPO, the EPBO sample depicted lower surface roughness (Ra = 6.07 nm) and smaller surface free energy (44.21 mJ/m2). The relatively lower corrosion rate (0.484 mpy) and smaller passive current density (0.619 μA/cm2) as determined from cyclic polarization scans was found to be related with the presence of OH, Cr(III), Fe(0), Fe(II) and Fe(III) species at the surface. These species assured the existence of relatively uniform passive oxide film over EPBO surface. Moreover, the relatively large charge transfer (Rct) and passive film resistance (Rf) registered by EPBO sample from impedance spectroscopy analysis confirmed its better electrochemical performance. The in vitro response of these polished samples toward MC3T3 pre-osteoblast cell proliferation was determined to be directly related with their surface and electrochemical properties.

Ce-Doped NiFe-Layered Double Hydroxide Ultrathin Nanosheets/Nanocarbon Hierarchical Nanocomposite as an Efficient Oxygen Evolution Catalyst.

PubMed

Xu, Huajie; Wang, Bingkai; Shan, Changfu; Xi, Pinxian; Liu, Weisheng; Tang, Yu

2018-02-21

Developing convenient doping to build highly active oxygen evolution reaction (OER) electrocatalysts is a practical process for solving the energy crisis. Herein, a facile and low-cost in situ self-assembly strategy for preparing a Ce-doped NiFe-LDH nanosheets/nanocarbon (denoted as NiFeCe-LDH/CNT, LDH = layered double hydroxide and CNT = carbon nanotube) hierarchical nanocomposite is established for enhanced OER, in which the novel material provides its overall advantageous structural features, including high intrinsic catalytic activity, rich redox properties, high, flexible coordination number of Ce 3+ , and strongly coupled interface. Further experimental results indicate that doped Ce into NiFe-LDH/CNT nanoarrays brings about the reinforced specific surface area, electrochemical surface area, lattice defects, and the electron transport between the LDH nanolayered structure and the framework of CNTs. The effective synergy prompts the NiFeCe-LDH/CNT nanocomposite to possess superior OER electrocatalytic activity with a low onset potential (227 mV) and Tafel slope (33 mV dec -1 ), better than the most non-noble metal-based OER electrocatalysts reported. Therefore, the combination of the remarkable catalytic ability and the facile normal temperature synthesis conditions endows the Ce-doped LDH nanocomposite as a promising catalyst to expand the field of lanthanide-doped layered materials for efficient water-splitting electrocatalysis with scale-up potential.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Dennis P.; Neuefeind, Joerg C.; Koczkur, Kallum M.

(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 inhomogeneitiesmore » 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.« less

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

PubMed

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, including the activity of metabolically versatile cyanobacteria, played an important role in delaying the oxygenation of Earth's surface ocean during the Proterozoic Eon. © 2015 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Effects of pH and Oxygen on Photosynthetic Reactions of Intact Chloroplasts 1

PubMed Central

Heber, Ulrich; Andrews, T. John; Boardman, N. Keith

1976-01-01

Oxygen inhibition of photosynthesis was studied with intact spinach (Spinacia oleracea L.) chloroplasts which exhibited very high rates of photosynthetic CO2 reduction and were insensitive to additions of photosynthetic intermediates when CO2 was available at saturating concentrations. Photosynthetic rates were measured polarographically as O2 evolution, and the extent of the reduction of substrate was estimated from the amount of O2 evolved. With CO2 as substrate, inhibition of photosynthesis by O2 was dependent on pH. At pH values above 8, rates of O2 evolution were strongly inhibited by O2 and only a fraction of the added bicarbonate was reduced before O2 evolution ceased. The extent of O2 evolution declined with increasing O2 concentration and decreasing initial bicarbonate concentration. At pH 7.2, the initial photosynthetic rate was inhibited about 30% at high O2 levels, but the extent of O2 evolution was unaffected and most of the added bicarbonate was reduced. Photosynthetic O2 evolution with 3-phosphoglycerate as substrate was similarly dependent on pH and O2 concentration. In contrast, there was little effect of O2 and pH on oxaloacetate-dependent oxygen evolution. Acid-base shift experiments with osmotically shocked chloroplasts showed that ATP formation was not affected by O2. The results are discussed in terms of a balance between photosynthetic O2 evolution and O2 consumption by the ribulose diphosphate oxygenase reaction. PMID:16659466

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mir, Showkat H.; Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John

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 themore » 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.« less

Nitric Oxide Accumulation: The Evolutionary Trigger for Phytopathogenesis

PubMed Central

Santana, Margarida M.; Gonzalez, Juan M.; Cruz, Cristina

2017-01-01

Many publications highlight the importance of nitric oxide (NO) in plant–bacteria interactions, either in the promotion of health and plant growth or in pathogenesis. However, the role of NO in the signaling between bacteria and plants and in the fate of their interaction, as well as the reconstruction of their interactive evolution, remains largely unknown. Despite the complexity of the evolution of life on Earth, we explore the hypothesis that denitrification and aerobic respiration were responsible for local NO accumulation, which triggered primordial antagonistic biotic interactions, namely the first phytopathogenic interactions. N-oxides, including NO, could globally accumulate via lightning synthesis in the early anoxic ocean and constitute pools for the evolution of denitrification, considered an early step of the biological nitrogen cycle. Interestingly, a common evolution may be proposed for components of denitrification and aerobic respiration pathways, namely for NO and oxygen reductases, a theory compatible with the presence of low amounts of oxygen before the great oxygenation event (GOE), which was generated by Cyanobacteria. During GOE, the increase in oxygen caused the decrease of Earth’s temperature and the consequent increase of oxygen dissolution and availability, making aerobic respiration an increasingly dominant trait of the expanding mesophilic lifestyle. Horizontal gene transfer was certainly important in the joint expansion of mesophily and aerobic respiration. First denitrification steps lead to NO formation through nitrite reductase activity, and NO may further accumulate when oxygen binds NO reductase, resulting in denitrification blockage. The consequent transient NO surplus in an oxic niche could have been a key factor for a successful outcome of an early denitrifying prokaryote able to scavenge oxygen by NO/oxygen reductase or by an independent heterotrophic aerobic respiration pathway. In fact, NO surplus could result in toxicity causing “the first disease” in oxygen-producing Cyanobacteria. We inspected in bacteria the presence of sequences similar to the NO-producing nitrite reductase nirS gene of Thermus thermophilus, an extreme thermophilic aerobe of the Thermus/Deinococcus group, which constitutes an ancient lineage related to Cyanobacteria. In silico analysis revealed the relationship between the presence of nirS genes and phytopathogenicity in Gram-negative bacteria. PMID:29067010

In situ XAS study of CoBi modified hematite photoanodes.

PubMed

Xi, Lifei; Schwanke, Christoph; Zhou, Dong; Drevon, Dorian; van de Krol, Roel; Lange, Kathrin M

2017-11-21

Solar water splitting is a potentially scalable method to store solar energy in the form of renewable hydrogen gas. In this study, we demonstrate that the photoelectrochemical (PEC) performance of hematite photoanodes can be improved by modification with the oxygen evolution catalyst CoB i . The current density at 1.23 V of the pristine hematite under one sun is 0.88 mA cm -2 and it increases to 1.12 mA cm -2 after CoB i modification (∼27% improvement). The presence of a CoB i cocatalayst layer is proposed to improve the oxygen evolution reaction (OER) kinetics and also to prevent electron-hole recombination at the surface via passivating surface defects as well as suppressing the tunneling of electrons from the hematite core, thus improving the photocurrents and resulting in a negative shift of photocurrent onset potentials. These effects of CoB i modification are supported by experimental data obtained by performing electrochemical impedance spectroscopy (EIS), PEC and incident photon-to-current efficiency (IPCE) measurements. To investigate the electronic structure of the CoB i cocatalyst deposited on hematite, XPS and in situ X-ray absorption spectroscopy (XAS) are employed. Co K-edge spectra at different potentials and light conditions are recorded. This makes the present work different from most of the previous studies. Using a quantitative analysis method, information on the mean oxidation state of Co in the CoB i film under applied potential and illumination is revealed. We also compare different methods for determining the oxidation state from the edge position and find that the integral method and half height methods are most suitable. In summary, the present work underlines the improvement of the semiconductor/cocatalyst interface of oxygen evolving photoanodes and strengthens the importance of in situ XAS spectroscopy when studying catalysts. This study is the first report so far combining the studies of the PEC performance of a CoB i modified hematite nanorod array photoanode and in situ XAS at the Co K-edge.

Tunable Bifunctional Activity of Mnx Co3-x O4 Nanocrystals Decorated on Carbon Nanotubes for Oxygen Electrocatalysis.

PubMed

Zhao, Tingting; Gadipelli, Srinivas; He, Guanjie; Ward, Matthew J; Do, David; Zhang, Peng; Guo, Zhengxiao

2018-04-25

Noble-metal-free electrocatalysts are attractive for cathodic oxygen catalysis in alkaline membrane fuel cells, metal-air batteries, and electrolyzers. However, much of the structure-activity relationship is poorly understood. Herein, the comprehensive development of manganese cobalt oxide/nitrogen-doped multiwalled carbon nanotube hybrids (Mn x Co 3-x O 4 @NCNTs) is reported for highly reversible oxygen reduction and evolution reactions (ORR and OER, respectively). The hybrid structures are rationally designed by fine control of surface chemistry and synthesis conditions, including tuning of functional groups at surfaces, congruent growth of nanocrystals with controllable phases and particle sizes, and ensuring strong coupling across catalyst-support interfaces. Electrochemical tests reveal distinctly different oxygen catalytic activities among the hybrids, Mn x Co 3-x O 4 @NCNTs. Nanocrystalline MnCo 2 O 4 @NCNTs (MCO@NCNTs) hybrids show superior ORR activity, with a favorable potential to reach 3 mA cm -2 and a high current density response, equivalent to that of the commercial Pt/C standard. Moreover, the hybrid structure exhibits tunable and durable catalytic activities for both ORR and OER, with a lowest overall potential of 0.93 V. It is clear that the long-term electrochemical activities can be ensured by rational design of hybrid structures from the nanoscale. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Benthic Marine Cyanobacterial Mat Ecosystems: Biogeochemistry and Biomarkers

NASA Technical Reports Server (NTRS)

DesMarais, David J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Cyanobacterial mats are complete ecosystems that can include processes of primary production, diagenesis and lithification. Light sustains oxygenic photosynthesis, which in turn provides energy, organic matter and oxygen to the community. Due to both absorption and scattering phenomena, incident light is transformed with depth in the mat, both in intensity and spectral composition. Mobile photo synthesizers optimize their position with respect to this light gradient. When photosynthesis ceases at night, the upper layers of the mat become reduced and sulfidic. Counteracting gradients of oxygen and sulfide combine to provide daily-contrasting environments separated on a scale of a few mm. The functional complexity of mats, coupled with the highly proximal and ordered spatial arrangement of biota, offers the potential for a staggering number of interactions. At a minimum, the products of each functional group of microorganisms affect the other groups both positively and negatively. For example, cyanobacteria generate organic matter (potential substrates) but also oxygen (a toxin for many anaerobes). Anaerobic activity recycles nutrients to the photosynthesizers but also generates potentially toxic sulfide. The combination of benefits and hazards of light, oxygen and sulfide promotes the allocation of the various essential mat processes between light and dark periods, and to various depths in the mat. Observations of mats have produced numerous surprises. For example, obligately anaerobic processes can occur in the presence of abundant oxygen, highly reduced gases are produced in the presence of abundant sulfate, meiofauna thrive at high sulfide concentrations, and the mats' constituent populations respond to environmental changes in complex ways. While photosynthetic bacteria dominate the biomass and productivity of the mat, nonphotosynthetic, anaerobic processes constitute the ultimate biological filter on the ecosystem's emergent biosignatures, including those sedimentary textures, organic compounds, and minerals that enter the fossil record. The ability of cyanobacterial mats to channel abundant solar energy into the creation and maintenance of complex structures and processes has created a multitude of consequences, both for sedimentation and for the early evolution of our biosphere.

Late Proterozoic rise in atmospheric oxygen concentration inferred from phylogenetic and sulphur-isotope studies

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Teske, A.

1996-01-01

The evolution of non-photosynthetic sulphide-oxidizing bacteria was contemporaneous with a large shift in the isotopic composition of biogenic sedimentary sulphides between 0.64 and 1.05 billion years ago. Both events were probably driven by a rise in atmospheric oxygen concentrations to greater than 5-18% of present levels--a change that may also have triggered the evolution of animals.

Evolution of multicellularity coincided with increased diversification of cyanobacteria and the Great Oxidation Event.

PubMed

Schirrmeister, Bettina E; de Vos, Jurriaan M; Antonelli, Alexandre; Bagheri, Homayoun C

2013-01-29

Cyanobacteria are among the most diverse prokaryotic phyla, with morphotypes ranging from unicellular to multicellular filamentous forms, including those able to terminally (i.e., irreversibly) differentiate in form and function. It has been suggested that cyanobacteria raised oxygen levels in the atmosphere around 2.45-2.32 billion y ago during the Great Oxidation Event (GOE), hence dramatically changing life on the planet. However, little is known about the temporal evolution of cyanobacterial lineages, and possible interplay between the origin of multicellularity, diversification of cyanobacteria, and the rise of atmospheric oxygen. We estimated divergence times of extant cyanobacterial lineages under Bayesian relaxed clocks for a dataset of 16S rRNA sequences representing the entire known diversity of this phylum. We tested whether the evolution of multicellularity overlaps with the GOE, and whether multicellularity is associated with significant shifts in diversification rates in cyanobacteria. Our results indicate an origin of cyanobacteria before the rise of atmospheric oxygen. The evolution of multicellular forms coincides with the onset of the GOE and an increase in diversification rates. These results suggest that multicellularity could have played a key role in triggering cyanobacterial evolution around the GOE.

Evolution of multicellularity coincided with increased diversification of cyanobacteria and the Great Oxidation Event

PubMed Central

Schirrmeister, Bettina E.; de Vos, Jurriaan M.; Antonelli, Alexandre; Bagheri, Homayoun C.

2013-01-01

Cyanobacteria are among the most diverse prokaryotic phyla, with morphotypes ranging from unicellular to multicellular filamentous forms, including those able to terminally (i.e., irreversibly) differentiate in form and function. It has been suggested that cyanobacteria raised oxygen levels in the atmosphere around 2.45–2.32 billion y ago during the Great Oxidation Event (GOE), hence dramatically changing life on the planet. However, little is known about the temporal evolution of cyanobacterial lineages, and possible interplay between the origin of multicellularity, diversification of cyanobacteria, and the rise of atmospheric oxygen. We estimated divergence times of extant cyanobacterial lineages under Bayesian relaxed clocks for a dataset of 16S rRNA sequences representing the entire known diversity of this phylum. We tested whether the evolution of multicellularity overlaps with the GOE, and whether multicellularity is associated with significant shifts in diversification rates in cyanobacteria. Our results indicate an origin of cyanobacteria before the rise of atmospheric oxygen. The evolution of multicellular forms coincides with the onset of the GOE and an increase in diversification rates. These results suggest that multicellularity could have played a key role in triggering cyanobacterial evolution around the GOE. PMID:23319632

Interfacial oxygen migration and its effect on the magnetic anisotropy in Pt/Co/MgO/Pt films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Xi; Feng, Chun, E-mail: fengchun@ustb.edu.cn, E-mail: ghyu@mater.ustb.edu.cn; Liu, Yang

2014-02-03

This paper reports the interfacial oxygen migration effect and its induced magnetic anisotropy evolution in Pt/Co/MgO/Pt films. During depositing the MgO layer, oxygen atoms from the MgO combine with the neighboring Co atoms, leading to the formation of CoO at the Co/MgO interface. Meanwhile, the films show in-plane magnetic anisotropy (IMA). After annealing, most of the oxygen atoms in CoO migrate back to the MgO layer, resulting in obvious improvement of Co/MgO interface and the enhancement of effective Co-O orbital hybridization. These favor the evolution of magnetic anisotropy from IMA to perpendicular magnetic anisotropy (PMA). The oxygen migration effect ismore » achieved by the redox reaction at the Co/MgO interface. On the contrary, the transfer from IMA to PMA cannot be observed in Pt/Co/Pt films due to the lack of interfacial oxygen migration.« less

Thermal evolution of defects in undoped zinc oxide grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Wang, Zilan; Su, Shichen; Ling, Francis Chi-Chung; Anwand, W.; Wagner, A.

2014-07-01

Undoped ZnO films are grown by pulsed laser deposition on c-plane sapphire with different oxygen pressures. Thermal evolutions of defects in the ZnO films are studied by secondary ion mass spectroscopy (SIMS), Raman spectroscopy, and positron annihilation spectroscopy (PAS), and with the electrical properties characterized by the room temperature Hall measurement. Oxygen deficient defect related Raman lines 560 cm-1 and 584 cm-1 are identified and their origins are discussed. Thermal annealing induces extensive Zn out-diffusion at the ZnO/sapphire interface and leaves out Zn-vacancy in the ZnO film. Two types of Zn-vacancy related defects with different microstructures are identified in the films. One of them dominates in the samples grown without oxygen. Annealing the sample grown without oxygen or growing the samples in oxygen would favor the Zn-vacancy with another microstructure, and this Zn-vacancy defect persists after 1100 °C annealing.

Structural evolution across the insulator-metal transition in oxygen-deficient BaTiO 3-δ studied using neutron total scattering and Rietveld analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jeong, I.-K.; Lee, Seunghun; Jeong, Se-Young

2011-08-29

Oxygen-deficient BaTiO 3-δ exhibits an insulator-metal transition with increasing δ. We performed neutron total scattering measurements to study structural evolution across an insulator-metal transition in BaTiO 3-δ. Despite its significant impact on resistivity, slight oxygen reduction (δ=0.09) caused only a small disturbance on the local doublet splitting of Ti-O bond. This finding implies that local polarization is well preserved under marginal electric conduction. In the highly oxygen-deficient metallic state (δ=0.25), however, doublet splitting of the Ti-O bond became smeared. The smearing of the local Ti-O doublet is complemented with long-range structural analysis and demonstrates that the metallic conduction in themore » highly oxygen-reduced BaTiO 3-δ is due to the appearance of nonferroelectric cubic lattice.« less

From the Cover: Environmental and biotic controls on the evolutionary history of insect body size

NASA Astrophysics Data System (ADS)

Clapham, Matthew E.; Karr, Jered A.

2012-07-01

Giant insects, with wingspans as large as 70 cm, ruled the Carboniferous and Permian skies. Gigantism has been linked to hyperoxic conditions because oxygen concentration is a key physiological control on body size, particularly in groups like flying insects that have high metabolic oxygen demands. Here we show, using a dataset of more than 10,500 fossil insect wing lengths, that size tracked atmospheric oxygen concentrations only for the first 150 Myr of insect evolution. The data are best explained by a model relating maximum size to atmospheric environmental oxygen concentration (pO2) until the end of the Jurassic, and then at constant sizes, independent of oxygen fluctuations, during the Cretaceous and, at a smaller size, the Cenozoic. Maximum insect size decreased even as atmospheric pO2 rose in the Early Cretaceous following the evolution and radiation of early birds, particularly as birds acquired adaptations that allowed more agile flight. A further decrease in maximum size during the Cenozoic may relate to the evolution of bats, the Cretaceous mass extinction, or further specialization of flying birds. The decoupling of insect size and atmospheric pO2 coincident with the radiation of birds suggests that biotic interactions, such as predation and competition, superseded oxygen as the most important constraint on maximum body size of the largest insects.

Oxygen and life on earth: an anesthesiologist's views on oxygen evolution, discovery, sensing, and utilization.

PubMed

Lindahl, Sten G E

2008-07-01

The advent of oxygenic photosynthesis and the accumulation of oxygen in our atmosphere opened up new possibilities for the development of life on Earth. The availability of oxygen, the most capable electron acceptor on our planet, allowed the development of highly efficient energy production from oxidative phosphorylation, which shaped the evolutionary development of aerobic life forms from the first multicellular organisms to the vertebrates.

Correcting speleothem oxygen isotopic variations for growth-rate controlled kinetic fractionation effects

NASA Astrophysics Data System (ADS)

Stoll, Heather; Moreno, Ana; Cacho, Isabel; Mendez Vicence, Ana; Gonzalez Lemos, Saul; Pirla Casasayas, Gemma; Cheng, Hai; Wang, Xianfeng; Edwards, R. Lawrence

2015-04-01

The oxygen isotopic signature may be the most widely used climate indicator in stalagmites, but recent experimental and theoretical studies indicate the potential for kinetic fractionation effects which may be significant, especially in situations where the primary signal from rainfall isotopic composition and cave temperature is limited to a few permil. Here we use a natural set of stalagmites to illustrate the magnitude of such effects and the potential for deconvolving kinetic signals from the primary temperature and rainfall signals. We compare isotopic records from 6 coeval stalagmites covering the interval 140 to 70 ka, from two proximal caves in NW Spain which experienced the same primary variations in temperature and rainfall d18O, but exhibit a large range in growth rates and temporal trends in growth rate. Stalagmites growing at faster rates near 50 microns/year have oxygen isotopic ratios more than 1 permil more negative than coeval stalagmites with very slow (5 micron/year) growth rates. Because growth rate variations also occur over time within any given stalagmite, the measured oxygen isotopic time series for a given stalagmite includes both climatic and kinetic components. Removal of the kinetic component of variation in each stalagmite, based on the dependence of the kinetic component on growth rate, is effective at distilling a common temporal evolution among the oxygen isotopic records of the multiple stalagmites. However, this approach is limited by the quality of the age model. For time periods characterized by very slow growth and long durations between dates, the presence of crypto-hiatus may result in average growth rates which underestimate the instantaneous speleothem deposition rates and which therefore underestimate the magnitude of kinetic effects. We compare the composite corrected oxygen isotopic record with other records of the timing of glacial inception in the North Atlantic realm.

Calcium-manganese oxides as structural and functional models for active site in oxygen evolving complex in photosystem II: lessons from simple models.

PubMed

Najafpour, Mohammad Mahdi

2011-01-01

The oxygen evolving complex in photosystem II which induces the oxidation of water to dioxygen in plants, algae and certain bacteria contains a cluster of one calcium and four manganese ions. It serves as a model to split water by sunlight. Reports on the mechanism and structure of photosystem II provide a more detailed architecture of the oxygen evolving complex and the surrounding amino acids. One challenge in this field is the development of artificial model compounds to study oxygen evolution reaction outside the complicated environment of the enzyme. Calcium-manganese oxides as structural and functional models for the active site of photosystem II are explained and reviewed in this paper. Because of related structures of these calcium-manganese oxides and the catalytic centers of active site of the oxygen evolving complex of photosystem II, the study may help to understand more about mechanism of oxygen evolution by the oxygen evolving complex of photosystem II. Copyright © 2010 Elsevier B.V. All rights reserved.

Nostoc sphaeroides Kützing, an excellent candidate producer for CELSS

NASA Astrophysics Data System (ADS)

Hao, Zongjie; Li, Dunhai; Li, Yanhui; Wang, Zhicong; Xiao, Yuan; Wang, Gaohong; Liu, Yongding; Hu, Chunxiang; Liu, Qifang

2011-11-01

Some phytoplankton can be regarded as possible candidates in the establishment of Controlled Ecological Life Support System (CELSS) for some intrinsic characteristics, the first characteristic is that they should grow rapidly, secondly, they should be able to endure some stress factors and develop some corresponding adaptive strategies; also it is very important that they could provide food rich in nutritious protein and vitamins for the crew; the last but not the least is they can also fulfill the other main functions of CELSS, including supplying oxygen, removing carbon dioxide and recycling the metabolic waste. According to these characteristics, Nostoc sphaeroides, a potential healthy food in China, was selected as the potential producer in CELSS. It was found that the oxygen average evolution rate of this algae is about 150 μmol O 2 mg -1 h -1, and the size of them are ranged from 2 to 20 mm. Also it can be cultured with high population density, which indicated that the potential productivity of Nostoc sphaeroides is higher than other algae in limited volume. We measured the nutrient contents of the cyanobacterium and concluded it was a good food for the crew. Based on above advantages, Nostoc sphaeroides was assumed to a suitable phytoplankton for the establishment of Controlled Ecological Life Support System. We plan to develop suitable bioreactor with the cyanobacterium for supplying oxygen and food in future space missions.

Development of Inorganic Nanomaterials as Photocatalysts for the Water Splitting Reaction

NASA Astrophysics Data System (ADS)

Frame, Fredrick Andrew

The photochemical water splitting reaction is of great interest for converting solar energy into usable fuels. This dissertation focuses on the development of inorganic nanoparticle catalysts for solar energy driven conversion of water into hydrogen and oxygen. The results from these selected studies have allowed greater insight into nanoparticle chemistry and the role of nanoparticles in photochemical conversion of water in to hydrogen and oxygen. Chapter 2 shows that CdSe nanoribbons have photocatalytic activity for hydrogen production from water in the presence of Na2S/Na2SO 3 as sacrificial electron donors in both UV and visible light. Quantum confinement of this material leads to an extended bandgap of 2.7 eV and enables the photocatalytic activity of this material. We report on the photocatalytic H2 evolution, and its dependence on platinum co-catalysts, the concentration of the electron donor, and the wavelength of incident radiation. Transient absorption measurements reveal decay of the excited state on multiple timescales, and an increase of lifetimes of trapped electrons due to the sacrificial electron donors. In chapter 3, we explore the catalytic activity of citrate-capped CdSe quantum dots. We show that the process is indeed catalytic for these dots in aqueous 0.1 M Na2S:Na2SO3, but not in pure water. Furthermore, optical spectroscopy was used to report electronic transitions in the dots and electron microscopy was used to obtain morphology of the catalyst. Interestingly, an increasing catalytic rate is noted for undialyzed catalyst. Dynamic light scattering experiments show an increased hydrodynamic radius in the case of undialyzed CdSe dots in donor solution. In chapter 4 we show that CdSe:MoS2 nanoparticle composites with improved catalytic activity can be assembled from CdSe and MoS2 nanoparticle building units. We report on the photocatalytic H 2 evolution, quantum efficiency using LED irriadiation, and its dependence on the co-catalyst loading. Furthermore, optical spectroscopy, cyclic voltammetry, and electron microscopy were used to obtain morphology, optical properties, and electronic structure of the catalysts. In chapter 5, illumination with visible light (lambda > 400 nm) photoconverts a red V2O5 gel in aqueous methanol solution into a green VO2 gel. The presence of V(4+) in the green VO2 gel is supported by Electron Energy Loss Spectra. High-resolution electron micrographs, powder X-ray diffraction, and selective area electron diffraction (SAED) data show that the crystalline structure of the V2O5 gel is retained upon reduction. After attachment of colloidal Pt nanoparticles, H2 evolution proceeds catalytically on the VO2 gel. The Pt nanoparticles reduce the H2 evolution overpotential. However, the activity of the new photocatalyst remains limited by the VO2 conduction band edge just below the proton reduction potential. Chapter 6 studies the ability of IrO2 to evolve oxygen from aqueous solutions under UV irradiation. We show that visible illumination (lambda > 400 nm) of iridium dioxide (IrO2) nanocrystals capped in succinic acid in aqueous sodium persulfate solution leads to catalytic oxygen evolution. While the majority of catalytic hydrogen evolution comes from UV light, the process can still be driven with visible light. Morphology, optical properties, surface photovoltage measurements, and oxygen evolution rates are discussed.

Use of Molecular Fossils for the Interpretation of Paleoenvironments on Early Earth: The Synthesis of Lipid Biomarkers by Methane-Oxidizing Bacteria

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Summons, Roger E.; Chang, Sherwood (Technical Monitor)

1994-01-01

Over the course of Earth's history, the most important biological influence has come from the evolution of oxygenic photosynthesis and the development of an oxygen-rich biosphere. Although the availability of free oxygen had profound effects on subsequent biological and planetary evolution, clear paleobiological evidence of the timing of this transition is lacking. Recent technical advances in the microanalysis of organic matter has made it possible to detect residual molecules (biomarkers) in proterozoic (2.5 to 0.6 billion years) sedimentary rock characteristic of specific groups of microorganisms. When coupled with the carbon isotopic fractionations characteristic of biological systems and the new field of compound specific isotope analysis, biomarkers could prove to be a powerful tool for decoding ancient biochemistry from the geological record. We have been studying the carbon isotope fractionations associated with the synthesis of organic biomarker molecules in several types of methane-oxidizing bacteria that should have been key to carbon cycling in paleoenvironments after the evolution of oxygenic photosynthesis.

The influence of coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti anodes for oxygen evolution

NASA Astrophysics Data System (ADS)

Kato, Zenta; Kashima, Ryo; Tatsumi, Kohei; Fukuyama, Shinnosuke; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2016-12-01

For oxygen formation without forming chlorine in seawater electrolysis for hydrogen production we have been using the anode consisting of three layers of MnO2-type multiple oxide catalyst, intermediate layer and titanium substrate. The intermediate layer was used for prevention of oxidation of the titanium substrate during anodic polarization for oxygen evolution and was prepared by calcination of butanol solutions of H2IrCl6 and SnCl4 coated on titanium. The protectiveness of Ir1-xSnxO2 layer formed was directly examined using Ir1-xSnxO2/Ti anodes in H2SO4 solution changing the preparation conditions of the layer. When the sum of Ir4+ and Sn4+ was 0.1 M, the highest protectiveness was observed at 0.06 M Sn4+. Although an increase in calcination temperature led to the formation of Ir1-x-ySnxTiyO2 triple oxide with a slightly lower catalytic activity for oxygen evolution, the anode calcined at 450 °C showed the highest protectiveness.

Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions.

PubMed

Gnanakumar, Edwin S; Ng, Wesley; Coşkuner Filiz, Bilge; Rothenberg, Gadi; Wang, Sheng; Xu, Hualong; Pastor-Pérez, Laura; Pastor-Blas, M Mercedes; Sepúlveda-Escribano, Antonio; Yan, Ning; Shiju, N Raveendran

2017-11-23

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO 2 supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

Reactive oxygen species may play an essential role in driving biological evolution: The Cambrian Explosion as an example.

PubMed

Yang, Dong; Guo, Xuejun; Xie, Tian; Luo, Xiaoyan

2018-01-01

The Cambrian Explosion is one of the most significant events in the history of life; essentially all easily fossilizable animal body plans first evolved during this event. Although many theories have been proposed to explain this event, its cause remains unresolved. Here, we propose that the elevated level of oxygen, in combination with the increased mobility and food intake of metazoans, led to increased cellular levels of reactive oxygen species (ROS), which drove evolution by enhancing mutation rates and providing new regulatory mechanisms. Our hypothesis may provide a unified explanation for the Cambrian Explosion as it incorporates both environmental and developmental factors and is also consistent with ecological explanations for animal radiation. Future studies should focus on testing this hypothesis, and may lead to important insights into evolution. Copyright © 2017. Published by Elsevier B.V.

Using surface segregation to design stable Ru-Ir oxides for the oxygen evolution reaction in acidic environments.

DOE PAGES

Danilovic, N.; Subbaraman, R.; Chang, K-C.; ...

2014-10-08

The methods used to improve catalytic activity are well-established, however elucidating the factors that simultaneously control activity and stability is still lacking, especially for oxygen evolution reaction (OER) catalysts. Here, by studying fundamental links between the activity and stability of well-characterized monometallic and bimetallic oxides, we found that there is generally an inverse relationship between activity and stability. To overcome this limitation, we developed a new synthesis strategy that is based on tuning the near-surface composition of Ru and Ir elements by surface segregation, thereby resulting in the formation of a nanosegregated domain that balances the stability and activity ofmore » surface atoms. We demonstrate that a Ru0.5Ir0.5 alloy synthesized by using this method exhibits four-times higher stability than the best Ru-Ir oxygen evolution reaction materials, while still preserving the same activity.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di, Jun; Chen, Chao; Yang, Shi -Ze

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

The Determination of Rate-Limiting Steps during Soot Formation

DTIC Science & Technology

1989-04-27

acceleration in chemistry due to the presence of oxygen . Quantitative prediction of soot production , should it become a reality, will require knowledge of...PAH ..... ... ..................... 7 Fig. 4 1.25% Benzene/1% Oxygen - Light Products ........ .................... 8 Fig. 5 1.25% Benzene/0.3% Oxygen ...Benzene/0.3% Oxygen - PAH Production ....... .................. 11 Fig. 8 Evolution of Closed Ring Aromatics (t(source) = oo) .................... .15 Fig

Multifunctional nanostructured electrocatalysts for energy conversion and storage: current status and perspectives.

PubMed

Ghosh, Srabanti; Basu, Rajendra N

2018-06-21

Electrocatalytic oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) have attracted widespread attention because of their important role in the application of various energy storage and conversion devices, such as fuel cells, metal-air batteries and water splitting devices. However, the sluggish kinetics of the HER/OER/ORR and their dependency on expensive noble metal catalysts (e.g., Pt) obstruct their large-scale application. Hence, the development of efficient and robust bifunctional or trifunctional electrocatalysts in nanodimension for both oxygen reduction/evolution and hydrogen evolution reactions is highly desired and challenging for their commercialization in renewable energy technologies. This review describes some recent developments in the discovery of bifunctional or trifunctional nanostructured catalysts with improved performances for application in rechargeable metal-air batteries and fuel cells. The role of the electronic structure and surface redox chemistry of nanocatalysts in the improvement of their performance for the ORR/OER/HER under an alkaline medium is highlighted and the associated reaction mechanisms developed in the recent literature are also summarized.

Toward a New Capability for Upper Atmospheric Research using Atomic Oxygen Lidar

NASA Astrophysics Data System (ADS)

Clemmons, J. H.; Steinvurzel, P.; Mu, X.; Beck, S. M.; Lotshaw, W. T.; Rose, T. S.; Hecht, J. H.; Westberg, K. R.; Larsen, M. F.; Chu, X.; Fritts, D. C.

2017-12-01

Progress on development of a lidar system for probing the upper atmosphere based on atomic oxygen resonance is presented and discussed. The promise of a fully-developed atomic oxygen lidar system, which must be based in space to measure the upper atmosphere, for yielding comprehensive new insights is discussed in terms of its potential to deliver global, height-resolved measurements of winds, temperature, and density at a high cadence. An overview of the system is given, and its measurement principles are described, including its use of 1) a two-photon transition to keep the optical depth low; 2) laser tuning to provide the Doppler information needed to measure winds; and 3) laser tuning to provide a Boltzmann temperature measurement. The current development status is presented with a focus on what has been done to demonstrate capability in the laboratory and its evolution to a funded sounding rocket investigation designed to make measurements of three-dimensional turbulence in the upper mesosphere and lower thermosphere.

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

PubMed Central

Zhao, Yunlong; Xu, Lin; Mai, Liqiang; Han, Chunhua; An, Qinyou; Xu, Xu; Liu, Xue; Zhang, Qingjie

2012-01-01

Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire. PMID:23150570

Supply and demand: How does variation in atmospheric oxygen during development affect insect tracheal and mitochondrial networks?

PubMed

VandenBrooks, John M; Gstrein, Gregory; Harmon, Jason; Friedman, Jessica; Olsen, Matthew; Ward, Anna; Parker, Gregory

2018-04-01

Atmospheric oxygen is one of the most important atmospheric component for all terrestrial organisms. Variation in atmospheric oxygen has wide ranging effects on animal physiology, development, and evolution. This variation in oxygen has the potential to affect both respiratory systems (the supply side) and mitochondrial networks (the demand side) in animals. Insect respiratory systems supplying oxygen to tissues in the gas phase through blind ended tracheal systems are particularly susceptible to this variation. While the large conducting tracheae have previously been shown to respond developmentally to changes in rearing oxygen, the effect of oxygen on the tracheolar network has been relatively unexplored, especially in adult insects. Similarly, mitochondrial networks that meet energy demand in insects and other animals are dynamic and their enzyme activities have been shown to vary in the presence of oxygen. These two systems together should be under selective pressure to meet the aerobic metabolic requirements of insects. To test this hypothesis, we reared Mito-YFP Drosophila under three different oxygen concentrations hypoxia (12%), normoxia (21%), and hyperoxia (31%) and imaged their tracheolar and mitochondrial networks within their flight muscle using confocal microscopy. In terms of oxygen supply, hypoxia increased mean (mid-length) tracheolar diameters, tracheolar tip diameters, the number of tracheoles per main branch and affected tracheal branching patterns, while the opposite was observed in hyperoxia. In terms of oxygen demand, hypoxia increased mitochondrial investment and mitochondrial to tracheolar volume ratios; while the opposite was observed in hyperoxia. Generally, hypoxia had a stronger effect on both systems than hyperoxia. These results show that insects are capable of developmentally changing investment in both their supply and demand networks to increase overall fitness. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous quantum yield measurements of carbon uptake and oxygen evolution in microalgal cultures

PubMed Central

Gholami, Pardis; Kline, David I.; DuPont, Christopher L.; Dickson, Andrew G.; Mendola, Dominick; Martz, Todd; Allen, Andrew E.; Mitchell, B. Greg

2018-01-01

The photosynthetic quantum yield (Φ), defined as carbon fixed or oxygen evolved per unit of light absorbed, is a fundamental but rarely determined biophysical parameter. A method to estimate Φ for both net carbon uptake and net oxygen evolution simultaneously can provide important insights into energy and mass fluxes. Here we present details for a novel system that allows quantification of carbon fluxes using pH oscillation and simultaneous oxygen fluxes by integration with a membrane inlet mass spectrometer. The pHOS system was validated using Phaeodactylum tricornutum cultured with continuous illumination of 110 μmole quanta m-2 s-1 at 25°C. Furthermore, simultaneous measurements of carbon and oxygen flux using the pHOS-MIMS and photon flux based on spectral absorption were carried out to explore the kinetics of Φ in P. tricornutum during its acclimation from low to high light (110 to 750 μmole quanta m-2 s-1). Comparing results at 0 and 24 hours, we observed strong decreases in cellular chlorophyll a (0.58 to 0.21 pg cell-1), Fv/Fm (0.71 to 0.59) and maximum ΦCO2 (0.019 to 0.004) and ΦO2 (0.028 to 0.007), confirming the transition toward high light acclimation. The Φ time-series indicated a non-synchronized acclimation response between carbon uptake and oxygen evolution, which has been previously inferred based on transcriptomic changes for a similar experimental design with the same diatom that lacked physiological data. The integrated pHOS-MIMS system can provide simultaneous carbon and oxygen measurements accurately, and at the time-resolution required to resolve high-resolution carbon and oxygen physiological dynamics. PMID:29920568

Observing the Electrochemical Oxidation of Co Metal at the Solid/Liquid Interface Using Ambient Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.; ...

2017-08-28

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

Photochemical escape of oxygen from Mars: First results from MAVEN in situ data

NASA Astrophysics Data System (ADS)

Lillis, Robert J.; Deighan, Justin; Fox, Jane L.; Bougher, Stephen W.; Lee, Yuni; Combi, Michael R.; Cravens, Thomas E.; Rahmati, Ali; Mahaffy, Paul R.; Benna, Mehdi; Elrod, Meredith K.; McFadden, James P.; Ergun, Robert. E.; Andersson, Laila; Fowler, Christopher M.; Jakosky, Bruce M.; Thiemann, Ed; Eparvier, Frank; Halekas, Jasper S.; Leblanc, François; Chaufray, Jean-Yves

2017-03-01

Photochemical escape of atomic oxygen is thought to be one of the dominant channels for Martian atmospheric loss today and played a potentially major role in climate evolution. Mars Atmosphere and Volatile Evolution Mission (MAVEN) is the first mission capable of measuring, in situ, the relevant quantities necessary to calculate photochemical escape fluxes. We utilize 18 months of data from three MAVEN instruments: Langmuir Probe and Waves, Neutral Gas and Ion Mass Spectrometer, and SupraThermal And Thermal Ion Composition. From these data, we calculate altitude profiles of the production rate of hot oxygen atoms from the dissociative recombination of O2+ and the probability that such atoms will escape the Mars atmosphere. From this, we determine escape fluxes for 815 periapsis passes. Derived average dayside hot O escape rates range from 1.2 to 5.5 × 1025 s-1, depending on season and EUV flux, consistent with several pre-MAVEN predictions and in broad agreement with estimates made with other MAVEN measurements. Hot O escape fluxes do not vary significantly with dayside solar zenith angle or crustal magnetic field strength but depend on CO2 photoionization frequency with a power law whose exponent is 2.6 ± 0.6, an unexpectedly high value which may be partially due to seasonal and geographic sampling. From this dependence and historical EUV measurements over 70 years, we estimate a modern-era average escape rate of 4.3 × 1025 s-1. Extrapolating this dependence to early solar system, EUV conditions gives total losses of 13, 49, 189, and 483 mbar of oxygen over 1-3 and 3.5 Gyr, respectively, with uncertainties significantly increasing with time in the past.

Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam

2012-01-01

Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

DOE PAGES

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.; ...

2015-12-07

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

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

NASA Astrophysics Data System (ADS)

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.

Effects of overexpressing photosynthetic carbon flux control enzymes in the cyanobacterium Synechocystis PCC 6803.

PubMed

Liang, Feiyan; Lindblad, Peter

2016-11-01

Synechocystis PCC 6803 is a model unicellular cyanobacterium used in e.g. photosynthesis and CO 2 assimilation research. In the present study we examined the effects of overexpressing Ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), sedoheptulose 1,7-biphosphatase (SBPase), fructose-bisphosphate aldolase (FBA) and transketolase (TK), confirmed carbon flux control enzymes of the Calvin-Bassham-Benson (CBB) cycle in higher plants, in Synechocystis PCC 6803. Overexpressing RuBisCO, SBPase and FBA resulted in increased in vivo oxygen evolution (maximal 115%), growth rate and biomass accumulation (maximal 52%) under 100μmolphotonsm -2 s -1 light condition. Cells overexpressing TK showed a chlorotic phenotype but increased biomass by approximately 42% under 100μmolphotonsm -2 s -1 light condition. Under 15μmolphotonsm -2 s -1 light condition, cells overexpressing TK showed enhanced in vivo oxygen evolution. This study demonstrates increased growth and biomass accumulation when overexpressing selected enzymes of the CBB cycle. RuBisCO, SBPase, FBA and TK are identified as four potential targets to improve growth and subsequently also yield of valuable products from Synechocystis PCC 6803. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage

PubMed Central

Shan, Xiaoqiang; Charles, Daniel S.; Lei, Yinkai; Qiao, Ruimin; Wang, Guofeng; Yang, Wanli; Feygenson, Mikhail; Su, Dong; Teng, Xiaowei

2016-01-01

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost and environmental friendliness. However, their applications have been limited by a narrow potential window (∼1.23 V), beyond which the hydrogen and oxygen evolution reactions occur. Here we report the formation of layered Mn5O8 pseudocapacitor electrode material with a well-ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0 V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge–discharge cycles. The interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn5O8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn2+/Mn4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn5O8. PMID:27845345

Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shan, Xiaoqiang; Charles, Daniel S.; Lei, Yinkai

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost, and environmental friendliness. However, their applications have been limited by a narrow potential window (~1.23 V), beyond which the hydrogen and oxygen evolution reactions occur. Here, we report the formation of layered Mn 5O 8 pseudocapacitor electrode material with a well ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0 V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge-discharge cycles. Furthermore,more » the interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn 5O 8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn 2+/Mn 4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn 5O 8.« less

Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage

DOE PAGES

Shan, Xiaoqiang; Charles, Daniel S.; Lei, Yinkai; ...

2016-11-15

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost, and environmental friendliness. However, their applications have been limited by a narrow potential window (~1.23 V), beyond which the hydrogen and oxygen evolution reactions occur. Here, we report the formation of layered Mn 5O 8 pseudocapacitor electrode material with a well ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0 V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge-discharge cycles. Furthermore,more » the interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn 5O 8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn 2+/Mn 4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn 5O 8.« less

IR-doped ruthenium oxide catalyst for oxygen evolution

NASA Technical Reports Server (NTRS)

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.

Molecular identification of an ABC transporter complex for manganese: analysis of a cyanobacterial mutant strain impaired in the photosynthetic oxygen evolution process.

PubMed Central

Bartsevich, V V; Pakrasi, H B

1995-01-01

During photosynthesis, the photosystem II (PSII) pigment-protein complex catalyzes oxygen evolution, a reaction in which a four-manganese ensemble plays a crucial role. Using a newly developed selection scheme, we have isolated BP13, a random photosynthesis-deficient mutant strain of the cyanobacterium, Synechocystis 6803. This mutant grew slowly under photoautotrophic conditions, and had a low oxygen evolution activity. Biochemical analysis revealed that the lesion in this mutant strain had specifically affected the Mn ensemble in PSII. Interestingly, incubation of BP13 cells with micromolar levels of added Mn induced rapid recovery of oxygen evolution activity. The mutant could be complemented with a fragment of wild-type chromosomal DNA containing three closely linked genes, mntA, mntB and mntC. These gene products showed significant sequence similarities with polypeptide components of bacterial permeases that are members of the 'ABC (ATP binding cassette) superfamily' of transporter proteins. We determined that in the BP13 strain, a single nucleotide change had resulted in the replacement of an alanine by an aspartic acid residue in MntA, a soluble protein containing ATP binding motifs. These results suggest that the mntCAB gene cluster encodes polypeptide components of a Mn transporter, the first such protein complex identified in any organism. PMID:7743991

The timetable of evolution

PubMed Central

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

The Evolution of Deepwater Dissolved Oxygen in the Northern South China Sea During the Past 400 ka

NASA Astrophysics Data System (ADS)

Wang, N.; Huang, B.; Dong, Y.

2016-12-01

Reconstruction of dissolved oxygen in paleo-ocean contributes toward understanding the history of ocean circulation, climate, causes of extinctions, and the evolution of marine organisms. Based on analysis of benthic foraminifera oxygen index (BFOI), the redox-sensitive trace elements (Mo/Al), the percentage of epifaunal benthic foraminifera and infaunal/epifaunal ratio at core MD12-3432, we reconstruct the evolution of deep water dissolved oxygen in northern South China Sea (SCS) during the past 400 ka and discuss the mechanisms of variable dissolved oxygen. Both BFOI and Mo/Al are redox indicators. Similar trends confirm that they reflect the variation of dissolved oxygen in seawater since 400 ka accurately. BFOI and Mo/Al indicate that dissolved oxygen was high in MIS 11-MIS 7 and decreased gradually during MIS 6- MIS 2. The percentage of epifauna decreased and infaunal/epifaunal ratio increased with decreasing dissolved oxygen. By comparison of dissolved oxygen and productivity indexes such as phytoplankton total (PT) and species abundances, we found that when PT fluctuated in the average range of 1000-1500 ng/g, the abundances of Bulimina and Uvigerina which represent high productivity increased. However, when PT reached the range of 2500-3000 ng/g, the abundances of Bulimina and Uvigerina didn't increase, but the abundances of dysoxic species Chilostomella oolina and Globobulimina pacifica increased and the dissolved oxygen reached low value. The reasons may be that the decomposition of excessive organic matter consumed more dissolved oxygen. The low dissolved oxygen suppressed the growth of Bulimina and Uvigerina and accelerated the boom of C. oolina and G. oolina. The dissolved oxygen is not only associated with productivity, but also affected by the thermohaline circulation. Benthic foraminifera F. favus is the representative species in Pacific deep water. Its appearance at 194 ka, 205 ka, 325, the 328 ka in MD12-3432 indicate that the upper border of western Pacific deep water was beyond the sill of Bashi Strait and high dissolved oxygen deep water was brought into Northern SCS. The millennium-scale rapid variability and decline of dissolved oxygen in MIS 4, 3, 2 may be caused by fluctuations and slowdown of thermohaline circulation transported from the northern Atlantic to the northern SCS.

On the origins of oxygenic photosynthesis and aerobic respiration in Cyanobacteria.

PubMed

Soo, Rochelle M; Hemp, James; Parks, Donovan H; Fischer, Woodward W; Hugenholtz, Philip

2017-03-31

The origin of oxygenic photosynthesis in Cyanobacteria led to the rise of oxygen on Earth ~2.3 billion years ago, profoundly altering the course of evolution by facilitating the development of aerobic respiration and complex multicellular life. Here we report the genomes of 41 uncultured organisms related to the photosynthetic Cyanobacteria (class Oxyphotobacteria ), including members of the class Melainabacteria and a new class of Cyanobacteria (class Sericytochromatia ) that is basal to the Melainabacteria and Oxyphotobacteria All members of the Melainabacteria and Sericytochromatia lack photosynthetic machinery, indicating that phototrophy was not an ancestral feature of the Cyanobacteria and that Oxyphotobacteria acquired the genes for photosynthesis relatively late in cyanobacterial evolution. We show that all three classes independently acquired aerobic respiratory complexes, supporting the hypothesis that aerobic respiration evolved after oxygenic photosynthesis. Copyright © 2017, American Association for the Advancement of Science.

The effects of oxygen on the evolution of microbial membranes

NASA Technical Reports Server (NTRS)

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.

Evolution of Structural and Electrical Properties of Oxygen-Deficient VO2 under Low Temperature Heating Process.

PubMed

Zhang, Jiasong; Zhao, Zhengjing; Li, Jingbo; Jin, Haibo; Rehman, Fida; Chen, Pengwan; Jiang, Yijie; Chen, Chunxu; Cao, Maosheng; Zhao, Yongjie

2017-08-16

Structural stability and functional performances of vanadium dioxide (VO 2 ) are strongly influenced by oxygen vacancies. However, the mechanism of metal-insulator transition (MIT) influenced by defects is still under debate. Here, we study the evolution of structure and electrical property of oxygen-deficient VO 2 by a low temperature annealing process (LTP) based on a truss-structured VO 2 nanonet. The oxygenation process of the oxygen-deficient VO 2 is greatly prolonged, which enables us to probe the gradual change of properties of the oxygen-deficient VO 2 . A continuous lattice reduction is observed during LTP. No recrystallization and structural collapse of the VO 2 nanonet can be found after LTP. The valence-band X-ray photoelectron spectroscopy (XPS) measurements indicate that the oxygen deficiency strongly affects the energy level of the valence band edge. Correspondingly, the resistance changes of the VO 2 films from 1 to 4.5 orders of magnitude are achieved by LTP. The effect of oxygen vacancy on the electric field driven MIT is investigated. The threshold value of voltage triggering the MIT decreases with increasing the oxygen vacancy concentration. This work demonstrates a novel and effective way to control the content of oxygen vacancies in VO 2 and the obvious impact of oxygen vacancy on MIT, facilitating further research on the role of oxygen vacancy in structure and MIT of VO 2 , which is important for the deep understanding of MIT and exploiting innovative functional application of VO 2 .

Solving the Puzzle of Metastasis: The Evolution of Cell Migration in Neoplasms

PubMed Central

Chen, Jun; Sprouffske, Kathleen; Huang, Qihong; Maley, Carlo C.

2011-01-01

Background Metastasis represents one of the most clinically important transitions in neoplastic progression. The evolution of metastasis is a puzzle because a metastatic clone is at a disadvantage in competition for space and resources with non-metastatic clones in the primary tumor. Metastatic clones waste some of their reproductive potential on emigrating cells with little chance of establishing metastases. We suggest that resource heterogeneity within primary tumors selects for cell migration, and that cell emigration is a by-product of that selection. Methods and Findings We developed an agent-based model to simulate the evolution of neoplastic cell migration. We simulated the essential dynamics of neoangiogenesis and blood vessel occlusion that lead to resource heterogeneity in neoplasms. We observed the probability and speed of cell migration that evolves with changes in parameters that control the degree of spatial and temporal resource heterogeneity. Across a broad range of realistic parameter values, increasing degrees of spatial and temporal heterogeneity select for the evolution of increased cell migration and emigration. Conclusions We showed that variability in resources within a neoplasm (e.g. oxygen and nutrients provided by angiogenesis) is sufficient to select for cells with high motility. These cells are also more likely to emigrate from the tumor, which is the first step in metastasis and the key to the puzzle of metastasis. Thus, we have identified a novel potential solution to the puzzle of metastasis. PMID:21556134

Assessment of electrochemical properties of a biogalvanic system for tissue characterisation

PubMed Central

Chandler, J.H.; Culmer, P.R.; Jayne, D.G.; Neville, A.

2015-01-01

Biogalvanic characterisation is a promising method for obtaining health-specific tissue information. However, there is a dearth of understanding in the literature regarding the underlying galvanic cell, electrode reactions and their controlling factors which limits the application of the technique. This work presents a parametric electrochemical investigation into a zinc–copper galvanic system using salt (NaCl) solution analogues at physiologically-relevant concentrations (1.71, 17.1 & 154 mM). The potential difference at open cell, closed cell maximum current and the internal resistance (based on published characterisation methods) were measured. Additionally, independent and relative polarisation scans of the electrodes were performed to improve understanding of the system. Our findings suggest that the prominent reaction at the cathode is that of oxygen-reduction, not hydrogen-evolution. Results indicate that cell potentials are influenced by the concentration of dissolved oxygen at low currents and maximum closed cell currents are limited by the rate of oxygen diffusion to the cathode. Characterised internal resistance values for the salt solutions did not correspond to theoretical values at the extremes of concentration (1.71 and 154 mM) due to electrode resistance and current limitation. Existing biogalvanic models do not consider these phenomena and should be improved to advance the technique and its practical application. PMID:25460609

Research on rechargeable oxygen electrodes.

NASA Technical Reports Server (NTRS)

Giner, J.; Holleck, G.; Malachesky, P. A.

1970-01-01

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Time-resolved spectral analysis of Radachlorin luminescence in water

NASA Astrophysics Data System (ADS)

Belik, V. P.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

2017-05-01

We report results of spectral- and time-resolved study of Radachlorin photosensitizer luminescence in water in the spectral range of 950-1350nm and for determination of the photosensitizer triplet state and the singlet oxygen lifetimes responsible for singlet oxygen generation and degradation. At any wavelength within the explored spectral range the luminescence decay contained two major contributions: a fast decay at the ns time scale and a slow evolution at the μs time scale. The fast decay was attributed to electric dipole fluorescence transitions in photosensitizer molecules and the slow evolution to intercombination phosphorescence transitions in singlet oxygen and photosensitizer molecules. Relatively high-amplitude ns peak observed at all wavelengths suggests that singlet oxygen monitoring with spectral isolation methods alone, without additional temporal resolution can be controversial. In the applied experimental conditions the total phosphorescence signal at any wavelength contained a contribution from the photosensitizer triplet state decay, while at 1274nm the singlet oxygen phosphorescence dominated. The results obtained can be used for optimization of the methods of singlet oxygen monitoring and imaging.

BLOOD SUBSTITUTES: EVOLUTION FROM NON-CARRYING TO OXYGEN AND GAS CARRYING FLUIDS

PubMed Central

Cabrales, Pedro; Intaglietta, Marcos

2013-01-01

The development of oxygen (O2) carrying blood substitutes has evolved from the goal of replicating blood O2 transports properties to that of preserving microvascular and organ function, reducing the inherent or potential toxicity of the material used to carry O2, and treating pathologies initiated by anemia and hypoxia. Furthermore, the emphasis has shifted from blood replacement fluid to “O2 therapeutics” that restore tissue oxygenation to specific tissues regions. This review covers the different alternatives, potential and limitations of hemoglobin based O2 carriers (HBOCs) and perfluorocarbon based O2 carriers (PFCOCs), with emphasis on the physiological conditions disturbed in the situation that they will be used. It describes how concepts learned from plasma expanders without O2 carrying capacity can be applied to maintain O2 delivery and summarizes the microvascular responses due to HBOCs and PFCOCs. This review also presents alternative applications of HBOCs and PFCOCs namely: 1) How HBOC O2 affinity can be engineered to target O2 delivery to hypoxic tissues; and 2) How the high gas solubility of PFCOCs provides new opportunities for carrying, dissolving and delivering gases with biological activity. It is concluded that current blood substitutes development has amplified their applications horizon by devising therapeutic functions for oxygen carriers requiring limited O2 delivery capacity restoration. Conversely, full, blood-like O2 carrying capacity re-establishment awaits control of O2 carrier toxicity. PMID:23820271

Electrolysis-driven bioremediation of crude oil-contaminated marine sediments.

PubMed

Bellagamba, Marco; Cruz Viggi, Carolina; Ademollo, Nicoletta; Rossetti, Simona; Aulenta, Federico

2017-09-25

Bioremediation is an effective technology to tackle crude oil spill disasters, which takes advantage of the capacity of naturally occurring microorganisms to degrade petroleum hydrocarbons under a range of environmental conditions. The enzymatic process of breaking down oil is usually more rapid in the presence of oxygen. However, in contaminated sediments, oxygen levels are typically too low to sustain the rapid and complete biodegradation of buried hydrocarbons. Here, we explored the possibility to electrochemically manipulate the redox potential of a crude oil-contaminated marine sediment in order to establish, in situ, conditions that are conducive to contaminants biodegradation by autochthonous microbial communities. The proposed approach is based on the exploitation of low-voltage (2V) seawater electrolysis to drive oxygen generation (while minimizing chlorine evolution) on Dimensionally Stable Anodes (DSA) placed within the contaminated sediment. Results, based on a laboratory scale setup with chronically polluted sediments spiked with crude oil, showed an increased redox potential and a decreased pH in the vicinity of the anode of 'electrified' treatments, consistent with the occurrence of oxygen generation. Accordingly, hydrocarbons biodegradation was substantially accelerated (up to 3-times) compared to 'non-electrified' controls, while sulfate reduction was severely inhibited. Intermittent application of electrolysis proved to be an effective strategy to minimize the energy requirements of the process, without adversely affecting degradation performance. Taken as a whole, this study suggests that electrolysis-driven bioremediation could be a sustainable technology for the management of contaminated sediments. Copyright © 2016 Elsevier B.V. All rights reserved.

Global modeling of wall material migration following boronization in NSTX-U

NASA Astrophysics Data System (ADS)

Nichols, J. H.; Jaworski, M. A.; Skinner, C. H.; Bedoya, F.; Scotti, F.; Soukhanovskii, V. A.; Schmid, K.

2017-10-01

NSTX-U operated in 2016 with graphite plasma facing components, periodically conditioned with boron to improve plasma performance. Following each boronization, spectroscopic diagnostics generally observed a decrease in oxygen influx from the walls, and an in-vacuo material probe (MAPP) observed a corresponding decrease in surface oxygen concentration at the lower divertor. However, oxygen levels tended to return to a pre-boronization state following repeated plasma exposure. This behavior is interpretively modeled using the WallDYN mixed-material migration code, which couples local erosion and deposition processes with plasma impurity transport in a non-iterative, self-consistent manner that maintains overall material balance. A spatially inhomogenous model of the thin films produced by the boronization process is presented. Plasma backgrounds representative of NSTX-U conditions are reconstructed from a combination of NSTX-U and NSTX datasets. Low-power NSTX-U fiducial discharges, which led to less apparent surface degradation than normal operations, are also modeled with WallDYN. Likely mechanisms driving the observed evolution of surface oxygen are examined, as well as remaining discrepancies between model and experiment and potential improvements to the model. Work supported by US DOE contract DE-AC02-09CH11466.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction

DOE PAGES

Favaro, Marco; Drisdell, Walter S.; Marcus, Matthew A.; ...

2016-12-27

The oxygen evolution reaction (OER) is a critical component of industrial processes such as electrowinning of metals and the chlor-alkali process. It also plays a central role in the development of a renewable energy field for generation a solar fuels by providing both the protons and electrons needed to generate fuels such as H 2 or reduced hydrocarbons from CO 2. To improve these processes, it is necessary to expand the fundamental understanding of catalytically active species at low overpotential, which will further the development of electrocatalysts with high activity and durability. In this context, performing experimental investigations of themore » electrocatalysts under realistic working regimes (i.e., under operando conditions) is of crucial importance. In this paper, we study a highly active quinary transition-metal-oxide-based OER electrocatalyst by means of operando ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy performed at the solid/liquid interface. We observe that the catalyst undergoes a clear chemical-structural evolution as a function of the applied potential with Ni, Fe, and Co oxyhydroxides comprising the active catalytic species. Finally, while CeO 2 is redox inactive under catalytic conditions, its influence on the redox processes of the transition metals boosts the catalytic activity at low overpotentials, introducing an important design principle for the optimization of electrocatalysts and tailoring of high-performance materials.« less

HELIUM ATMOSPHERES ON WARM NEPTUNE- AND SUB-NEPTUNE-SIZED EXOPLANETS AND APPLICATIONS TO GJ 436b

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Renyu; Yung, Yuk L.; Seager, Sara, E-mail: renyu.hu@jpl.nasa.gov

2015-07-01

Warm Neptune- and sub-Neptune-sized exoplanets in orbits smaller than Mercury’s are thought to have experienced extensive atmospheric evolution. Here we propose that a potential outcome of this atmospheric evolution is the formation of helium-dominated atmospheres. The hydrodynamic escape rates of Neptune- and sub-Neptune-sized exoplanets are comparable to the diffusion-limited escape rate of hydrogen, and therefore the escape is heavily affected by diffusive separation between hydrogen and helium. A helium atmosphere can thus be formed—from a primordial hydrogen–helium atmosphere—via atmospheric hydrodynamic escape from the planet. The helium atmosphere has very different abundances of major carbon and oxygen species from those ofmore » a hydrogen atmosphere, leading to distinctive transmission and thermal emission spectral features. In particular, the hypothesis of a helium-dominated atmosphere can explain the thermal emission spectrum of GJ 436b, a warm Neptune-sized exoplanet, while also being consistent with the transmission spectrum. This model atmosphere contains trace amounts of hydrogen, carbon, and oxygen, with the predominance of CO over CH{sub 4} as the main form of carbon. With our atmospheric evolution model, we find that if the mass of the initial atmosphere envelope is 10{sup −3} planetary mass, hydrodynamic escape can reduce the hydrogen abundance in the atmosphere by several orders of magnitude in ∼10 billion years. Observations of exoplanet transits may thus detect signatures of helium atmospheres and probe the evolutionary history of small exoplanets.« less

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

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kane, Joshua J.; Contescu, Cristian I.; Smith, Rebecca E.

A thorough understanding of oxidation is important when considering the health and integrity of graphite components in graphite reactors. For the next generation of graphite reactors, HTGRs specifically, an unlikely air ingress has been deemed significant enough to have made its way into the licensing applications of many international licensing bodies. While a substantial body of literature exists on nuclear graphite oxidation in the presence of molecular oxygen and significant efforts have been made to characterize oxidation kinetics of various grades, the value of existing information is somewhat limited. Often, multiple competing processes, including reaction kinetics, mass transfer, and microstructuralmore » evolution, are lumped together into a single rate expression that limits the ability to translate this information to different conditions. This article reviews the reaction of graphite with molecular oxygen in terms of the reaction kinetics, gas transport, and microstructural evolution of graphite. It also presents the foundations of a model for the graphite-molecular oxygen reaction system that is kinetically independent of graphite grade, and is capable of describing both the bulk and local oxidation rates under a wide range of conditions applicable to air-ingress.« less

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

DOE PAGES

Kane, Joshua J.; Contescu, Cristian I.; Smith, Rebecca E.; ...

2017-06-08

A thorough understanding of oxidation is important when considering the health and integrity of graphite components in graphite reactors. For the next generation of graphite reactors, HTGRs specifically, an unlikely air ingress has been deemed significant enough to have made its way into the licensing applications of many international licensing bodies. While a substantial body of literature exists on nuclear graphite oxidation in the presence of molecular oxygen and significant efforts have been made to characterize oxidation kinetics of various grades, the value of existing information is somewhat limited. Often, multiple competing processes, including reaction kinetics, mass transfer, and microstructuralmore » evolution, are lumped together into a single rate expression that limits the ability to translate this information to different conditions. This article reviews the reaction of graphite with molecular oxygen in terms of the reaction kinetics, gas transport, and microstructural evolution of graphite. It also presents the foundations of a model for the graphite-molecular oxygen reaction system that is kinetically independent of graphite grade, and is capable of describing both the bulk and local oxidation rates under a wide range of conditions applicable to air-ingress.« less

Direct observation of localized radial oxygen migration in functioning tantalum oxide memristors

DOE PAGES

Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul; ...

2016-02-02

Oxygen migration in tantalum oxide, a promising next-generation storage material, is studied using in operando x-ray absorption spectromicroscopy and is used to microphysically describe accelerated evolution of conduction channel and device failure. Furthermore, the resulting ring-like patterns of oxygen concentration are modeled using thermophoretic forces and Fick diffusion, establishing the critical role of temperature-activated oxygen migration that has been under question lately.

Life sciences and space research XXIII(2): Planetary biology and origins of life; Proceedings of the Topical Meeting and Workshops XX, XXI and XXIII of the 27th COSPAR Plenary Meeting, Espoo, Finland, July 18-29, 1988

NASA Technical Reports Server (NTRS)

Schwartz, A. W. (Editor); Dose, K. (Editor); Raup, D. M. (Editor); Klein, H. P. (Editor); Devincenzi, D. L. (Editor)

1989-01-01

This volume includes chapters on exobiology in space, chemical and early biochemical evolution, life without oxygen, potential for chemical evolution in the early environment of Mars, planetary protection issues and sample return missions, and the modulation of biological evolution by astrophysical phenomena. Papers are presented on the results of spaceflight missions, the action of some factors of space medium on the abiogenic synthesis of nucleotides, early peptidic enzymes, microbiology and biochemistry of the methanogenic archaeobacteria, and present-day biogeochemical activities of anaerobic bacteria and their relevance to future exobiological investigations. Consideration is also given to the development of the Alba Patera volcano on Mars, biological nitrogen fixation under primordial Martian partial pressures of dinitrogen, the planetary protection issues in advance of human exploration of Mars, and the difficulty with astronomical explanations of periodic mass extinctions.

A prototype of an electric-discharge gas flow oxygen-iodine laser: I. Modeling of the processes of singlet oxygen generation in a transverse cryogenic slab RF discharge

NASA Astrophysics Data System (ADS)

Vagin, N. P.; Ionin, A. A.; Kochetov, I. V.; Napartovich, A. P.; Sinitsyn, D. V.; Yuryshev, N. N.

2017-03-01

The existing kinetic model describing self-sustained and electroionization discharges in mixtures enriched with singlet oxygen has been modified to calculate the characteristics of a flow RF discharge in molecular oxygen and its mixtures with helium. The simulations were performed in the gas plug-flow approximation, i.e., the evolution of the plasma components during their motion along the channel was represented as their evolution in time. The calculations were carried out for the O2: He = 1: 0, 1: 1, 1: 2, and 1: 3 mixtures at an oxygen partial pressure of 7.5 Torr. It is shown that, under these conditions, volumetric gas heating in a discharge in pure molecular oxygen prevails over gas cooling via heat conduction even at an electrode temperature as low as 100 K. When molecular oxygen is diluted with helium, the behavior of the gas temperature changes substantially: heat removal begins to prevail over volumetric gas heating, and the gas temperature at the outlet of the discharge zone drops to 220-230 K at room gas temperature at the inlet, which is very important in the context of achieving the generation threshold in an electric-discharge oxygen-iodine laser based on a slab cryogenic RF discharge.

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

NASA Astrophysics Data System (ADS)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

The evolution of glutathione metabolism in phototrophic microorganisms

NASA Technical Reports Server (NTRS)

Fahey, R. C.; Buschbacher, R. M.; Newton, G. L.

1987-01-01

Of the many roles ascribed to glutathione (GSH) the one most clearly established is its role in the protection of higher eucaryotes against oxygen toxicity through destruction of thiol-reactive oxygen byproducts. If this is the primary function of GSH then GSH metabolism should have evolved during or after the evolution of oxygenic photosynthesis. That many bacteria do not produce GSH is consistent with this view. In the present study we have examined the low-molecular-weight thiol composition of a variety of phototrophic microorganisms to ascertain how evolution of GSH production is related to evolution of oxygenic photosynthesis. Cells were extracted in the presence of monobromobimane (mBBr) to convert thiols to fluorescent derivatives, which were analyzed by high-pressure liquid chromatography. Significant levels of GSH were not found in the green bacteria (Chlorobium thiosulfatophilum and Chloroflexus aurantiacus). Substantial levels of GSH were present in the purple bacteria (Chromatium vinosum, Rhodospirillum rubrum, Rhodobacter sphaeroides, and Rhodocyclus gelatinosa), the cyanobacteria [Anacystis nidulans, Microcoleus chthonoplastes S.G., Nostoc muscorum, Oscillatoria amphigranulata, Oscillatoria limnetica, Oscillatoria sp. (Stinky Spring, Utah), Oscillatoria terebriformis, Plectonema boryanum, and Synechococcus lividus], and eucaryotic algae (Chlorella pyrenoidsa, Chlorella vulgaris, Euglena gracilis, Scenedesmus obliquus, and Chlamydomonas reinhardtii). Other thiols measured included cysteine, gamma-glutamylcysteine, thiosulfate, coenzyme A, and sulfide; several unidentified thiols were also detected. Many of the organisms examined also exhibited a marked ability to reduce mBBr to syn-(methyl,methyl)bimane, an ability that was quenched by treatment with 2-pyridyl disulfide or 5,5'-bisdithio-(2-nitrobenzoic acid) prior to reaction with mBBr. These observations indicate the presence of a reducing system capable of electron transfer to mBBr and reduction of reactive disulfides. The distribution of GSH in phototrophic eubacteria indicates that GSH synthesis evolved at or around the time that oxygenic photosynthesis evolved.

Insights into highly improved solar-driven photocatalytic oxygen evolution over integrated Ag3PO4/MoS2 heterostructures

NASA Astrophysics Data System (ADS)

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

2018-04-01

Oxygen evolution has been considered as the rate-determining step in photocatalytic water splitting due to its sluggish four-electron half-reaction rate, the development of oxygen-evolving photocatalysts with well-defined morphologies and superior interfacial contact is highly important for achieving high-performance solar water splitting. Herein, we report the fabrication of Ag3PO4/MoS2 nanocomposites and, for the first time, their use in photocatalytic water splitting into oxygen under LED light illumination. Ag3PO4 nanoparticles were found to be anchored evenly on the surface of MoS2 nanosheets, confirming an efficient hybridization of two semiconductor materials. A maximum oxygen-generating rate of 201.6 mol L-1 g-1 h-1 was determined when 200 mg MoS2 nanosheets were incorporated into Ag3PO4 nanoparticles, which is around 5 times higher than that of bulk Ag3PO4. Obvious enhancements in light-harvesting property, as well as electron-hole separation and charge transportation are revealed by the combination of different characterizations. ESR analysis verified that more active oxygen-containing radicals generate over illuminated Ag3PO4/MoS2 composite photocatalysts rather than irradiated Ag3PO4. The improvement in oxygen evolution performance of Ag3PO4/MoS2 composite photocatalysts is ascribed to wide spectra response in the visible-light region, more efficient charge separation and enhanced oxidation capacity in the valence band (VB). This study provides new insights into the design and development of novel composite photocatalytic materials for solar-to-fuel conversion.

The evolution of photosynthesis...again?

PubMed

Rothschild, Lynn J

2008-08-27

'Replaying the tape' is an intriguing 'would it happen again?' exercise. With respect to broad evolutionary innovations, such as photosynthesis, the answers are central to our search for life elsewhere. Photosynthesis permits a large planetary biomass on Earth. Specifically, oxygenic photosynthesis has allowed an oxygenated atmosphere and the evolution of large metabolically demanding creatures, including ourselves. There are at least six prerequisites for the evolution of biological carbon fixation: a carbon-based life form; the presence of inorganic carbon; the availability of reductants; the presence of light; a light-harvesting mechanism to convert the light energy into chemical energy; and carboxylating enzymes. All were present on the early Earth. To provide the evolutionary pressure, organic carbon must be a scarce resource in contrast to inorganic carbon. The probability of evolving a carboxylase is approached by creating an inventory of carbon-fixation enzymes and comparing them, leading to the conclusion that carbon fixation in general is basic to life and has arisen multiple times. Certainly, the evolutionary pressure to evolve new pathways for carbon fixation would have been present early in evolution. From knowledge about planetary systems and extraterrestrial chemistry, if organic carbon-based life occurs elsewhere, photosynthesis -- although perhaps not oxygenic photosynthesis -- would also have evolved.

Efficient carbon dots/NiFe-layered double hydroxide/BiVO4 photoanodes for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Lv, Xiaowei; Xiao, Xin; Cao, Minglei; Bu, Yi; Wang, Chuanqing; Wang, Mingkui; Shen, Yan

2018-05-01

Modification of semiconductor photoanodes with oxygen evolution catalyst (OEC) is an effective approach for improving photoelectrochemical (PEC) water splitting efficiency. In the configuration, how to increase the activity of OEC is crucial to further improve PEC performance. Herein, a ternary photoanode system was designed to enhance PEC efficiency of photoelectrodes through introducing carbon dots (CDs), NiFe-layered double hydroxide (NiFe-LDH) nanosheets on BiVO4 particles. Systematic research shows that NiFe-LDH serves as an OEC which accelerates oxygen evolution kinetics, while the introduction of CDs can further reduce charge transfer resistance and overpotential for oxygen evolution. Under the synergistic effect of NiFe-LDH and CDs, the photocurrent and incident photon to current conversion efficiency (IPCE) of the resulting CDs/NiFe-LDH/BiVO4 photoanode is improved significantly than those of the NiFe-LDH/BiVO4 electrode. Consequently, such a ternary heterostructure could be an alternative way to further enhance PEC water splitting performance.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Oxygen and hydrogen evolution reaction on oriented single crystals of ruthenium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berger, L I; Pollak, F H; Canivez, Y

1979-01-01

A novel design for water electrolysis using a solid polymer electrolyte is being developed by General Electric. Ruthenium is one of the best electrocatalysts for the oxygen evolution reaction. There are problems connected with the significant loss in electrocatalytic activity with time. This performance degradation is presumably due to the gradual formation of an RuO/sub 2/ film. We have performed electrochemical measurements on (100), (110) and (111) oriented single crystals of RuO/sub 2/ in order to elucidate the mechanism of the electrocatalytic process. Large single crystals were grown by the vapor transport method. Our investigation has revealed several interesting differencesmore » for the various orientations. This study indicates that RuO/sub 3/ may be an important intermediate species prior to oxygen evolution and that the formation of the RuO/sub 3/ is the rate limiting process. Similar results were previously obtained for IrO/sub 2/.« less

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

NASA Technical Reports Server (NTRS)

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.

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event.

PubMed

Luo, Genming; Junium, Christopher K; Izon, Gareth; Ono, Shuhei; Beukes, Nicolas J; Algeo, Thomas J; Cui, Ying; Xie, Shucheng; Summons, Roger E

2018-03-07

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte-Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.

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

NASA Astrophysics Data System (ADS)

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.

Properties of the outer regions of spiral disks: abundances, colors and ages

NASA Astrophysics Data System (ADS)

Mollá, Mercedes; Díaz, Angeles I.; Gibson, Brad K.; Cavichia, Oscar; López-Sánchez, Ángel-R.

2017-03-01

We summarize the results obtained from our suite of chemical evolution models for spiral disks, computed for different total masses and star formation efficiencies. Once the gas, stars and star formation radial distributions are reproduced, we analyze the Oxygen abundances radial profiles for gas and stars, in addition to stellar averaged ages and global metallicity. We examine scenarios for the potential origin of the apparent flattening of abundance gradients in the outskirts of disk galaxies, in particular the role of molecular gas formation prescriptions.

Spectropolarimetry of Photosynthetic Pigments as Global Surface Biosignatures

NASA Astrophysics Data System (ADS)

Sparks, W. B.; Parenteau, M. N.; Blankenship, R. E.; Germer, T. A.; Meadows, V. S.; Telesco, C. M.

2015-12-01

Photosynthesis is an ancient metabolic process on the early Earth. The most primitive phototrophs used reductants such as H2, H2S, and Fe(II) and were widespread in marine, intertidal, and likely continental habitats. These anoxygenic phototrophs were the key primary producers for the first ~1 billion years before the evolution of oxygenic photosynthesis at 2.7 Ga. The potential clearly exists for this type of primitive photosynthesis to operate on habitable exoplanets. Anoxygenic phototrophs are not known to emit gases that are uniquely biogenic in origin, so we focus on surface pigments signatures as having the strongest promise to offer identifiable biosignatures for a pre-oxygenic habitable exoplanet. Following our earlier work that showed photosynthetic cyanobacteria yield a polarization signature potentially useful in remote sensing, here we seek to characterize the remotely detectable polarization biosignatures associated with anoxygenic phototrophs. The six major pigments of anoxygenic phototrophs (bacteriochlorophylls [Bchls]) absorb in the near-infrared (NIR) from ~705 - 1040 nm. The lower symmetry of the pigment structure relative to chlorophylls shifts the energy absorption bands to longer wavelengths. As a result, Bchls are well suited to absorbing the relatively higher flux of red and NIR radiation of M dwarf stars, the most abundant type of star in the Galaxy, as well as the plentiful flux of typical main sequence stars. Homochirality is a powerful biosignature, and because of the optical activity of biological molecules, it can, in principle, be remotely observed on macroscopic scales using circular polarization spectroscopy. Bchls and Chls are optically active molecules with several chiral centers, strongly interacting with the incident light. We measured the reflectance and transmission full Stokes polarization spectra of pure cultures of anoxygenic phototrophs and environmental samples of microbial mats, and found strong correlations between spectral and polarization features. This work characterizing polarization biosignatures associated with the pigments of anoxygenic phototrophs informs the search for life on exoplanets at a similar stage of evolution or biogeochemical state as the Archean Earth (i.e., pre-oxygenic photosynthesis).

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Redox state of the Archean mantle: Evidence from V partitioning in 3.5-2.4 Ga komatiites

NASA Astrophysics Data System (ADS)

Nicklas, Robert W.; Puchtel, Igor S.; Ash, Richard D.

2018-02-01

Oxygen fugacity of the mantle is a crucial thermodynamic parameter that controls such fundamental processes as planetary differentiation, mantle melting, and possible core-mantle exchange. Constraining the evolution of the redox state of the mantle is of paramount importance for understanding the chemical evolution of major terrestrial reservoirs, including the core, mantle, and atmosphere. In order to evaluate the secular evolution of the redox state of the mantle, oxygen fugacities of six komatiite systems, ranging in age from 3.48 to 2.41 Ga, were determined using high-precision partitioning data of the redox-sensitive element vanadium between liquidus olivine, chromite and komatiitic melt. The calculated oxygen fugacities range from -0.11 ± 0.30 ΔFMQ log units in the 3.48 Ga Komati system to +0.43 ± 0.26 ΔFMQ log units in the 2.41 Ga Vetreny system. Although there is a slight hint in the data for an increase in the oxygen fugacity of the mantle between 3.48 and 2.41 Ga, these values generally overlap within their respective uncertainties; they are also largely within the range of oxygen fugacity estimates for modern MORB lavas of +0.60 ± 0.30 ΔFMQ log units that we obtained using the same technique. Our results are consistent with the previous findings that argued for little change in the mantle oxygen fugacity since the early Archean and indicate that the mantle had reached its nearly-present day redox state by at least 3.48 Ga.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Photosynthetic water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenbaum, E.

1981-01-01

The photosynthetic unit of hydrogen evolution, the turnover time of photosynthetic hydrogen production, and hydrogenic photosynthesis are discussed in the section on previous work. Recent results are given on simultaneous photoproduction of hydrogen and oxygen, kinetic studies, microscopic marine algae-seaweeds, and oxygen profiles.

Impact of Increasing Levels of Oxygen Consumption on the Evolution of Color, Phenolic, and Volatile Compounds of Nebbiolo Wines.

PubMed

Petrozziello, Maurizio; Torchio, Fabrizio; Piano, Federico; Giacosa, Simone; Ugliano, Maurizio; Bosso, Antonella; Rolle, Luca

2018-01-01

Since the end of the last century, many works have been carried out to verify the effect of controlled oxygen intake on the chemical and organoleptic characteristics of red wines. In spite of the large number of studies on this subject, oxygen remains a cutting-edge research topic in oenology. Oxygen consumption leads to complex and not univocal changes in wine composition, sometimes positive such as color stabilization, softening of mouthfeel, increase of aroma complexity. However, the variability of these effects, which depend both on the oxygenation conditions and the composition of the wine, require more efforts in this research field to effectively manage wine oxygen exposure. The present study is focused on the evolution of the chemical composition of four different Nebbiolo wines, each of them added with 4 different doses of oxygen (7, 14, 21, and 28 mg/L total intake) during the first month of storage. In this perspective, the evolution over time of wine color and polyphenols was studied. Acetaldehyde, glyceraldehyde and glyoxylic acid were quantified by HPLC. These compounds can play a role in wine aging creating condensed colored and stable products involving anthocyanins with or without tannins. Moreover, some volatile aldehydes correlated with oxidized olfactory notes, including methional and (E)-2-alkenals, have been quantified by GC-MS. Overall, during storage a decrease of color intensity, total and free anthocyanins and an increase in polymeric pigments (in particular the contribution to the red color of pigments not-bleachable by SO 2 or dTAT%) and some minor aldehydes was observed. Nevertheless, the differences in color parameters between the samples with different doses of oxygen were modest. These evidences were in contrast with an evident and detectable increase of free acetaldehyde content at increasing doses of oxygen measured after 60 days of storage. The effect of oxygen on color and production of SO 2 non-bleachable pigments during aging varies with wine composition, with Nebbiolo wines appearing not very reactive in this respect, probably due to their low content in anthocyanins and high content in tannins.

Impact of Increasing Levels of Oxygen Consumption on the Evolution of Color, Phenolic, and Volatile Compounds of Nebbiolo Wines

PubMed Central

Petrozziello, Maurizio; Torchio, Fabrizio; Piano, Federico; Giacosa, Simone; Ugliano, Maurizio; Bosso, Antonella; Rolle, Luca

2018-01-01

Since the end of the last century, many works have been carried out to verify the effect of controlled oxygen intake on the chemical and organoleptic characteristics of red wines. In spite of the large number of studies on this subject, oxygen remains a cutting-edge research topic in oenology. Oxygen consumption leads to complex and not univocal changes in wine composition, sometimes positive such as color stabilization, softening of mouthfeel, increase of aroma complexity. However, the variability of these effects, which depend both on the oxygenation conditions and the composition of the wine, require more efforts in this research field to effectively manage wine oxygen exposure. The present study is focused on the evolution of the chemical composition of four different Nebbiolo wines, each of them added with 4 different doses of oxygen (7, 14, 21, and 28 mg/L total intake) during the first month of storage. In this perspective, the evolution over time of wine color and polyphenols was studied. Acetaldehyde, glyceraldehyde and glyoxylic acid were quantified by HPLC. These compounds can play a role in wine aging creating condensed colored and stable products involving anthocyanins with or without tannins. Moreover, some volatile aldehydes correlated with oxidized olfactory notes, including methional and (E)-2-alkenals, have been quantified by GC-MS. Overall, during storage a decrease of color intensity, total and free anthocyanins and an increase in polymeric pigments (in particular the contribution to the red color of pigments not-bleachable by SO2 or dTAT%) and some minor aldehydes was observed. Nevertheless, the differences in color parameters between the samples with different doses of oxygen were modest. These evidences were in contrast with an evident and detectable increase of free acetaldehyde content at increasing doses of oxygen measured after 60 days of storage. The effect of oxygen on color and production of SO2 non-bleachable pigments during aging varies with wine composition, with Nebbiolo wines appearing not very reactive in this respect, probably due to their low content in anthocyanins and high content in tannins. PMID:29755971

Impact of increasing levels of oxygen consumption on the evolution of color, phenolic and volatile compounds of Nebbiolo wines

NASA Astrophysics Data System (ADS)

Petrozziello, Maurizio; Torchio, Fabrizio; Piano, Federico; Giacosa, Simone; Ugliano, Maurizio; Bosso, Antonella; Rolle, Luca

2018-04-01

Since the end of the last century, many works have been carried out to verify the effect of controlled oxygen intake on the chemical and organoleptic characteristics of red wines. In spite of the large number of studies on this subject, oxygen remains a cutting-edge research topic in oenology. Oxygen consumption leads to complex and not univocal changes in wine composition, sometimes positive such as color stabilization, softening of mouthfeel, increase of aroma complexity. However, the variability of these effects, which depend both on the oxygenation conditions and the composition of the wine, require more efforts in this research field to effectively manage wine oxygen exposure. The present study is focused on the evolution of the chemical composition of four different Nebbiolo wines, each of them added with 4 different doses of oxygen (7, 14, 21, and 28 mg/L total intake) during the first month of storage. In this perspective, the evolution over time of wine color and polyphenols was studied. Acetaldehyde, glyceraldehyde and glyoxylic acid were quantified by HPLC. These compounds can play a role in wine aging creating condensed colored and stable products involving anthocyanins with or without tannins. Moreover, some volatile aldehydes correlated with oxidized olfactory notes, including methional and (E)-2-alkenals, have been quantified by GC-MS. Overall, during storage a decrease of color intensity, total and free anthocyanins and an increase in polymeric pigments (in particular the contribution to the red color of pigments not-bleachable by SO2 or dTAT%) and some minor aldehydes was observed. Nevertheless, the differences in color parameters between the samples with different doses of oxygen were modest. These evidences were in contrast with an evident and detectable increase of free acetaldehyde content at increasing doses of oxygen measured after 60 days of storage. The effect of oxygen on color and production of SO2 non-bleachable pigments during ageing varies with wine composition, with Nebbiolo wines appearing not very reactive in this respect, probably due to their low content in anthocyanins and high content in tannins.

Oxygen no longer plays a major role in Body Size Evolution

NASA Astrophysics Data System (ADS)

Datta, H.; Sachson, W.; Heim, N. A.; Payne, J.

2015-12-01

When observing the long-term relationship between atmospheric oxygen and the maximum size in organisms across the Geozoic (~3.8 Ga - present), it appears that as oxygen increases, organism size grows. However, during the Phanerozoic (541 Ma - Present) oxygen levels varied, so we set out to test the hypothesis that oxygen levels drive patterns marine animal body size evolution. Expected decreases in maximum size due to a lack of oxygen do not occur, and instead, body size continues to increase regardless. In the oxygen data, a relatively low atmospheric oxygen percentage can support increasing body size, so our research tries to determine whether lifestyle affects body size in marine organisms. The genera in the data set were organized based on their tiering, motility, and feeding, such as a pelagic, fully-motile, predator. When organisms fill a certain ecological niche to take advantage of resources, they will have certain life modes, rather than randomly selected traits. For example, even in terrestrial environments, large animals have to constantly feed themselves to support their expensive terrestrial lifestyle which involves fairly consistent movement, and the structural support necessary for that movement. Only organisms with access to high energy food sources or large amounts of food can support themselves, and that is before they expend energy elsewhere. Organisms that expend energy frugally when active or have slower metabolisms in comparison to body size have a more efficient lifestyle and are generally able to grow larger, while those who have higher energy demands like predators are limited to comparatively smaller sizes. Therefore, in respect to the fossil record and modern measurements of animals, the metabolism and lifestyle of an organism dictate its body size in general. With this further clarification on the patterns of evolution, it will be easier to observe and understand the reasons for the ecological traits of organisms today.

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

NASA Astrophysics Data System (ADS)

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.

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

ERIC Educational Resources Information Center

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…

Effects of oxygen partial pressure on Li-air battery performance

NASA Astrophysics Data System (ADS)

Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

2017-10-01

For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

PubMed

Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

2018-03-19

By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Oxygen Sensing for Industrial Safety — Evolution and New Approaches

PubMed Central

Willett, Martin

2014-01-01

The requirement for the detection of oxygen in industrial safety applications has historically been met by electrochemical technologies based on the consumption of metal anodes. Products using this approach have been technically and commercially successful for more than three decades. However, a combination of new requirements is driving the development of alternative approaches offering fresh opportunities and challenges. This paper reviews some key aspects in the evolution of consumable anode products and highlights recent developments in alternative technologies aimed at meeting current and anticipated future needs in this important application. PMID:24681673

Oxygen sensing for industrial safety - evolution and new approaches.

PubMed

Willett, Martin

2014-03-27

The requirement for the detection of oxygen in industrial safety applications has historically been met by electrochemical technologies based on the consumption of metal anodes. Products using this approach have been technically and commercially successful for more than three decades. However, a combination of new requirements is driving the development of alternative approaches offering fresh opportunities and challenges. This paper reviews some key aspects in the evolution of consumable anode products and highlights recent developments in alternative technologies aimed at meeting current and anticipated future needs in this important application.

An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical evolution of oxygen.

PubMed

Louie, Mary W; Bell, Alexis T

2013-08-21

A detailed investigation has been carried out of the structure and electrochemical activity of electrodeposited Ni-Fe films for the oxygen evolution reaction (OER) in alkaline electrolytes. Ni-Fe films with a bulk and surface composition of 40% Fe exhibit OER activities that are roughly 2 orders of magnitude higher than that of a freshly deposited Ni film and about 3 orders of magnitude higher than that of an Fe film. The freshly deposited Ni film increases in activity by as much as 20-fold during exposure to the electrolyte (KOH); however, all films containing Fe are stable as deposited. The oxidation of Ni(OH)2 to NiOOH in Ni films occurs at potentials below the onset of the OER. Incorporation of Fe into the film increases the potential at which Ni(OH)2/NiOOH redox occurs and decreases the average oxidation state of Ni in NiOOH. The Tafel slope (40 mV dec(-1)) and reaction order in OH(-) (1) for the mixed Ni-Fe films (containing up to 95% Fe) are the same as those for aged Ni films. In situ Raman spectra acquired in 0.1 M KOH at OER potentials show two bands characteristic of NiOOH. The relative intensities of these bands vary with Fe content, indicating a change in the local environment of Ni-O. Similar changes in the relative intensities of the bands and an increase in OER activity are observed when pure Ni films are aged. These observations suggest that the OER is catalyzed by Ni in Ni-Fe films and that the presence of Fe alters the redox properties of Ni, causing a positive shift in the potential at which Ni(OH)2/NiOOH redox occurs, a decrease in the average oxidation state of the Ni sites, and a concurrent increase in the activity of Ni cations for the OER.

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

NASA Technical Reports Server (NTRS)

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.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

PubMed

Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

2018-04-25

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Evolution of Space Station EMU PLSS technology recommendations

NASA Technical Reports Server (NTRS)

Wilde, Richard C.

1990-01-01

Viewgraphs on extravehicular mobility unit (EMU) portable life support system (PLSS) technology recommendations are presented. Topics covered include: oxygen supply storage; oxygen supply regulators; carbon dioxide control; prime movers; crew comfort; heat rejection; power sources; controls; display devices; and sensor technology.

Balancing the generation and elimination of reactive oxygen species

USGS Publications Warehouse

Rodriguez, Rusty; Redman, Regina

2005-01-01

Fossil records suggest that bacteria developed the ability to photosynthesize ≈3,500 million years ago (mya), initiating a very slow accumulation of atmospheric oxygen (1). Recent geochemical models suggest that atmospheric oxygen did not accumulate to levels conducive for aerobic life until 500–1,000 mya (2, 3). The oxygenation of Earth's atmosphere resulted in the emergence of aerobic organisms followed by a great diversification of biological species and the eventual evolution of humans.

The Rate of Oxygen Utilization by Cells

PubMed Central

Wagner, Brett A.; Venkataraman, Sujatha; Buettner, Garry R.

2011-01-01

The discovery of oxygen is considered by some to be the most important scientific discovery of all time – from both physical-chemical/astrophysics and biology/evolution viewpoints. One of the major developments during evolution is the ability to capture dioxygen in the environment and deliver it to each cell in the multicellular, complex mammalian body -- on demand, i.e. just-in-time. Humans use oxygen to extract approximately 2550 Calories (10.4 MJ) from food to meet daily energy requirements. This combustion requires about 22 moles of dioxygen per day, or 2.5 × 10-4 mol s-1. This is an average rate of oxygen utilization of 2.5 × 10-18 mol cell-1 s-1, i.e. 2.5 amol cell-1 s-1. Cells have a wide range of oxygen utilization, depending on cell type, function, and biological status. Measured rates of oxygen utilization by mammalian cells in culture range from <1 to >350 amol cell-1 s-1. There is a loose positive linear correlation of the rate of oxygen consumption (OCR) by mammalian cells in culture with cell volume and cell protein. The use of oxygen by cells and tissues is an essential aspect of the basic redox biology of cells and tissues. This type of quantitative information is fundamental to investigations in quantitative redox biology, especially redox systems biology. PMID:21664270

Boosting water oxidation layer-by-layer.

PubMed

Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

2016-04-07

Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology.

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

DOE PAGES

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong; ...

2015-12-03

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Ultra Uniform Pb0.865La0.09(Zr0.65Ti0.35)O3 Thin Films with Tunable Optical Properties Fabricated via Pulsed Laser Deposition

PubMed Central

Jiang, Shenglin; Huang, Chi; Gu, Honggang; Liu, Shiyuan; Zhu, Shuai; Li, Ming-Yu; Yao, Lingmin; Wu, Yunyi; Zhang, Guangzu

2018-01-01

Ferroelectric thin films have been utilized in a wide range of electronic and optical applications, in which their morphologies and properties can be inherently tuned by a qualitative control during growth. In this work, we demonstrate the evolution of the Pb0.865La0.09(Zr0.65Ti0.35)O3 (PLZT) thin films on MgO (200) with high uniformity and optimized optical property via the controls of the deposition temperatures and oxygen pressures. The perovskite phase can only be obtained at the deposition temperature above 700 °C and oxygen pressure over 50 Pa due to the improved crystallinity. Meanwhile, the surface morphologies gradually become smooth and compact owing to spontaneously increased nucleation sites with the elevated temperatures, and the crystallization of PLZT thin films also sensitively respond to the oxygen vacancies with the variation of oxygen pressures. Correspondingly, the refractive indices gradually develop with variations of the deposition temperatures and oxygen pressures resulted from the various slight loss, and the extinction coefficient for each sample is similarly near to zero due to the relatively smooth morphology. The resulting PLZT thin films exhibit the ferroelectricity, and the dielectric constant sensitively varies as a function of electric filed, which can be potentially applied in the electronic and optical applications. PMID:29596398

Catalyst Stability Benchmarking for the Oxygen Evolution Reaction: The Importance of Backing Electrode Material and Dissolution in Accelerated Aging Studies.

PubMed

Geiger, Simon; Kasian, Olga; Mingers, Andrea M; Nicley, Shannon S; Haenen, Ken; Mayrhofer, Karl J J; Cherevko, Serhiy

2017-09-18

In searching for alternative oxygen evolution reaction (OER) catalysts for acidic water splitting, fast screening of the material intrinsic activity and stability in half-cell tests is of vital importance. The screening process significantly accelerates the discovery of new promising materials without the need of time-consuming real-cell analysis. In commonly employed tests, a conclusion on the catalyst stability is drawn solely on the basis of electrochemical data, for example, by evaluating potential-versus-time profiles. Herein important limitations of such approaches, which are related to the degradation of the backing electrode material, are demonstrated. State-of-the-art Ir-black powder is investigated for OER activity and for dissolution as a function of the backing electrode material. Even at very short time intervals materials like glassy carbon passivate, increasing the contact resistance and concealing the degradation phenomena of the electrocatalyst itself. Alternative backing electrodes like gold and boron-doped diamond show better stability and are thus recommended for short accelerated aging investigations. Moreover, parallel quantification of dissolution products in the electrolyte is shown to be of great importance for comparing OER catalyst feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heteroatom (P, B, or S) incorporated NiFe-based nanocubes as efficient electrocatalysts for the oxygen evolution reaction

DOE PAGES

Xuan, Cuijuan; Wang, Jie; Xia, Weiwei; ...

2018-03-21

Exploring low-cost and highly efficient electrocatalysts toward the oxygen evolution reaction (OER) is of significant importance, although facing great challenges for sustainable energy systems. In this study, amorphous NiFe-based porous nanocubes (Ni–Fe–O–P, Ni–Fe–O–B, and Ni–Fe–O–S) are successfully synthesized via simple and cost-effective one-step calcination of Ni–Fe based metal–organic frameworks (MOFs) and heteroatom containing molecules. The resulting three materials maintain a well-defined porous nanocube morphology with heteroatoms uniformly distributed in the structure. The unique porous structure can effectively provide more active sites and shorten the mass transport distance. Additionally, the introduction of P, B or S can tune the electronic structure,more » which is favorable for accelerating the charge transfer, and may lead to the formation of the higher average oxidative valence of Ni species during the OER process. Benefiting from the above desirable properties, all three materials exhibit excellent OER electrocatalytic activities and outstanding long-term stability in a home-made zinc air battery. Lastly, this work not only provides a general approach for the synthesis of highly efficient electrocatalysts based on earth-abundant elements but also highlights the potential prospects of MOFs in energy conversion and storage devices.« less

Heteroatom (P, B, or S) incorporated NiFe-based nanocubes as efficient electrocatalysts for the oxygen evolution reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xuan, Cuijuan; Wang, Jie; Xia, Weiwei

Exploring low-cost and highly efficient electrocatalysts toward the oxygen evolution reaction (OER) is of significant importance, although facing great challenges for sustainable energy systems. In this study, amorphous NiFe-based porous nanocubes (Ni–Fe–O–P, Ni–Fe–O–B, and Ni–Fe–O–S) are successfully synthesized via simple and cost-effective one-step calcination of Ni–Fe based metal–organic frameworks (MOFs) and heteroatom containing molecules. The resulting three materials maintain a well-defined porous nanocube morphology with heteroatoms uniformly distributed in the structure. The unique porous structure can effectively provide more active sites and shorten the mass transport distance. Additionally, the introduction of P, B or S can tune the electronic structure,more » which is favorable for accelerating the charge transfer, and may lead to the formation of the higher average oxidative valence of Ni species during the OER process. Benefiting from the above desirable properties, all three materials exhibit excellent OER electrocatalytic activities and outstanding long-term stability in a home-made zinc air battery. Lastly, this work not only provides a general approach for the synthesis of highly efficient electrocatalysts based on earth-abundant elements but also highlights the potential prospects of MOFs in energy conversion and storage devices.« less

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

PubMed

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.

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

PubMed

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.

Oceanic oxygenation events in the anoxic Ediacaran ocean.

PubMed

Sahoo, S K; Planavsky, N J; Jiang, G; Kendall, B; Owens, J D; Wang, X; Shi, X; Anbar, A D; Lyons, T W

2016-09-01

The ocean-atmosphere system is typically envisioned to have gone through a unidirectional oxygenation with significant oxygen increases in the earliest (ca. 635 Ma), middle (ca. 580 Ma), or late (ca. 560 Ma) Ediacaran Period. However, temporally discontinuous geochemical data and the patchy metazoan fossil record have been inadequate to chart the details of Ediacaran ocean oxygenation, raising fundamental debates about the timing of ocean oxygenation, its purported unidirectional rise, and its causal relationship, if any, with the evolution of early animal life. To better understand the Ediacaran ocean redox evolution, we have conducted a multi-proxy paleoredox study of a relatively continuous, deep-water section in South China that was paleogeographically connected with the open ocean. Iron speciation and pyrite morphology indicate locally euxinic (anoxic and sulfidic) environments throughout the Ediacaran in this section. In the same rocks, redox sensitive element enrichments and sulfur isotope data provide evidence for multiple oceanic oxygenation events (OOEs) in a predominantly anoxic global Ediacaran-early Cambrian ocean. This dynamic redox landscape contrasts with a recent view of a redox-static Ediacaran ocean without significant change in oxygen content. The duration of the Ediacaran OOEs may be comparable to those of the oceanic anoxic events (OAEs) in otherwise well-oxygenated Phanerozoic oceans. Anoxic events caused mass extinctions followed by fast recovery in biologically diversified Phanerozoic oceans. In contrast, oxygenation events in otherwise ecologically monotonous anoxic Ediacaran-early Cambrian oceans may have stimulated biotic innovations followed by prolonged evolutionary stasis. © 2016 John Wiley & Sons Ltd.

Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces

NASA Astrophysics Data System (ADS)

Nellist, Michael R.; Laskowski, Forrest A. L.; Qiu, Jingjing; Hajibabaei, Hamed; Sivula, Kevin; Hamann, Thomas W.; Boettcher, Shannon W.

2018-01-01

Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the "surface" electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.

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

ERIC Educational Resources Information Center

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…

Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

NASA Technical Reports Server (NTRS)

Freund, Friedemann

2001-01-01

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

Manganese-oxidizing photosynthesis before the rise of cyanobacteria.

PubMed

Johnson, Jena E; Webb, Samuel M; Thomas, Katherine; Ono, Shuhei; Kirschvink, Joseph L; Fischer, Woodward W

2013-07-09

The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however, the processes that led to the evolution of biological water splitting have remained largely unknown. To illuminate this history, we examined the behavior of the ancient Mn cycle using newly obtained scientific drill cores through an early Paleoproterozoic succession (2.415 Ga) preserved in South Africa. These strata contain substantial Mn enrichments (up to ∼17 wt %) well before those associated with the rise of oxygen such as the ∼2.2 Ga Kalahari Mn deposit. Using microscale X-ray spectroscopic techniques coupled to optical and electron microscopy and carbon isotope ratios, we demonstrate that the Mn is hosted exclusively in carbonate mineral phases derived from reduction of Mn oxides during diagenesis of primary sediments. Additional observations of independent proxies for O2--multiple S isotopes (measured by isotope-ratio mass spectrometry and secondary ion mass spectrometry) and redox-sensitive detrital grains--reveal that the original Mn-oxide phases were not produced by reactions with O2, which points to a different high-potential oxidant. These results show that the oxidative branch of the Mn cycle predates the rise of oxygen, and provide strong support for the hypothesis that the water-oxidizing complex of photosystem II evolved from a former transitional photosystem capable of single-electron oxidation reactions of Mn.

LASERS IN MEDICINE: Light-oxygen effect in cells and its potential applications in tumour therapy (review)

NASA Astrophysics Data System (ADS)

Zakharov, S. D.; Ivanov, Andrei V.

1999-12-01

The light-oxygen effect (POE) represents damage (and at low optical doses, activation) of cells by photogeneration of molecular singlet oxygen from O2 dissolved in cells, in accordance with the reaction: 3O2+hν→1O2→ biological effect. The phases of evolution of the LOE are similar to the phases, observed in cell experiments, of the photodynamic effect (PDE) the mechanism of which is the basis of the familiar method of photodynamic cancer therapy. The reported proofs of the occurrence of the LOE are in the form of detailed spectra of the biological action of optical radiation on cells recorded in four spectral intervals with the aid of tunable lasers. Allowances are made for the relationships governing a new type of cell excitation, associated with reversible structural transitions in the biomembrane. A demonstration is reported of the same efficiency of cw and pulsed irradiation. An analysis is made of the reasons why the optical doses initiating the PDE and the LOE are comparable. The results are given of the first experimental applications of the LOE in tumour therapy. Identification of the primary photoacceptor (O2) in cell biostimulation and photodestruction provides a scientific basis for the development of low-intensity laser light-oxygen cancer therapy methods.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae

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 factormore » 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.« less

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

DOE PAGES

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

2017-09-25

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

Design Strategy of Multi-electron Transfer Catalysts Based on a Bioinformatic Analysis of Oxygen Evolution and Reduction Enzymes.

PubMed

Ooka, Hideshi; Hashimoto, Kazuhito; Nakamura, Ryuhei

2018-05-14

Understanding the design strategy of photosynthetic and respiratory enzymes is important to develop efficient artificial catalysts for oxygen evolution and reduction reactions. Here, based on a bioinformatic analysis of cyanobacterial oxygen evolution and reduction enzymes (photosystem II: PS II and cytochrome c oxidase: COX, respectively), the gene encoding the catalytic D1 subunit of PS II was found to be expressed individually across 38 phylogenetically diverse strains, which is in contrast to the operon structure of the genes encoding major COX subunits. Selective synthesis of the D1 subunit minimizes the repair cost of PS II, which allows compensation for its instability by lowering the turnover number required to generate a net positive energy yield. The different bioenergetics observed between PS II and COX suggest that in addition to the catalytic activity rationalized by the Sabatier principle, stability factors have also provided a major influence on the design strategy of biological multi-electron transfer enzymes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

NASA Astrophysics Data System (ADS)

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-05-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm-2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec-1. Moreover, we achieve 10 mA cm-2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2.

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

Bifunctional catalytic electrode

NASA Technical Reports Server (NTRS)

Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

2005-01-01

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Hays, Charles C. (Inventor)

2015-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor); Narayan, Sri R. (Inventor)

2013-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Evolution of the atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.

1985-01-01

Theories on the origin of the Earth atmosphere and chemical composition are presented. The role of oxygenic photosynthesis on the determination of the Earth's origin is discussed. The research suggests that further analysis of the geologic record is needed to more accurately estimate the history of atmospheric oxygen.

Observations of the Evolution of Ion Outflow During a Sawtooth Event

NASA Astrophysics Data System (ADS)

Lund, E. J.; Nowrouzi, N.; Kistler, L. M.; Cai, X.; Frey, H. U.

2015-12-01

Sawtooth oscillations are one of several convection modes known to exist in the magnetosphere. Recent simulations have suggested that O+^+ ions transported from the high-latitude ionosphere to the magnetotail can drive sawtooth events. We present observational case studies of sawtooth events using data from FAST near the noon-midnight meridional plane, Cluster in the magnetotail, GOES and LANL energetic particle sensors at geosynchronous orbit, and ACE solar wind data to investigate the evolution of ion outflow during sawtooth events and the question of whether O+^+ outflow from one tooth helps to drive subsequent teeth. We find that oxygen enters the tail from the lobes after each tooth onset, the oxygen fraction in the magnetotail often increases after a tooth onset, and that the oxygen fraction of outflowing ions increases after a tooth event both in the cusp and on the nightside. However, a significant amount of low energy oxygen (≲1 keV) can end up in the dayside inner magnetosphere.

Operando Evidence for a Universal Oxygen Evolution Mechanism on Thermal and Electrochemical Iridium Oxides.

PubMed

Saveleva, Viktoriia A; Wang, Li; Teschner, Detre; Jones, Travis; Gago, Aldo S; Friedrich, K Andreas; Zafeiratos, Spyridon; Schlögl, Robert; Savinova, Elena R

2018-06-07

Progress in the development of proton exchange membrane (PEM) water electrolysis technology requires decreasing the anode overpotential, where the sluggish multistep oxygen evolution reaction (OER) occurs. This calls for an understanding of the nature of the active OER sites and reaction intermediates, which are still being debated. In this work, we apply synchrotron radiation-based near-ambient pressure X-ray photoelectron and absorption spectroscopies under operando conditions in order to unveil the nature of the reaction intermediates and shed light on the OER mechanism on electrocatalysts most widely used in PEM electrolyzers-electrochemical and thermal iridium oxides. Analysis of the O K-edge and Ir 4f spectra backed by density functional calculations reveals a universal oxygen anion red-ox mechanism regardless of the nature (electrochemical or thermal) of the iridium oxide. The formation of molecular oxygen is considered to occur through a chemical step from the electrophilic O I- species, which itself is formed in an electrochemical step.

Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

PubMed

Hodel, F; Macouin, M; Trindade, R I F; Triantafyllou, A; Ganne, J; Chavagnac, V; Berger, J; Rospabé, M; Destrigneville, C; Carlut, J; Ennih, N; Agrinier, P

2018-04-13

The evolution of the seawater oxygen isotopic composition (δ 18 O) through geological time remains controversial. Yet, the past δ 18 O seawater is key to assess past seawater temperatures, providing insights into past climate change and life evolution. Here we provide a new and unprecedentedly precise δ 18 O value of -1.33 ± 0.98‰ for the Neoproterozoic bottom seawater supporting a constant oxygen isotope composition through time. We demonstrate that the Aït Ahmane ultramafic unit of the ca. 760 Ma Bou Azzer ophiolite (Morocco) host a fossil black smoker-type hydrothermal system. In this system we analyzed an untapped archive for the ocean oxygen isotopic composition consisting in pure magnetite veins directly precipitated from a Neoproterozoic seawater-derived fluid. Our results suggest that, while δ 18 O seawater and submarine hydrothermal processes were likely similar to present day, Neoproterozoic oceans were 15-30 °C warmer on the eve of the Sturtian glaciation and the major life diversification that followed.

The oxidative environment: a mediator of interspecies communication that drives symbiosis evolution.

PubMed

Moné, Yves; Monnin, David; Kremer, Natacha

2014-06-22

Symbiotic interactions are ubiquitous in nature and play a major role in driving the evolution of life. Interactions between partners are often mediated by shared signalling pathways, which strongly influence both partners' biology and the evolution of the association in various environments. As an example of 'common language', the regulation of the oxidative environment plays an important role in driving the evolution of symbiotic associations. Such processes have been occurring for billions of years, including the increase in Earth's atmospheric oxygen and the subsequent evolution of mitochondria. The effect of reactive oxygen species and reactive nitrogen species (RONS) has been characterized functionally, but the molecular dialogue between partners has not been integrated within a broader evolutionary context yet. Given the pleiotropic role of RONS in cell-cell communication, development and immunity, but also their associated physiological costs, we discuss here how their regulation can influence the establishment, the maintenance and the breakdown of various symbiotic associations. By synthesizing recent developments in redox biology, we aim to provide an interdisciplinary understanding of the influence of such mediators of interspecies communication on the evolution and stability of symbioses, which in turn can shape ecosystems and play a role in health and disease.

Novel MOF-Derived Co@N-C Bifunctional Catalysts for Highly Efficient Zn-Air Batteries and Water Splitting.

PubMed

Zhang, Mingdao; Dai, Quanbin; Zheng, Hegen; Chen, Mindong; Dai, Liming

2018-03-01

Metal-organic frameworks (MOFs) and MOF-derived materials have recently attracted considerable interest as alternatives to noble-metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N-C materials (C-MOF-C2-T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C-MOF-C2-900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N-doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO 2 , respectively. Primary Zn-air batteries based on C-MOF-900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g Zn -1 under 10 mA cm -2 . Rechargeable Zn-air batteries based on C-MOF-C2-900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm -2 ), along with an excellent cycling stability with no increase in polarization even after 120 h - outperform their counterparts based on noble-metal-based air electrodes. The resultant rechargeable Zn-air batteries are used to efficiently power electrochemical water-splitting systems, demonstrating promising potential as integrated green energy systems for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Molecular evolution of globin genes in Gymnotiform electric fishes: relation to hypoxia tolerance.

PubMed

Tian, Ran; Losilla, Mauricio; Lu, Ying; Yang, Guang; Zakon, Harold

2017-02-13

Nocturnally active gymnotiform weakly electric fish generate electric signals for communication and navigation, which can be energetically taxing. These fish mainly inhabit the Amazon basin, where some species prefer well-oxygenated waters and others live in oxygen-poor, stagnant habitats. The latter species show morphological, physiological, and behavioral adaptations for hypoxia-tolerance. However, there have been no studies of hypoxia tolerance on the molecular level. Globins are classic respiratory proteins. They function principally in oxygen-binding and -delivery in various tissues and organs. Here, we investigate the molecular evolution of alpha and beta hemoglobins, myoglobin, and neuroglobin in 12 gymnotiforms compared with other teleost fish. The present study identified positively selected sites (PSS) on hemoglobin (Hb) and myoglobin (Mb) genes using different maximum likelihood (ML) methods; some PSS fall in structurally important protein regions. This evidence for the positive selection of globin genes suggests that the adaptive evolution of these genes has helped to enhance the capacity for oxygen storage and transport. Interestingly, a substitution of a Cys at a key site in the obligate air-breathing electric eel (Electrophorus electricus) is predicted to enhance oxygen storage of Mb and contribute to NO delivery during hypoxia. A parallel Cys substitution was also noted in an air-breathing African electric fish (Gymnarchus niloticus). Moreover, the expected pattern under normoxic conditions of high expression of myoglobin in heart and neuroglobin in the brain in two hypoxia-tolerant species suggests that the main effect of selection on these globin genes is on their sequence rather than their basal expression patterns. Results indicate a clear signature of positive selection in the globin genes of most hypoxia-tolerant gymnotiform fishes, which are obligate or facultative air breathers. These findings highlight the critical role of globin genes in hypoxia tolerance evolution of Gymnotiform electric fishes.

Sensitivity of ocean oxygenation to variations in tropical zonal wind stress magnitude

NASA Astrophysics Data System (ADS)

Ridder, Nina N.; England, Matthew H.

2014-09-01

Ocean oxygenation has been observed to have changed over the past few decades and is projected to change further under global climate change due to an interplay of several mechanisms. In this study we isolate the effect of modified tropical surface wind stress conditions on the evolution of ocean oxygenation in a numerical climate model. We find that ocean oxygenation varies inversely with low-latitude surface wind stress. Approximately one third of this response is driven by sea surface temperature anomalies; the remaining two thirds result from changes in ocean circulation and marine biology. Global mean O2 concentration changes reach maximum values of +4 μM and -3.6 μM in the two most extreme perturbation cases of -30% and +30% wind change, respectively. Localized changes lie between +92 μM under 30% reduced winds and -56 μM for 30% increased winds. Overall, we find that the extent of the global low-oxygen volume varies with the same sign as the wind perturbation; namely, weaker winds reduce the low-oxygen volume on the global scale and vice versa for increased trade winds. We identify two regions, one in the Pacific Ocean off Chile and the other in the Indian Ocean off Somalia, that are of particular importance for the evolution of oxygen minimum zones in the global ocean.

Early photosynthetic microorganisms and environmental evolution

NASA Technical Reports Server (NTRS)

Golubic, S.

1980-01-01

Microfossils which are preserved as shrivelled kerogenous residues provide little information about cellular organization and almost none about the metabolic properties of the organisms. The distinction between prokaryotic vs eukaryotic, and phototrophic vs chemo- and organotrophic fossil microorganisms rests entirely on morphological comparisons with recent counterparts. The residual nature of the microbial fossil record promotes the conclusion that it must be biased toward (a) most abundant organisms, (b) those most resistant to degradation, and (c) those inhabiting environments with high preservation potential e.g., stromatolites. These criteria support the cyanophyte identity of most Precambrian microbial fossils on the following grounds: (1) as primary producers they dominate prokaryotic communities in modern extreme environments, e.g., intertidal zone; (2) several morphological counterparts of modern cyanophytes and microbial fossils have been established based on structure, cell division patterns and degradation sequences. The impact of anaerobic and oxygenic microbial photosynthesis on the evolution of Precambrian environments is discussed.

Fuel Cells | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion, Electrochimica Acta (2016) Suppression of Oxygen Reduction Reaction Activity on Pt-Based Electrocatalysts from Ionomer Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction, Journal of the Electrochemical Society

Free-standing, flexible β-Ni(OH)2/electrochemically-exfoliated graphene film electrode for efficient oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Lanlan; Zhang, Jian; Jiang, Weitao; Zhao, Hong; Liu, Hongzhong

2018-03-01

The oxidation of water into molecular oxygen (oxygen evolution reaction, OER) is a pivotal reaction in many energy conversion devices. The high cost of IrO2, however, seriously hinder its large-scale applications in water oxidation. Here, we have at first reported a free-standing and flexible film electrode consisting of 2D β-Ni(OH)2/electrochemically-exfoliated graphene hybrid nanosheets (NiG-2), which is synthesized by a solvothermal reaction and an assembly process. The as-obtained NiG-2 film electrode exhibited an excellent electrocatalytic OER activity with an extremely low OER onset overpotential of ∼250 mV in a 1 M KOH aqueous solution, which is lower than these of the commercial Ir/C (370 mV at 10 mA cm-2) catalyst.

Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

NASA Astrophysics Data System (ADS)

Bouhadja, M.; Jakse, N.; Pasturel, A.

2014-06-01

Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al2O3)1-x(SiO2)x, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO5 structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution of the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.

Broad Phylogenetic Occurrence of the Oxygen-Binding Hemerythrins in Bilaterians.

PubMed

Costa-Paiva, Elisa M; Schrago, Carlos G; Halanych, Kenneth M

2017-10-01

Animal tissues need to be properly oxygenated for carrying out catabolic respiration and, as such, natural selection has presumably favored special molecules that can reversibly bind and transport oxygen. Hemoglobins, hemocyanins, and hemerythrins (Hrs) fulfill this role, with Hrs being the least studied. Knowledge of oxygen-binding proteins is crucial for understanding animal physiology. Hr genes are present in the three domains of life, Archaea, Bacteria, and Eukaryota; however, within Animalia, Hrs has been reported only in marine species in six phyla (Annelida, Brachiopoda, Priapulida, Bryozoa, Cnidaria, and Arthropoda). Given this observed Hr distribution, whether all metazoan Hrs share a common origin is circumspect. We investigated Hr diversity and evolution in metazoans, by employing in silico approaches to survey for Hrs from of 120 metazoan transcriptomes and genomes. We found 58 candidate Hr genes actively transcribed in 36 species distributed in 11 animal phyla, with new records in Echinodermata, Hemichordata, Mollusca, Nemertea, Phoronida, and Platyhelminthes. Moreover, we found that "Hrs" reported from Cnidaria and Arthropoda were not consistent with that of other metazoan Hrs. Contrary to previous suggestions that Hr genes were absent in deuterostomes, we find Hr genes present in deuterostomes and were likely present in early bilaterians, but not in nonbilaterian animal lineages. As expected, the Hr gene tree did not mirror metazoan phylogeny, suggesting that Hrs evolutionary history was complex and besides the oxygen carrying capacity, the drivers of Hr evolution may also consist of secondary functional specializations of the proteins, like immunological functions. © The Author(s) 2017. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Evolution and development of gas exchange structures in Mammalia: the placenta and the lung.

PubMed

Mess, Andrea M; Ferner, Kirsten J

2010-08-31

Appropriate oxygen supply is crucial for organisms. Here we examine the evolution of structures associated with the delivery of oxygen in the pre- and postnatal phases in mammals. There is an enormous structural and functional variability in the placenta that has facilitated the evolution of specialized reproductive strategies, such as precociality. In particular the cell layers separating fetal and maternal blood differ markedly: a non-invasive epitheliochorial placenta, which increases the diffusion distance, represents a derived state in ungulates. Rodents and their relatives have an invasive haemochorial placental type as optimum for the diffusion distance. In contrast, lung development is highly conserved and differences in the lungs of neonates can be explained by different developmental rates. Monotremes and marsupials have altricial stages with lungs at the early saccular phase, whereas newborn eutherians have lungs at the late saccular or alveolar phase. In conclusion, the evolution of exchange structures in the pre- and postnatal periods does not follow similar principles. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Powered by light: Phototrophy and photosynthesis in prokaryotes and its evolution.

PubMed

Nowicka, Beatrycze; Kruk, Jerzy

2016-01-01

Photosynthesis is a complex metabolic process enabling photosynthetic organisms to use solar energy for the reduction of carbon dioxide into biomass. This ancient pathway has revolutionized life on Earth. The most important event was the development of oxygenic photosynthesis. It had a tremendous impact on the Earth's geochemistry and the evolution of living beings, as the rise of atmospheric molecular oxygen enabled the development of a highly efficient aerobic metabolism, which later led to the evolution of complex multicellular organisms. The mechanism of photosynthesis has been the subject of intensive research and a great body of data has been accumulated. However, the evolution of this process is not fully understood, and the development of photosynthesis in prokaryota in particular remains an unresolved question. This review is devoted to the occurrence and main features of phototrophy and photosynthesis in prokaryotes. Hypotheses concerning the origin and spread of photosynthetic traits in bacteria are also discussed. Copyright © 2016 Elsevier GmbH. All rights reserved.

SU-E-T-191: First Principle Calculation of Quantum Yield in Photodynamic Therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abolfath, R; Guo, F; Chen, Z

Purpose: We present a first-principle method to calculate the spin transfer efficiency in oxygen induced by any photon fields especially in MeV energy range. The optical pumping is mediated through photosensitizers, e.g., porphyrin and/or ensemble of quantum dots. Methods: Under normal conditions, oxygen molecules are in the relatively non-reactive triplet state. In the presence of certain photosensitizer compounds such as porphyrins, electromagnetic radiation of specific wavelengths can excite oxygen to highly reactive singlet state. With selective uptake of photosensitizers by certain malignant cells, photon irradiation of phosensitized tumors can lead to selective killing of cancer cells. This is the basismore » of photodynamic therapy (PDT). Despite several attempts, PDT has not been clinically successful except in limited superficial cancers. Many parameters such as photon energy, conjugation with quantum dots etc. can be potentially combined with PDT in order to extend the role of PDT in cancer management. The key quantity for this optimization is the spin transfer efficiency in oxygen by any photon field. The first principle calculation model presented here, is an attempt to fill this need. We employ stochastic density matrix description of the quantum jumps and the rate equation methods in quantum optics based on Markov/Poisson processes and calculate time evolution of the population of the optically pumped singlet oxygen. Results: The results demonstrate the feasibility of our model in showing the dependence of the optical yield in generating spin-singlet oxygen on the experimental conditions. The adjustable variables can be tuned to maximize the population of the singlet oxygen hence the efficacy of the photodynamic therapy. Conclusion: The present model can be employed to fit and analyze the experimental data and possibly to assist researchers in optimizing the experimental conditions in photodynamic therapy.« less

Cell–cell signaling drives the evolution of complex traits: introduction—lung evo-devo

PubMed Central

Torday, John S.; Rehan, V. K.

2009-01-01

Physiology integrates biology with the environment through cell–cell interactions at multiple levels. The evolution of the respiratory system has been “deconvoluted” (Torday and Rehan in Am J Respir Cell Mol Biol 31:8–12, 2004) through Gene Regulatory Networks (GRNs) applied to cell–cell communication for all aspects of lung biology development, homeostasis, regeneration, and aging. Using this approach, we have predicted the phenotypic consequences of failed signaling for lung development, homeostasis, and regeneration based on evolutionary principles. This cell–cell communication model predicts other aspects of vertebrate physiology as adaptational responses. For example, the oxygen-induced differentiation of alveolar myocytes into alveolar adipocytes was critical for the evolution of the lung in land dwelling animals adapting to fluctuating Phanarezoic oxygen levels over the past 500 million years. Adipocytes prevent lung injury due to oxygen radicals and facilitate the rise of endothermy. In addition, they produce the class I cytokine leptin, which augments pulmonary surfactant activity and alveolar surface area, increasing selection pressure for both respiratory oxygenation and metabolic demand initially constrained by high-systemic vascular pressure, but subsequently compensated by the evolution of the adrenomedullary beta-adrenergic receptor mechanism. Conserted positive selection for the lung and adrenals created further selection pressure for the heart, which becomes progressively more complex phylogenetically in tandem with the lung. Developmentally, increasing heart complexity and size impinges precociously on the gut mesoderm to induce the liver. That evolutionary-developmental interaction is significant because the liver provides regulated sources of glucose and glycogen to the evolving physiologic system, which is necessary for the evolution of the neocortex. Evolution of neocortical control furthers integration of physiologic systems. Such an evolutionary vertical integration of cell-to-tissue-to-organ-to-physiology of intrinsic cell–cell signaling and extrinsic factors is the reverse of the “top-down” conventional way in which physiologic systems are usually regarded. This novel mechanistic approach, incorporating a “middle-out” cell–cell signaling component, will lead to a readily available algorithm for integrating genes and phenotypes. This symposium surveyed the phylogenetic origins of such vertically integrated mechanisms for the evolution of cell–cell communication as the basis for complex physiologic traits, from sponges to man. PMID:20607136

The 2.1 Ga old Francevillian biota: biogenicity, taphonomy and biodiversity.

PubMed

El Albani, Abderrazak; Bengtson, Stefan; Canfield, Donald E; Riboulleau, Armelle; Rollion Bard, Claire; Macchiarelli, Roberto; Ngombi Pemba, Lauriss; Hammarlund, Emma; Meunier, Alain; Moubiya Mouele, Idalina; Benzerara, Karim; Bernard, Sylvain; Boulvais, Philippe; Chaussidon, Marc; Cesari, Christian; Fontaine, Claude; Chi-Fru, Ernest; Garcia Ruiz, Juan Manuel; Gauthier-Lafaye, François; Mazurier, Arnaud; Pierson-Wickmann, Anne Catherine; Rouxel, Olivier; Trentesaux, Alain; Vecoli, Marco; Versteegh, Gerard J M; White, Lee; Whitehouse, Martin; Bekker, Andrey

2014-01-01

The Paleoproterozoic Era witnessed crucial steps in the evolution of Earth's surface environments following the first appreciable rise of free atmospheric oxygen concentrations ∼2.3 to 2.1 Ga ago, and concomitant shallow ocean oxygenation. While most sedimentary successions deposited during this time interval have experienced thermal overprinting from burial diagenesis and metamorphism, the ca. 2.1 Ga black shales of the Francevillian B Formation (FB2) cropping out in southeastern Gabon have not. The Francevillian Formation contains centimeter-sized structures interpreted as organized and spatially discrete populations of colonial organisms living in an oxygenated marine ecosystem. Here, new material from the FB2 black shales is presented and analyzed to further explore its biogenicity and taphonomy. Our extended record comprises variably sized, shaped, and structured pyritized macrofossils of lobate, elongated, and rod-shaped morphologies as well as abundant non-pyritized disk-shaped macrofossils and organic-walled acritarchs. Combined microtomography, geochemistry, and sedimentary analysis suggest a biota fossilized during early diagenesis. The emergence of this biota follows a rise in atmospheric oxygen, which is consistent with the idea that surface oxygenation allowed the evolution and ecological expansion of complex megascopic life.

SOME EFFECTS OF CADMIUM ON CONIFEROUS FOREST SOIL AND LITTER MICROCOSMS

EPA Science Inventory

Description and criticism is given of a preliminary design and use of a soil/litter microcosm in which oxygen, temperature, and humidity are kept constant, and oxygen generation and carbon dioxide and heat evolution rates are monitored. Using four microcosms, one acting as a dead...

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

PubMed

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.

Metabolic costs imposed by hydrostatic pressure constrain bathymetric range in the lithodid crab Lithodes maja.

PubMed

Brown, Alastair; Thatje, Sven; Morris, James P; Oliphant, Andrew; Morgan, Elizabeth A; Hauton, Chris; Jones, Daniel O B; Pond, David W

2017-11-01

The changing climate is shifting the distributions of marine species, yet the potential for shifts in depth distributions is virtually unexplored. Hydrostatic pressure is proposed to contribute to a physiological bottleneck constraining depth range extension in shallow-water taxa. However, bathymetric limitation by hydrostatic pressure remains undemonstrated, and the mechanism limiting hyperbaric tolerance remains hypothetical. Here, we assess the effects of hydrostatic pressure in the lithodid crab Lithodes maja (bathymetric range 4-790 m depth, approximately equivalent to 0.1 to 7.9 MPa hydrostatic pressure). Heart rate decreased with increasing hydrostatic pressure, and was significantly lower at ≥10.0 MPa than at 0.1 MPa. Oxygen consumption increased with increasing hydrostatic pressure to 12.5 MPa, before decreasing as hydrostatic pressure increased to 20.0 MPa; oxygen consumption was significantly higher at 7.5-17.5 MPa than at 0.1 MPa. Increases in expression of genes associated with neurotransmission, metabolism and stress were observed between 7.5 and 12.5 MPa. We suggest that hyperbaric tolerance in L maja may be oxygen-limited by hyperbaric effects on heart rate and metabolic rate, but that L maja 's bathymetric range is limited by metabolic costs imposed by the effects of high hydrostatic pressure. These results advocate including hydrostatic pressure in a complex model of environmental tolerance, where energy limitation constrains biogeographic range, and facilitate the incorporation of hydrostatic pressure into the broader metabolic framework for ecology and evolution. Such an approach is crucial for accurately projecting biogeographic responses to changing climate, and for understanding the ecology and evolution of life at depth. © 2017. Published by The Company of Biologists Ltd.

Co3O4-x-Carbon@Fe2-yCoyO3 Heterostructural Hollow Polyhedrons for the Oxygen Evolution Reaction.

PubMed

Xu, Wangwang; Xie, Weiwei; Wang, Ying

2017-08-30

Hollow heterostructured nanomaterials have received tremendous interest in new-generation electrocatalyst applications. However, the design and fabrication of such materials remain a significant challenge. In this work, we present Co 3 O 4-x -carbon@Fe 2-y Co y O 3 heterostructural hollow polyhedrons that have been fabricated by facile thermal treatment followed by solution-phase growth for application as efficient oxygen evolution reaction (OER) electrocatalysts. Starting from a single ZIF-67 hollow polyhedron, a novel complex structured composite material constructed from Co 3 O 4-x nanocrystallite-embedded carbon matrix embedded with Fe 2-y Co y O 3 nanowires was successfully prepared. The Co 3 O 4-x nanocrystallite with oxygen vacancies provides both heterogeneous nucleation sites and growth platform for Fe 2-y Co y O 3 nanowires. The resultant heterostructure combines the advantages of Fe 2-y Co y O 3 nanowires with the large surface area and surface defects of Co 3 O 4-x nanocrystallite, resulting in improved electrocatalytic activity and electrical conductivity. As a result, such novel heterostructured OER electrocatalysts exhibit much lower onset potential (1.52 V) and higher current density (70 mA/cm 2 at 1.7 V) than Co 3 O 4-x -carbon hollow polyhedrons (onset 1.55 V, 35 mA/cm 2 at 1.7 V) and pure Co 3 O 4 hollow polyhedrons (onset 1.62 V, 5 mA/cm 2 at 1.7 V). Furthermore, the design and synthesis of metal-organic framework (MOF)-derived nanomaterials in this work offer new opportunities for developing novel and efficient electrocatalysts in electrochemical devices.

Convergent Metabolic Specialization through Distinct Evolutionary Paths in Pseudomonas aeruginosa

PubMed Central

Johansen, Helle Krogh; Molin, Søren

2018-01-01

ABSTRACT Evolution by natural selection under complex and dynamic environmental conditions occurs through intricate and often counterintuitive trajectories affecting many genes and metabolic solutions. To study short- and long-term evolution of bacteria in vivo, we used the natural model system of cystic fibrosis (CF) infection. In this work, we investigated how and through which trajectories evolution of Pseudomonas aeruginosa occurs when migrating from the environment to the airways of CF patients, and specifically, we determined reduction of growth rate and metabolic specialization as signatures of adaptive evolution. We show that central metabolic pathways of three distinct Pseudomonas aeruginosa lineages coevolving within the same environment become restructured at the cost of versatility during long-term colonization. Cell physiology changes from naive to adapted phenotypes resulted in (i) alteration of growth potential that particularly converged to a slow-growth phenotype, (ii) alteration of nutritional requirements due to auxotrophy, (iii) tailored preference for carbon source assimilation from CF sputum, (iv) reduced arginine and pyruvate fermentation processes, and (v) increased oxygen requirements. Interestingly, although convergence was evidenced at the phenotypic level of metabolic specialization, comparative genomics disclosed diverse mutational patterns underlying the different evolutionary trajectories. Therefore, distinct combinations of genetic and regulatory changes converge to common metabolic adaptive trajectories leading to within-host metabolic specialization. This study gives new insight into bacterial metabolic evolution during long-term colonization of a new environmental niche. PMID:29636437

Bio-inspired co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

NASA Astrophysics Data System (ADS)

Hou, Yidong; Abrams, Billie L.; Vesborg, Peter C. K.; Bjørketun, Mårten E.; Herbst, Konrad; Bech, Lone; Seger, Brian; Pedersen, Thomas; Hansen, Ole; Rossmeisl, Jan; Dahl, Søren; Nørskov, Jens K.; Chorkendorff, Ib

2011-10-01

The production of fuels directly or indirectly from sunlight represents one of the major challenges to the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and while platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth-abundant alternatives are needed for largescale use. We show that bio-inspired molecular clusters based on molybdenum sulfides and tungsten sulfides mimic nature's enzymes for hydrogen evolution, molybdenum sulfides evolve hydrogen at a slightly higher overpotential than platinum when deposited on various supports. It will be demonstrated how this overpotential can be eliminated by depositing the same type of hydrogen evolution catalyst on p-type Si which can harvest the red part of the solar spectrum. Such a system could constitute the cathode part of a tandem dream device where the red part of the spectrum is utilized for hydrogen evolution while the blue part is reserved for the more difficult oxygen evolution. The samples have been illuminated with a simulated red part of the solar spectrum i.e. long wavelength (" > 620 nm) part of simulated AM 1.5G radiation. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by DFT calculations of the Mo3S4 cluster adsorbed on the hydrogen-terminated silicon surface providing insights into the nature of the active site.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, I

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, I, included the following reports:Oxygen in the Solar System: Origins of Isotopic and Redox Complexity; The Origin of Oxygen Isotope Variations in the Early Solar System; Solar and Solar-Wind Oxygen Isotopes and the Genesis Mission; Solar 18O/17O and the Setting for Solar Birth; Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites; Insight into Primordial Solar System Oxygen Reservoirs from Returned Cometary Samples; Tracing Meteorites to Their Sources Through Asteroid Spectroscopy; Redox Conditions Among the Terrestrial Planets; Redox Complexity in Martian Meteorites: Implications for Oxygen in the Terrestrial Planets; Implications of Sulfur Isotopes for the Evolution of Atmospheric Oxygen; Oxygen in the Outer Solar System; and On the Oxidation States of the Galilean Satellites: Implications for Internal Structures.

A Bacillus paralicheniformis Iron-Containing Urease Reduces Urea Concentrations in Rice Wine.

PubMed

Liu, Qingtao; Chen, Yuqi; Yuan, Minglai; Du, Guocheng; Chen, Jian; Kang, Zhen

2017-09-01

Urease, a nickel-containing metalloenzyme, was the first enzyme to be crystallized and has a prominent position in the history of biochemistry. In the present study, we identified a nickel urease gene cluster, ureABCEFGDH , in Bacillus paralicheniformis ATCC 9945a and characterized it in Escherichia coli Enzymatic assays demonstrate that this oxygen-stable urease is also an iron-containing acid urease. Heterologous expression assays of UreH suggest that this accessory protein is involved in the transmembrane transportation of nickel and iron ions. Moreover, this iron-containing acid urease has a potential application in the degradation of urea in rice wine. The present study not only enhances our understanding of the mechanism of activation of urease but also provides insight into the evolution of metalloenzymes. IMPORTANCE An iron-containing, oxygen-stable acid urease from B. paralicheniformis ATCC 9945a with good enzymatic properties was characterized. This acid urease shows activities toward both urea and ethyl carbamate. After digestion with 6 U/ml urease, approximately 92% of the urea in rice wine was removed, suggesting that this urease has great potential in the food industry. Copyright © 2017 American Society for Microbiology.

A Bacillus paralicheniformis Iron-Containing Urease Reduces Urea Concentrations in Rice Wine

PubMed Central

Liu, Qingtao; Chen, Yuqi; Yuan, Minglai; Chen, Jian

2017-01-01

ABSTRACT Urease, a nickel-containing metalloenzyme, was the first enzyme to be crystallized and has a prominent position in the history of biochemistry. In the present study, we identified a nickel urease gene cluster, ureABCEFGDH, in Bacillus paralicheniformis ATCC 9945a and characterized it in Escherichia coli. Enzymatic assays demonstrate that this oxygen-stable urease is also an iron-containing acid urease. Heterologous expression assays of UreH suggest that this accessory protein is involved in the transmembrane transportation of nickel and iron ions. Moreover, this iron-containing acid urease has a potential application in the degradation of urea in rice wine. The present study not only enhances our understanding of the mechanism of activation of urease but also provides insight into the evolution of metalloenzymes. IMPORTANCE An iron-containing, oxygen-stable acid urease from B. paralicheniformis ATCC 9945a with good enzymatic properties was characterized. This acid urease shows activities toward both urea and ethyl carbamate. After digestion with 6 U/ml urease, approximately 92% of the urea in rice wine was removed, suggesting that this urease has great potential in the food industry. PMID:28646111

Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

PubMed

Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

2018-08-15

The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

2016-09-01

The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

Earth-Abundant Oxygen Evolution Catalysts Coupled onto ZnO Nanowire Arrays for Efficient Photoelectrochemical Water Cleavage

PubMed Central

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

2014-01-01

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. PMID:25156820

Controlling the Interfacial Environment in the Electrosynthesis of MnOx Nanostructures for High-Performance Oxygen Reduction/Evolution Electrocatalysis.

PubMed

Hosseini-Benhangi, Pooya; Kung, Chun Haow; Alfantazi, Akram; Gyenge, Elöd L

2017-08-16

High-performance, nonprecious metal bifunctional electrocatalysts for the oxygen reduction and evolution reactions (ORR and OER, respectively) are of great importance for rechargeable metal-air batteries and regenerative fuel cells. A comprehensive study based on statistical design of experiments is presented to investigate and optimize the surfactant-assisted structure and the resultant bifunctional ORR/OER activity of anodically deposited manganese oxide (MnO x ) catalysts. Three classes of surfactants are studied: anionic (sodium dodecyl sulfate, SDS), non-ionic (t-octylphenoxypolyethoxyethanol, Triton X-100), and cationic (cetyltrimethylammonium bromide, CTAB). The adsorption of surfactants has two main effects: increased deposition current density due to higher Mn 2+ and Mn 3+ concentrations at the outer Helmholtz plane (Frumkin effect on the electrodeposition kinetics) and templating of the MnO x nanostructure. CTAB produces MnO x with nanoneedle (1D) morphology, whereas nanospherical- and nanopetal-like morphologies are obtained with SDS and Triton, respectively. The bifunctional performance is assessed based on three criteria: OER/ORR onset potential window (defined at 2 and -2 mA cm -2 ) and separately the ORR and OER mass activities. The best compromise among these three criteria is obtained either with Triton X-100 deposited catalyst composed of MnOOH and Mn 3 O 4 or SDS deposited catalyst containing a combination of α- and β-MnO 2 , MnOOH, and Mn 3 O 4 .The interaction effects among the deposition variables (surfactant type and concentration, anode potential, Mn 2+ concentration, and temperature) reveal the optimal strategy for high-activity bifunctional MnO x catalyst synthesis. Mass activities for OER and ORR up to 49 A g -1 (at 1556 mV RHE ) and -1.36 A g -1 (at 656 mV RHE ) are obtained, respectively.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

The potential of planets orbiting red dwarf stars to support oxygenic photosynthesis and complex life

NASA Astrophysics Data System (ADS)

Gale, Joseph; Wandel, Amri

2017-01-01

We review the latest findings on extra-solar planets and their potential of having environmental conditions that could support Earth-like life. Focusing on planets orbiting red dwarf (RD) stars, the most abundant stellar type in the Milky Way, we show that including RDs as potential life supporting host stars could increase the probability of finding biotic planets by a factor of up to a thousand, and reduce the estimate of the distance to our nearest biotic neighbour by up to 10. We argue that binary and multiple star systems need to be taken into account when discussing habitability and the abundance of biotic exoplanets, in particular RDs in such systems. Early considerations indicated that conditions on RD planets would be inimical to life, as their habitable zones would be so close to the host star as to make planets tidally locked. This was thought to cause an erratic climate and expose life forms to flares of ionizing radiation. Recent calculations show that these negative factors are less severe than originally thought. It has also been argued that the lesser photon energy of the radiation of the relatively cool RDs would not suffice for oxygenic photosynthesis (OP) and other related energy expending reactions. Numerous authors suggest that OP on RD planets may evolve to utilize photons in the infrared. We however argue, by analogy to the evolution of OP and the environmental physiology and distribution of land-based vegetation on Earth, that the evolutionary pressure to utilize infrared radiation would be small. This is because vegetation on RD planets could enjoy continuous illumination of moderate intensity, containing a significant component of photosynthetic 400-700 nm radiation. We conclude that conditions for OP could exist on RD planets and consequently the evolution of complex life might be possible. Furthermore, the huge number and the long lifetime of RDs make it more likely to find planets with photosynthesis and life around RDs than around Solar type stars.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

NASA Astrophysics Data System (ADS)

Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

2009-07-01

Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

Biochar activated by oxygen plasma for supercapacitors

NASA Astrophysics Data System (ADS)

Gupta, Rakesh Kumar; Dubey, Mukul; Kharel, Parashu; Gu, Zhengrong; Fan, Qi Hua

2015-01-01

Biochar, also known as black carbon, is a byproduct of biomass pyrolysis. As a low-cost, environmental-friendly material, biochar has the potential to replace more expensive synthesized carbon nanomaterials (e.g. carbon nanotubes) for use in future supercapacitors. To achieve high capacitance, biochar requires proper activation. A conventional approach involves mixing biochar with a strong base and baking at a high temperature. However, this process is time consuming and energy inefficient (requiring temperatures >900 °C). This work demonstrates a low-temperature (<150 °C) plasma treatment that efficiently activates a yellow pine biochar. Particularly, the effects of oxygen plasma on the biochar microstructure and supercapacitor characteristics are studied. Significant enhancement of the capacitance is achieved: 171.4 F g-1 for a 5-min oxygen plasma activation, in comparison to 99.5 F g-1 for a conventional chemical activation and 60.4 F g-1 for untreated biochar. This enhancement of the charge storage capacity is attributed to the creation of a broad distribution in pore size and a larger surface area. The plasma activation mechanisms in terms of the evolution of the biochar surface and microstructure are further discussed.

Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

PubMed

Yeo, Boon Siang; Bell, Alexis T

2011-04-13

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed. © 2011 American Chemical Society

A lyophilized and thermal two step synthesis of CoFe alloy nanoparticles embedded in N-doped carbon nanosheets/carbon nanotubes for highly-efficient oxygen evolution reaction.

PubMed

Liu, Yang; Li, Feng; Yang, Haidong; Li, Jing; Ma, Ping; Zhu, Yan; Ma, Jiantai

2018-05-22

There is a vital need to explore highly-efficient and stable nonprecious-metal catalysts for oxygen evolution reaction (OER) to reduce the overpotential and further improve the energy conversion efficiency. Herein, we report a unique and cost-effective lyophilized and thermal two step procedure to synthesize high-performance CoFe alloy nanoparticles embedded in N-doped carbon nanosheets interspersed with carbon nanotubes (CoFe-N-CN/CNTs) hybrid. The lyophilization step during catalysts preparation is beneficial to uniform the dispersion of carbon-like precursors and avoid the agglomeration of metal particles. Meanwhile, the inserted CNTs and doped N in this hybrid provide better electrical conductivity, more chemically active sites, improved mass transport capability and effective gas adsorption/release channels. And all these lead to a high specific surface area of 240.67 m2 g-1, favorable stability and remarkable OER activities with an overpotential of only 285 mV at the current density of 10 mA cm-2 and a Tafel slope of 51.09 mV dec-1 in 1.0 M KOH electrolyte, which is even superior to commercial IrO2 catalysts. The CoFe-N-CN/CNTs hybrid thus exhibits great potential as a highly efficient and earth-abundant anode OER electrocatalyst. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Evolution via Gravitational Differentiation on Low-mass Planets: Implications for Abiotic Oxygen, Water Loss, and Habitability

NASA Astrophysics Data System (ADS)

Wordsworth, R. D.; Schaefer, L. K.; Fischer, R. A.

2018-05-01

The oxidation of rocky planet surfaces and atmospheres, which arises from the twin forces of stellar nucleosynthesis and gravitational differentiation, is a universal process of key importance to habitability and exoplanet biosignature detection. Here we take a generalized approach to this phenomenon. Using a single parameter to describe the redox state, we model the evolution of terrestrial planets around nearby M stars and the Sun. Our model includes atmospheric photochemistry, diffusion and escape, line-by-line climate calculations, and interior thermodynamics and chemistry. In most cases, we find abiotic atmospheric {{{O}}}2 buildup around M stars during the pre-main-sequence phase to be much less than calculated previously, because the planet’s magma ocean absorbs most oxygen liberated from {{{H}}}2{{O}} photolysis. However, loss of noncondensing atmospheric gases after the mantle solidifies remains a significant potential route to abiotic atmospheric {{{O}}}2 subsequently. In all cases, we predict that exoplanets that receive lower stellar fluxes, such as LHS1140b and TRAPPIST-1f and g, have the lowest probability of abiotic {{{O}}}2 buildup and hence may be the most interesting targets for future searches for biogenic {{{O}}}2. Key remaining uncertainties can be minimized in future by comparing our predictions for the atmospheres of hot, sterile exoplanets such as GJ1132b and TRAPPIST-1b and c with observations.

Impact of IrRu Oxygen Evolution Reaction Catalysts on Pt Nanostructured Thin Films under Start-Up/Shutdown Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullen, David A; More, Karren Leslie; Atanasoska, Liliana

Electron microscopy and X-ray photoelectron spectroscopy (XPS) methods have been utilized to study the role of oxygen evolution reaction (OER) catalysts in mitigating degradation arising from start-up/shutdown events. Pt nanostructured thin films (NSTF) were coated with a Ru0.1Ir0.9 OER catalyst at loadings ranging from 1 to 10 g/cm2 and submitted to 5,000 potential cycles within a membrane electrode assembly. Analysis of the as-deposited catalyst showed that Ir and Ru coating is primarily metallic, and further evidence is provided to support the previously reported interaction between Ru and the perylene-red support. Aberration-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopymore » were used to observe the impact of the OER catalysts on Pt dissolution and migration through the membrane. Elemental mapping showed a high percentage of the Ir catalyst was maintained on the NSTF whisker surfaces following testing. The presence of the OER catalysts greatly reduced the smoothing of the Pt NSTF whiskers, which has been correlated with Pt dissolution and losses in electrochemically active surface area. The dissolution of both Ir and Pt led to the formation of IrPt nanoparticle clusters in the membrane close to the cathode, as well as the formation of a Pt band deeper in the membrane.« less

Pyrite-Induced Hydrogen Peroxide Formation as a Driving Force in the Evolution of Photosynthetic Organisms on an Early Earth

NASA Astrophysics Data System (ADS)

Borda, Michael J.; Elsetinow, Alicia R.; Schoonen, Martin A.; Strongin, Daniel R.

2001-09-01

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

PubMed Central

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-01-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2. PMID:28485395

A New Design Strategy for Observing Lithium Oxide Growth-Evolution Interactions Using Geometric Catalyst Positioning.

PubMed

Ryu, Won-Hee; Gittleson, Forrest S; Li, Jinyang; Tong, Xiao; Taylor, André D

2016-08-10

Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O2 cells by characterizing products that grow from the electrode surface. Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. The influence of the catalyst position on product composition is further verified by ex situ X-ray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.

Mass and charge transport relevant to the formation of toroidal lithium peroxide nanoparticles in an aprotic lithium-oxygen battery: An experimental and theoretical modeling study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Xiangyi; Amine, Rachid; Lau, Kah Chun

2017-05-26

The discharge and charge mechanisms of rechargeable Li-O-2 batteries have been the subject of extensive investigation recently. However, they are not fully understood yet. Here we report a systematic study of the morphological transition of Li2O2 from a single crystalline structure to a toroid like particle during the discharge-charge cycle, with the help of a theoretical model to explain the evolution of the Li2O2 at different stages of this process. The model suggests that the transition starts in the first monolayer of Li2O2, and is subsequently followed by a transition from particle growth to film growth if the applied currentmore » exceeds the exchange current for the oxygen reduction reaction in a Li-O-2 cell. Furthermore, a sustainable mass transport of the diffusive active species (e.g., O-2 and Li+) and evolution of the underlying interfaces are critical to dictate desirable oxygen reduction (discharge) and evolution (charge) reactions in the porous carbon electrode of a Li-O-2 cell.« less

A new design strategy for observing lithium oxide growth-evolution interactions using geometric catalyst positioning

DOE PAGES

Ryu, Won -Hee; Gittleson, Forrest S.; Li, Jinyang; ...

2016-06-21

Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O 2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O 2 cells by characterizing products that grow from the electrode surface.more » Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. Lastly, the influence of the catalyst position on product composition is further verified by ex situ Xray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.« less

Fe3O4@NiSx/rGO composites with amounts of heterointerfaces and enhanced electrocatalytic properties for oxygen evolution

NASA Astrophysics Data System (ADS)

Zhu, Guoxing; Xie, Xulan; Liu, Yuanjun; Li, Xiaoyun; Xu, Keqiang; Shen, Xiaoping; Yao, Yinjie; Shah, Sayyar Ali

2018-06-01

The sluggish oxygen evolution kinetics involved in water splitting and various metal-air batteries makes the effective and inexpensive electrocatalysts be highly desirable for oxygen evolution reaction (OER). Herein, an effective and facile two-step route is developed to construct Fe3O4@NiSx composite loaded on reduced graphene oxide (rGO). The morphology and microstructure of the composites were characterized by different characterization techniques. The obtained composites show amounts of heterointerfaces. The shift of binding energy in X-ray photoelectron spectrum demonstrates the existence of interfacial charge transfer effect between Fe3O4 and NiSx. The optimized Fe3O4@NiSx/rGO sample exhibits excellent electrocatalytic performance toward OER in alkaline media, showing 10 mA·cm-2 at η = 330 mV, lower Tafel slope (35.5 mV·dec-1), and good durability, demonstrating a great perspective. The excellent OER performance can be ascribed to the synergetic effect between Fe and Ni species. It is believed that the heterointerfaces between Fe3O4 and NiSx perform as active centers for OER.

Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.

PubMed

Kleidon, Axel

2010-01-13

The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society

Evolution of availability of curcumin inside poly-lactic-co-glycolic acid nanoparticles: impact on antioxidant and antinitrosant properties

PubMed Central

Betbeder, Didier; Lipka, Emmanuelle; Howsam, Mike; Carpentier, Rodolphe

2015-01-01

Purpose Curcumin exhibits antioxidant properties potentially beneficial for human health; however, its use in clinical applications is limited by its poor solubility and relative instability. Nanoparticles exhibit interesting features for the efficient distribution and delivery of curcumin into cells, and could also increase curcumin stability in biological systems. There is a paucity of information regarding the evolution of the antioxidant properties of nanoparticle-encapsulated curcumin. Method We described a simple method of curcumin encapsulation in poly-lactic-co-glycolic acid (PLGA) nanoparticles without the use of detergent. We assessed, in epithelial cells and in an acellular model, the evolution of direct antioxidant and antinitrosant properties of free versus PLGA-encapsulated curcumin after storage under different conditions (light vs darkness, 4°C vs 25°C vs 37°C). Results In epithelial cells, endocytosis and efflux pump inhibitors showed that the increased antioxidant activity of PLGA-encapsulated curcumin relied on bypassing the efflux pump system. Acellular assays showed that the antioxidant effect of curcumin was greater when loaded in PLGA nanoparticles. Furthermore, we observed that light decreased, though heat restored, antioxidant activity of PLGA-encapsulated curcumin, probably by modulating the accessibility of curcumin to reactive oxygen species, an observation supported by results from quenching experiments. Moreover, we demonstrated a direct antinitrosant activity of curcumin, enhanced by PLGA encapsulation, which was increased by light exposure. Conclusion These results suggest that the antioxidant and antinitrosant activities of encapsulated curcumin are light sensitive and that nanoparticle modifications over time and with temperature may facilitate curcumin contact with reactive oxygen species. These results highlight the importance of understanding effects of nanoparticle maturation on an encapsulated drug’s activity. PMID:26345627

Oxygen potentials and phase equilibria in the system Ca–Co–O and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacob, K.T., E-mail: katob@materials.iisc.ernet.in; Gupta, Preeti

2015-01-15

Oxygen potentials established by the equilibrium between three condensed phases, CaO{sub ss}+CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6} and CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6}+Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}, are measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen as the reference electrode. Cation non-stoichiometry and oxygen non-stoichiometry in Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ} are determined using different techniques under defined conditions. Decomposition temperatures and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163} are calculated from the results. The standard entropy and enthalpy of formation of Ca{sub 3}Co{sub 2}O{sub 6} atmore » 298.15 K are evaluated. Using thermodynamic data from this study and auxiliary information from the literature, phase diagram for the ternary system Ca–Co–O is computed. Isothermal sections at representative temperatures are displayed to demonstrate the evolution of phase relations with temperature. - Graphical abstract: Isothermal section of the phase diagram of the system Ca–Co–O at 1250 K. - Highlights: • Improved definition of cation and oxygen nonstoichiometry of Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}. • Measurement of Δμ{sub O{sub 2}} associated with two 3-phase fields as a function of temperature. • Use of solid-state electrochemical cells for accurate measurement of Δμ{sub O{sub 2}}. • Decomposition temperatures and thermodynamic properties for ternary oxides. • Characterization of ternary phase diagram of the system Ca–Co–O.« less

The effect of a lignosulphate type additive on the lead—acid battery positive plate reactions

NASA Astrophysics Data System (ADS)

Ovuru, S. E.; Harrison, J. A.

The electrochemical formation of lead dioxide has been investigated at a lead electrode in a 5 M sulphuric acid solution, and in the presence of phosphoric acid and lignosulphate-type additive. The formation of lead dioxide from lead sulphate, and the reverse reaction, have been investigated by the linear potential sweep method, by an impedance method in which the impedance was measured at the end of each pulse during a potential pulse train, and by a charging curve method in which the current and charge was measured during a similar potential pulse train. The charge measurements prove that the main effect of the additive is to decrease the accompanying oxygen evolution reaction. The impedance measurements, however, show that the additive has a small but significant effect on the structure of the solid lead sulphate and lead dioxide layers.

Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bouhadja, M.; Jakse, N.; Pasturel, A.

2014-06-21

Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al{sub 2}O{sub 3}){sub 1−x}(SiO{sub 2}){sub x}, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO{sub 5} structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution ofmore » the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.« less

Oxygen evolution reaction in nanoconfined carbon nanotubes

NASA Astrophysics Data System (ADS)

Li, Ying; Lu, Xuefeng; Li, Yunfang; Zhang, Xueqing

2018-05-01

Improving oxygen electrochemistry through nanoscopic confinement has recently been highlighted as a promising strategy. In-depth understanding the role of confinement is therefore required. In this study, we simulate the oxygen evolution reaction (OER) on iron oxide nanoclusters under confinement of (7,7) and (8,8) armchair carbon nanotubes (CNTs). The free energies of the four proton coupled electron transfer (PCET) steps and the OER overpotentials are calculated. The Fe4O6 nanocluster confined in (7,7) CNT is found to be the most active for OER among the systems considered in this work. This leads to an increase in catalytic efficiency of OER compared to the hematite (110) surface, which was reported recently as an active surface towards OER. The calculated results show that the OER overpotential depends strongly on the magnetic properties of the iron oxide nanocluster. These findings are helpful for experimental design of efficient catalyst for water splitting applications.

Iron carbide encapsulated by porous carbon nitride as bifunctional electrocatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Wei, Liangqin; Sun, Hongdi; Yang, Tiantian; Deng, Shenzhen; Wu, Mingbo; Li, Zhongtao

2018-05-01

Herein, the study reports a facile and scale-up able strategy to synthesize metal organic frameworks (MOFs) Fe-7,7,8,8-Tetracyanoquinodimethane (Fe-TCNQ) as precursors to develop non-precious metal bifunctional electrocatalysts through a one-step hydrothermal route. Then, Fe3C/carbon nitride (Fe3C@CNx) core-shell structure composites are readily available through pyrolyzing Fe-TCNQ at reasonable temperature, during which hierarchical porous structures with multimodal porosity formed. Nitrogen doped porosity carbon layers can facilitate mass access to active sites and accelerate reaction. Consequently, the optimized catalyst exhibits superior oxygen reduction reaction (ORR) electrocatalytic activity and better catalytic activity for oxygen evolution reaction (OER) in alkaline medium than that of Pt/C, which can be attributed to the synergistic effect of strong coupling between Fe3C and nitrogen doped carbon shells, active sites Fe-NX, optimal level of nitrogen doping, and appropriate multimodal porosity.

Evolution of native point defects in ZnO bulk probed by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Cheng-Xiao; Wang, Ke-Fan; Zhang, Yang; Guo, Feng-Li; Weng, Hui-Min; Ye, Bang-Jiao

2009-05-01

This paper studies the evolution of native point defects with temperature in ZnO single crystals by positron lifetime and coincidence Doppler broadening (CDB) spectroscopy, combined with the calculated results of positron lifetime and electron momentum distribution. The calculated and experimental results of the positron lifetime in ZnO bulk ensure the presence of zinc monovacancy, and zinc monovacancy concentration begins to decrease above 600 °C annealing treatment. CDB is an effective method to distinguish the elemental species, here we combine this technique with calculated electron momentum distribution to determine the oxygen vacancies, which do not trap positrons due to their positive charge. The CDB spectra show that oxygen vacancies do not appear until 600 °C annealing treatment, and increase with the increase of annealing temperature. This study supports the idea that green luminescence has a close relation with oxygen vacancies.

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

NASA Astrophysics Data System (ADS)

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.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Yi; Deng, Ya-Ping; Fu, Jing

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

DOE PAGES

Jiang, Yi; Deng, Ya-Ping; Fu, Jing; ...

2018-01-31

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

FeO2 and FeOOH under deep lower-mantle conditions and Earth's oxygen-hydrogen cycles.

PubMed

Hu, Qingyang; Kim, Duck Young; Yang, Wenge; Yang, Liuxiang; Meng, Yue; Zhang, Li; Mao, Ho-Kwang

2016-06-09

The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.

Oxygen Issue in Core Collapse Supernovae

NASA Astrophysics Data System (ADS)

Elmhamdi, A.

2011-06-01

We study the spectroscopic properties of a selected sample of 26 events within Core Collapse Supernovae (CCSNe) family. Special attention is paid to the nebular oxygen forbidden line [OI] 6300, 6364 Å doublet. We analyze the line flux ratio F6300/F6364 and infer information about the optical depth evolution, densities, volume-filling factors in the oxygen emitting zones. The line luminosity is measured for the sample events and its evolution is discussed on the basis of the bolometric light curve properties in type II and in type Ib-c SNe. The luminosities are then translated into oxygen abundances using two different methods. The results are combined with the determined 56Ni masses and compared with theoretical models by means of the [O/Fe] vs. Mms diagram. Two distinguishable and continuous populations, corresponding to Ib-c and type II SNe, are found. The higher mass nature of the ejecta in type II objects is also imprinted in the [CaII] 7291, 7324Å to [OI] 6300, 6364Å luminosity ratios. Our results may be used as input parameters for theoretical models studying the chemical enrichment of galaxies.

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery – Part 1

PubMed Central

Purushothaman, B. K.; Wainright, J. S.

2012-01-01

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H2 storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1st hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body. PMID:22423175

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery - Part 1.

PubMed

Purushothaman, B K; Wainright, J S

2012-05-15

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H(2) storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1(st) hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body.

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

PubMed

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

2011-05-02

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

Formation of crack-free nanoporous tin oxide layers via simple one-step anodic oxidation in NaOH at low applied voltages

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Gilek, Dominika; Gawlak, Karolina; Jaskuła, Marian; Sulka, Grzegorz D.

2016-12-01

A simple anodic oxidation of metallic tin in fluoride-free alkaline electrolyte at low potentials was proposed as a new and effective strategy for fabrication of crack-free nanoporous tin oxide layers. A low-purity Sn foil (98.8%) was used as a starting material, and a series of anodizations were performed in 1 M NaOH at different conditions such as anodizing potential, and duration of the process. It was proved for the first time that nanostructured tin oxides with ultra-small nanochannels having diameters of <15 nm can be synthesized by simple anodization of metallic tin at a potential of 2 V in 1 M NaOH electrolyte. Increasing anodizing potential to 3 and 4 V allowed for formation of tin oxide layers with much larger pores (40-50 nm in diameter) which were still free from internal cracks and transversal pores. Applying such low potentials significantly reduces the oxide growth rate and suppresses vigorous oxygen evolution at the anode. As a result mechanical deterioration of the oxide structure is prevented while strongly alkaline electrolyte is responsible for formation of the porous layer with completely open pores even at such low potentials. On the contrary, when anodization was carried out at potentials of 5 and 6 V, much faster formation of anodic layer, accompanied by vigorous oxygen gas formation, was observed. In consequence, as grown oxide layers exhibited typical cracked or even stacked internal structure. Finally, we demonstrated for the first time that nanoporous tin oxide layers with segments of different channel sizes can be successfully obtained by simple altering potential during anodization.

Evolution of phenolic compounds and astringency during aging of red wine: effect of oxygen exposure before and after bottling.

PubMed

Gambuti, Angelita; Rinaldi, Alessandra; Ugliano, Maurizio; Moio, Luigi

2013-02-27

The aim of this study was to evaluate the effect of oxygen exposure of red wine, before (micro-oxygenation) and after (nano-oxygenation) bottling, on the phenolic composition and astringency of wine. The astringency was evaluated by sensory analysis and by a method based on the SDS-PAGE of salivary proteins after reaction of saliva with wine (SPI, saliva precipitation index). Micro-oxygenation caused a stabilization of color, but this effect disappeared after long aging. For the wine with the lower pH a decrease of wine astringency and SPI was observed 42 months after micro-oxygenation. Oxygen ingress through the closure postbottling was positively correlated with the decrease of SPI. Therefore, the astringency and reactivity of wines toward salivary proteins of a bottled red wine can be modulated by controlled oxygen exposure during aging. For both experiments the effect of oxygen exposure depended on wine composition.

A prototype of an electric-discharge gas flow oxygen−iodine laser: I. Modeling of the processes of singlet oxygen generation in a transverse cryogenic slab RF discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vagin, N. P.; Ionin, A. A., E-mail: aion@sci.lebedev.ru; Kochetov, I. V.

The existing kinetic model describing self-sustained and electroionization discharges in mixtures enriched with singlet oxygen has been modified to calculate the characteristics of a flow RF discharge in molecular oxygen and its mixtures with helium. The simulations were performed in the gas plug-flow approximation, i.e., the evolution of the plasma components during their motion along the channel was represented as their evolution in time. The calculations were carried out for the O{sub 2}: He = 1: 0, 1: 1, 1: 2, and 1: 3 mixtures at an oxygen partial pressure of 7.5 Torr. It is shown that, under these conditions,more » volumetric gas heating in a discharge in pure molecular oxygen prevails over gas cooling via heat conduction even at an electrode temperature as low as ~100 K. When molecular oxygen is diluted with helium, the behavior of the gas temperature changes substantially: heat removal begins to prevail over volumetric gas heating, and the gas temperature at the outlet of the discharge zone drops to ~220–230 K at room gas temperature at the inlet, which is very important in the context of achieving the generation threshold in an electric-discharge oxygen−iodine laser based on a slab cryogenic RF discharge.« less

Spherical α-MnO₂ Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al-Air Battery.

PubMed

Chen, Kui; Wang, Mei; Li, Guangli; He, Quanguo; Liu, Jun; Li, Fuzhi

2018-04-13

Traditional noble metal platinum (Pt) is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO₂ and nitrogen-doped Ketjenblack (N-KB) (denoted as MnO₂-SM150-0.5) is examined as a potential electrocatalyst in oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). This α-MnO₂ is prepared by redox reaction between K₂S₂O₈ and MnSO₄ in acid conditions with a facile hydrothermal process (named the SM method). As a result, MnO₂-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V) at a discharge density of 50 mA cm -2 in homemade Al-air batteries that is higher than commercial 20% Pt/C (~1.19 V). The superior electrocatalytic performance of MnO₂-SM150-0.5 could be attributed to its higher Mn 3+ /Mn 4+ ratio and the synergistic effect between MnO₂ and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO₂-based composite electrocatalyst.

Light-oxygen effect in cells and its potential applications in tumour therapy (review)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zakharov, S D; Ivanov, Andrei V

1999-12-31

The light-oxygen effect (POE) represents damage (and at low optical doses, activation) of cells by photogeneration of molecular singlet oxygen from O{sub 2} dissolved in cells, in accordance with the reaction: {sup 3}O{sub 2}+h{nu}{yields}{sup 1}O{sub 2}{yields} biological effect. The phases of evolution of the LOE are similar to the phases, observed in cell experiments, of the photodynamic effect (PDE) the mechanism of which is the basis of the familiar method of photodynamic cancer therapy. The reported proofs of the occurrence of the LOE are in the form of detailed spectra of the biological action of optical radiation on cells recordedmore » in four spectral intervals with the aid of tunable lasers. Allowances are made for the relationships governing a new type of cell excitation, associated with reversible structural transitions in the biomembrane. A demonstration is reported of the same efficiency of cw and pulsed irradiation. An analysis is made of the reasons why the optical doses initiating the PDE and the LOE are comparable. The results are given of the first experimental applications of the LOE in tumour therapy. Identification of the primary photoacceptor (O{sub 2}) in cell biostimulation and photodestruction provides a scientific basis for the development of low-intensity laser light-oxygen cancer therapy methods. (lasers in medicine)« less

Geochemistry and the origin of life

NASA Technical Reports Server (NTRS)

Kvenvolden, K. A.

1974-01-01

The origin of life on earth is examined from a viewpoint stressing the validity of the concept of chemical evolution. The different geological formations supporting the mechanisms of the theory are described; the stage of chemical evolution (preceding that of biological evolution) would have taken place from the time of the origin of the earth and meteorites, 4.6 billion years ago, to the early Precambrian period, about 3.2 billion years ago. Specific aspects of the problem discussed include amino acids from spark discharges and their comparison with the Murchison meteorite amino acids, the properties and theory of genesis of the carbonaceous complex within the cold Bokevelt meteorite, ammonion ion concentration in the primitive ocean, the oxygen isotope chemistry of ancient charts, the origin and rise of oxygen concentration in the earth's atmosphere, Precambrian microorganisms and evolutionary events prior to the origin of vascular plants, and biogenicity and significance of the oldest known stromatolites.

Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

2018-05-01

Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

Evolution of the Radial Abundance Gradient and Cold Gas along the Milky Way Disk

NASA Astrophysics Data System (ADS)

Chen, Q. S.; Chang, R. X.; Yin, J.

2014-03-01

We have constructed a phenomenological model of the chemical evolution of the Milky Way disk, and treated the molecular and atomic gas separately. Using this model, we explore the radial profiles of oxygen abundance, the surface density of cold gas, and their time evolutions. It is shown that the model predictions are very sensitive to the adopted infall time-scale. By comparing the model predictions with the observations, we find that the model adopting the star formation law based on H_2 can properly predict the observed radial distributions of cold gas and oxygen abundance gradient along the disk. We also compare the model results with the predictions of the model which adopts the instantaneous recycling approximation (IRA), and find that the IRA assumption has little influence on the model results, especially in the low-density gas region.

Survey of selected seaweeds for simultaneous photoproduction of hydrogen and oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenbaum, E.; Ramus, J.

1983-03-01

Then seaweed species were surveyed for simultaneous photoevolution of hydrogen and oxygen. In an attempt to induce hydrogenase activity (as measured by hydrogen photoproduction) the seaweeds were maintained under anaerobiosis in CO/sub 2/-free seawater for varying lengths of time. Although oxygen evolution was observed in every alga studied, hydrogen evolution was not observed. One conclusion of this research is that, in contrast to the microscopic algae, there is not a single example of a macroscopic alga for which the photoevolution of hydrogen has been observed, in spite of the fact that there are now at least nine macroscopic algal speciesmore » known for which hydrogenase activity has been reported (either by dark hydrogen evolution or light-activated hydrogen uptake). These results are in conflict with the conventional view that algal hydrogenase can catalyze a multiplicity of reactions, one of which is the photoproduction of molecular hydrogen. Two possible explanations for the lack of hydrogen photoproduction in macroscopic algae are presented. It is postulated that electron acceptors other than carbon dioxide can take up reducing equivalents from Photosystem I to the measurable exclusion of hydrogen photoproduction. Alternatively, the hydrogenase system in macroscopic algae may be primarily a hydrogen-uptake system with respect to light-activated reactions. A simple kinetic argument based on recent measurements of the photosynthetic turnover times of simultaneous light-activated hydrogen and oxygen production is presented that supports the second explanation. 25 references, 3 figures, 1 table.« less

Electrochemical Sensing for a Rapidly Evolving World

NASA Astrophysics Data System (ADS)

Mullen, Max Robertson

This dissertation focuses on three projects involving the development of harsh environment gas sensors. The first project discusses the development of a multipurpose oxygen sensor electrode for use in sealing with the common electrolyte yttria stabilized zirconia. The purpose of the sealing function is to produce an internal reference environment maintained by a metal/metal oxide mixture, a criteria for miniaturization of potentiometric oxygen sensing technology. This sensor measures a potential between the internal reference and a sensing environment. The second project discusses the miniaturization of an oxygen sensor and the fabrication of a more generalized electrochemical sensing platform. The third project discusses the discovery of a new mechanism in the electrochemical sensing of ammonia through molecular recognition and the utilization of a sensor taking advantage of the new mechanism. An initial study involving the development of a microwave synthesized La0.8Sr0.2Al0.9Mn0.1O3 sensor electrode material illustrates the ability of the material developed to meet ionic and electronic conducting requirements for effective and Nernstian oxygen sensing. In addition the material deforms plastically under hot isostatic pressing conditions in a similar temperature and pressure regime with yttria stabilized zirconia to produce a seal and survive temperatures up to 1350 °C. In the second project we show novel methods to seal an oxygen environment inside a device cavity to produce an electrochemical sensor body using room temperature plasma-activated bonding and low temperature and pressure assisted plasma-activated bonding with silicon bodies, both in a clean room environment. The evolution from isostatic hot pressing methods towards room temperature complementary metal oxide semiconductor (CMOS) compatible technologies using single crystal silicon substrates in the clean room allows the sealing of devices on a much larger scale. Through this evolution in bonding technology we move from performing non-scalable experiments to produce one sensor at a time to scalable experiments producing six. The bonding methods we use are compatible with wafer scale processing. Practically speaking this means that the oxygen sensor design is scalable to produce thousands of sensors from one single bond. Using this bonding technology we develop a generalized sensing platform that could be used for a variety of sensing applications, including oxygen sensing, but also potentially involving CO2 or NOx as well. Future efforts will involve completing of O2 sensor construction and adaption of the design for CO2 and NOx sensing. The final project focuses on a novel ammonia sensor and sensing mechanism in Ag loaded zeolite Y. The sensor resistance changes upon exposure to ammonia due to the molecular recognition of Ag+ and ammonia, producing Ag(NH3)x+ species. The sensing mechanism is a Grothuss like mechanism based on the hoping of Ag+ centers. The hopping frequency of Ag+ changes upon introduction of ammonia due to the reduced electrostatic interactions between Ag+ and the negatively charged zeolite framework upon formation of Ag(NH3) x+. The change in hopping frequency results in a measurable change in impedance.

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

PubMed

Kuriki, Ryo; Ichibha, Tom; Hongo, Kenta; Lu, Daling; Maezono, Ryo; Kageyama, Hiroshi; Ishitani, Osamu; Oka, Kengo; Maeda, Kazuhiko

2018-05-30

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N 3- , S 2- ) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb 2 Ti 2 O 5.4 F 1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb 2 Ti 2 O 5.4 F 1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb 2 Ti 2 O 5.4 F 1.2 worked as a stable photocatalyst for visible-light-driven H 2 evolution and CO 2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb 2 Ti 2 O 5.4 F 1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Let the right one in: a microeconomic approach to partner choice in mutualisms.

PubMed

Archetti, Marco; Ubeda, Francisco; Fudenberg, Drew; Green, Jerry; Pierce, Naomi E; Yu, Douglas W

2011-01-01

One of the main problems impeding the evolution of cooperation is partner choice. When information is asymmetric (the quality of a potential partner is known only to himself), it may seem that partner choice is not possible without signaling. Many mutualisms, however, exist without signaling, and the mechanisms by which hosts might select the right partners are unclear. Here we propose a general mechanism of partner choice, "screening," that is similar to the economic theory of mechanism design. Imposing the appropriate costs and rewards may induce the informed individuals to screen themselves according to their types and therefore allow a noninformed individual to establish associations with the correct partners in the absence of signaling. Several types of biological symbioses are good candidates for screening, including bobtail squid, ant-plants, gut microbiomes, and many animal and plant species that produce reactive oxygen species. We describe a series of diagnostic tests for screening. Screening games can apply to the cases where by-products, partner fidelity feedback, or host sanctions do not apply, therefore explaining the evolution of mutualism in systems where it is impossible for potential symbionts to signal their cooperativeness beforehand and where the host does not punish symbiont misbehavior.

Chemical potential of oxygen in (U, Pu) mixed oxide with Pu/(U+Pu) = 0.46

NASA Astrophysics Data System (ADS)

Dawar, Rimpi; Chandramouli, V.; Anthonysamy, S.

2016-05-01

Chemical potential of oxygen in (U,Pu) mixed oxide with Pu/(U + Pu) = 0.46 was measured for the first time using H2/H2O gas equilibration combined with solid electrolyte EMF technique at 1073, 1273 and 1473 K covering an oxygen potential range of -525 to -325 kJ mol-1. The effect of oxygen potential on the oxygen to metal ratio was determined. Increase in oxygen potential increases the O/M. In this study the minimum O/M obtained was 1.985 below which reduction was not possible. Partial molar enthalpy ΔHbar O2 and entropy ΔSbar O2 of oxygen were calculated from the oxygen potential data. The values of -752.36 kJ mol-1 and 0.25 kJ mol-1 were obtained for ΔHbar O2 and ΔSbar O2 respectively.

A handheld wireless device for diffuse optical spectroscopic assessment of infantile hemangiomas

NASA Astrophysics Data System (ADS)

Fong, Christopher J.; Flexman, Molly; Hoi, Jennifer W.; Geller, Lauren; Garzon, Maria; Kim, Hyun K.; Hielscher, Andreas H.

2013-03-01

Infantile hemangiomas (IH) are common vascular growths that occur in 5-10% of neonates and have the potential to cause disfiguring and even life-threatening complications. With no objective tool to monitor IH, a handheld wireless device (HWD) that uses diffuse optical spectroscopy has been developed for use in assessment of IH by measurements in absolute oxygenated and deoxygenated hemoglobin concentration as well as scattering in tissue. Reconstructions of these variables can be computed using a multispectral evolution algorithm. We validated the new system by experimental studies using phantom experiments and a clinical study is under way to assess the utility of DOI for IH.

Si photoanode protected by a metal modified ITO layer with ultrathin NiO(x) for solar water oxidation.

PubMed

Sun, Ke; Shen, Shaohua; Cheung, Justin S; Pang, Xiaolu; Park, Namseok; Zhou, Jigang; Hu, Yongfeng; Sun, Zhelin; Noh, Sun Young; Riley, Conor T; Yu, Paul K L; Jin, Sungho; Wang, Deli

2014-03-14

We report an ultrathin NiOx catalyzed Si np(+) junction photoanode for a stable and efficient solar driven oxygen evolution reaction (OER) in water. A stable semi-transparent ITO/Au/ITO hole conducting oxide layer, sandwiched between the OER catalyst and the Si photoanode, is used to protect the Si from corrosion in an alkaline working environment, enhance the hole transportation, and provide a pre-activation contact to the NiOx catalyst. The NiOx catalyzed Si photoanode generates a photocurrent of 1.98 mA cm(-2) at the equilibrium water oxidation potential (EOER = 0.415 V vs. NHE in 1 M NaOH solution). A thermodynamic solar-to-oxygen conversion efficiency (SOCE) of 0.07% under 0.51-sun illumination is observed. The successful development of a low cost, highly efficient, and stable photoelectrochemical electrode based on earth abundant elements is essential for the realization of a large-scale practical solar fuel conversion.

Characterizing infantile hemangiomas with a near-infrared spectroscopic handheld wireless device

NASA Astrophysics Data System (ADS)

Fong, Christopher J.; Hoi, Jennifer W.; Kim, Hyun K.; Behr, Gerald; Geller, Lauren; Antonov, Nina; Flexman, Molly; Garzon, Maria; Hielscher, Andreas H.

2015-03-01

Infantile hemangiomas (IH) are common vascular growths that occur in 5-10% of neonates and have the potential to cause disfiguring and even life-threatening complications. Currently, no objective tool exist to monitor either progression or treatment of IH. To address this unmet clinical need, we have developed a handheld wireless device (HWD) that uses diffuse optical spectroscopy for the assessment of IH. The system employs 4 wavelengths (l=780nm, 805nm, 850nm, and 905nm) and 6 source-detector pairs with distances between 0.6 and 20 mm. Placed on the skin surface, backreflection data is obtained and a multispectral evolution algorithm is used to determine total hemoglobin concentration and tissue oxygen saturation. First results of an ongoing pilot study involving 13 patients (average enrollment age = 25 months) suggest that an increase in hypoxic stress over time can lead to the proliferation of IH. Involuting IH lesions showed an increase in tissue oxygen saturation as well as a decrease in total hemoglobin.

One-Step Electrochemical Preparation of Multilayer Graphene Functionalized with Nitrogen

NASA Astrophysics Data System (ADS)

Ustavytska, Olena; Kurys, Yaroslav; Koshechko, Vyacheslav; Pokhodenko, Vitaly

2017-03-01

A new environmentally friendly one-step method for producing multilayer (preferably 7-9 layers) nitrogen-doped graphene (N-MLG) with a slight amount of oxygen-containing defects was developed. The approach is based on the electrochemical exfoliation of graphite electrode in the presence of azide ions under the conditions of electrolysis with pulse changing of the electrode polarization potential. It was found that usage of azide anions lead not only to the exfoliation of graphite but also to the simultaneous functionalization of graphene sheets by nitrogen atoms (as a result of electrochemical decomposition of azide anions with ammonia evolution). Composition, morphology, structure, and electrochemical properties of N-MLG were characterized by C,H,N analysis, transmission electron microscopy, atomic force microscopy, FTIR, UV-Vis, and Raman spectroscopy, as well as cyclic voltammetry. The perspective of using N-MLG as oxygen reduction reaction electrocatalyst and for the electrochemical analysis of biomarkers (dopamine, ascorbic acid, and uric acid) in their mixtures was shown.

Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst.

PubMed

Sordello, Fabrizio; Ghibaudo, Manuel; Minero, Claudio

2017-07-19

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 μm. This catalyst, coupled with TiO 2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2-13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O 2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

High surface area LaMnO3 nanoparticles enhancing electrochemical catalytic activity for rechargeable lithium-air batteries

NASA Astrophysics Data System (ADS)

Li, Chuanhua; Yu, Zhiyong; Liu, Hanxing; Chen, Kang

2018-02-01

To improve sluggish kinetics of ORR and OER (oxygen reduction and evolution reaction) on the air electrode, the high surface area LaMnO3 nanoparticle catalysts were synthesized by sol-gel method. The specific surface area of as-synthesized pure phase LaMnO3 nanoparticles is 21.21 m2 g-1. The onset potential of high surface area LaMnO3 in alkaline solution is -0.0202 V which is comparable to commercial Pt/C. When the assembled high surface area LaMnO3-based lithium-air batteries were measured at 100 mA g-1, the initial discharge specific capacity could reach 6851.9 mA h g-1(carbon). In addition, lithium-oxygen batteries including high surface area LaMnO3 catalysts could be cycled for 52 cycles at 200 mA g-1 under a limited discharge-charge depth of 500 mA h gcarbon-1.

Evolution of cytochrome oxidase, an enzyme older than atmospheric oxygen.

PubMed

Castresana, J; Lübben, M; Saraste, M; Higgins, D G

1994-06-01

Cytochrome oxidase is a key enzyme in aerobic metabolism. All the recorded eubacterial (domain Bacteria) and archaebacterial (Archaea) sequences of subunits 1 and 2 of this protein complex have been used for a comprehensive evolutionary analysis. The phylogenetic trees reveal several processes of gene duplication. Some of these are ancient, having occurred in the common ancestor of Bacteria and Archaea, whereas others have occurred in specific lines of Bacteria. We show that eubacterial quinol oxidase was derived from cytochrome c oxidase in Gram-positive bacteria and that archaebacterial quinol oxidase has an independent origin. A considerable amount of evidence suggests that Proteobacteria (Purple bacteria) acquired quinol oxidase through a lateral gene transfer from Gram-positive bacteria. The prevalent hypothesis that aerobic metabolism arose several times in evolution after oxygenic photosynthesis, is not sustained by two aspects of the molecular data. First, cytochrome oxidase was present in the common ancestor of Archaea and Bacteria whereas oxygenic photosynthesis appeared in Bacteria. Second, an extant cytochrome oxidase in nitrogen-fixing bacteria shows that aerobic metabolism is possible in an environment with a very low level of oxygen, such as the root nodules of leguminous plants. Therefore, we propose that aerobic metabolism in organisms with cytochrome oxidase has a monophyletic and ancient origin, prior to the appearance of eubacterial oxygenic photosynthetic organisms.

The evolutionary puzzle of egg size, oxygenation and parental care in aquatic environments.

PubMed

Braga Goncalves, Ines; Ahnesjö, Ingrid; Kvarnemo, Charlotta

2015-08-22

Offspring fitness generally improves with increasing egg size. Yet, eggs of most aquatic organisms are small. A common but largely untested assumption is that larger embryos require more oxygen than they can acquire through diffusion via the egg surface, constraining egg size evolution. However, we found no detrimental effects of large egg size on embryo growth and survival under hypoxic conditions. We tested this in the broad-nosed pipefish, Syngnathus typhle, whose males provide extensive care (nourishment, osmoregulation and oxygenation) to their young in a brood pouch on their bodies. We took advantage of this species' pronounced variation in egg size, correlating positively with female size, and tested the effect of hypoxia (40% dissolved oxygen) versus fully oxygenated (100%) water on embryo size and survival of large versus small eggs after 18 days of paternal brooding. Egg size did not affect embryo survival, regardless of O2 treatment. While hypoxia affected embryo size negatively, both large and small eggs showed similar reductions in growth. Males in hypoxia ventilated more and males with large eggs swam more, but neither treatment affected their position in the water column. Overall, our results call into question the most common explanation for constrained egg size evolution in aquatic environments. © 2015 The Author(s).

Rising levels of atmospheric oxygen and evolution of Nrf2.

PubMed

Gacesa, Ranko; Dunlap, Walter C; Barlow, David J; Laskowski, Roman A; Long, Paul F

2016-06-14

In mammals, the master transcription regulator of antioxidant defences is provided by the Nrf2 protein. Phylogenetic analyses of Nrf2 sequences are used here to derive a molecular clock that manifests persuasive evidence that Nrf2 orthologues emerged, and then diverged, at two time points that correlate with well-established geochemical and palaeobiological chronologies during progression of the 'Great Oxygenation Event'. We demonstrate that orthologues of Nrf2 first appeared in fungi around 1.5 Ga during the Paleoproterozoic when photosynthetic oxygen was being absorbed into the oceans. A subsequent significant divergence in Nrf2 is seen during the split between fungi and the Metazoa approximately 1.0-1.2 Ga, at a time when oceanic ventilation released free oxygen to the atmosphere, but with most being absorbed by methane oxidation and oxidative weathering of land surfaces until approximately 800 Ma. Atmospheric oxygen levels thereafter accumulated giving rise to metazoan success known as the Cambrian explosion commencing at ~541 Ma. Atmospheric O2 levels then rose in the mid Paleozoic (359-252 Ma), and Nrf2 diverged once again at the division between mammals and non-mammalian vertebrates during the Permian-Triassic boundary (~252 Ma). Understanding Nrf2 evolution as an effective antioxidant response may have repercussions for improved human health.

The evolutionary puzzle of egg size, oxygenation and parental care in aquatic environments

PubMed Central

Braga Goncalves, Ines; Ahnesjö, Ingrid; Kvarnemo, Charlotta

2015-01-01

Offspring fitness generally improves with increasing egg size. Yet, eggs of most aquatic organisms are small. A common but largely untested assumption is that larger embryos require more oxygen than they can acquire through diffusion via the egg surface, constraining egg size evolution. However, we found no detrimental effects of large egg size on embryo growth and survival under hypoxic conditions. We tested this in the broad-nosed pipefish, Syngnathus typhle, whose males provide extensive care (nourishment, osmoregulation and oxygenation) to their young in a brood pouch on their bodies. We took advantage of this species' pronounced variation in egg size, correlating positively with female size, and tested the effect of hypoxia (40% dissolved oxygen) versus fully oxygenated (100%) water on embryo size and survival of large versus small eggs after 18 days of paternal brooding. Egg size did not affect embryo survival, regardless of O2 treatment. While hypoxia affected embryo size negatively, both large and small eggs showed similar reductions in growth. Males in hypoxia ventilated more and males with large eggs swam more, but neither treatment affected their position in the water column. Overall, our results call into question the most common explanation for constrained egg size evolution in aquatic environments. PMID:26290070

Free Electrons to Molecular Bonds and Back: Closing the Energetic Oxygen Reduction (ORR)-Oxygen Evolution (OER) Cycle Using Core-Shell Nanoelectrocatalysts.

PubMed

Strasser, Peter

2016-11-15

Nanomaterial science and electrocatalytic science have entered a successful "nanoelectrochemical" symbiosis, in which novel nanomaterials offer new frontiers for studies on electrocatalytic charge transfer, while electrocatalytic processes give meaning and often practical importance to novel nanomaterial concepts. Examples of this fruitful symbiosis are dealloyed core-shell nanoparticle electrocatalysts, which often exhibit enhanced kinetic charge transfer rates at greatly improved atom-efficiency. As such, they represent ideal electrocatalyst architectures for the acidic oxygen reduction reaction to water (ORR) and the acidic oxygen evolution reaction from water (OER) that require scarce Pt- and Ir-based catalysts. Together, these two reactions constitute the "O-cycle", a key elemental process loop in the field of electrochemical energy interconversion between electricity (free electrons) and molecular bonds (H 2 O/O 2 ), realized in the combination of water electrolyzers and hydrogen/oxygen fuel cells. In this Account, we describe our recent efforts to design, synthesize, understand, and test noble metal-poor dealloyed Pt and Ir core-shell nanoparticles for deployment in acidic polymer electrolyte membrane (PEM) electrolyzers and PEM fuel cells. Spherical dealloyed Pt core-shell particles, derived from PtNi 3 precursor alloys, showed favorable ORR activity. More detailed size-activity correlation studies further revealed that the 6-8 nm diameter range is a most desirable initial particle size range in order to maximize the particle Ni content after ORR testing and to preserve performance stability. Similarly, dealloyed and oxidized IrO x core-shell particles derived from Ni-rich Ir-Ni precursor particles proved highly efficient oxygen evolution reaction (OER) catalysts in acidic conditions. In addition to the noble metal savings in the particle cores, the Pt core-shell particles are believed to benefit in terms of their mass-based electrochemical kinetics from surface lattice strain effects that tune the adsorption energies and barriers of elementary steps. The molecular mechanism of the kinetic benefit of the dealloyed IrO x particle needs more attention, but there is mounting evidence for ligand hole effects in defect-rich IrO x shells that generate preactive oxygen centers.

The evolution of the metallicity gradient and the star formation efficiency in disc galaxies

NASA Astrophysics Data System (ADS)

Sillero, Emanuel; Tissera, Patricia B.; Lambas, Diego G.; Michel-Dansac, Leo

2017-12-01

We study the oxygen abundance profiles of the gas-phase components in hydrodynamical simulations of pre-prepared disc galaxies including major mergers, close encounters and isolated configurations. We analyse the evolution of the slope of oxygen abundance profiles and the specific star formation rate (sSFR) along their evolution. We find that galaxy-galaxy interactions could generate either positive or negative gas-phase oxygen profiles, depending on the state of evolution. Along the interaction, galaxies are found to have metallicity gradients and sSFR consistent with observations, on average. Strong gas inflows produced during galaxy-galaxy interactions or as a result of strong local instabilities in gas-rich discs are able to produce both a quick dilution of the central gas-phase metallicity and a sudden increase of the sSFR. Our simulations show that, during these events, a correlation between the metallicity gradients and the sSFR can be set up if strong gas inflows are triggered in the central regions in short time-scales. Simulated galaxies without experiencing strong disturbances evolve smoothly without modifying the metallicity gradients. Gas-rich systems show large dispersion along the correlation. The dispersion in the observed relation could be interpreted as produced by the combination of galaxies with different gas-richness and/or experiencing different types of interactions. Hence, our findings suggest that the observed relation might be the smoking gun of galaxies forming in a hierarchical clustering scenario.

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

PubMed Central

Li, Hong; Ke, Fei; Zhu, Junfa

2018-01-01

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. PMID:29414838

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon.

PubMed

Genovese, Chiara; Schuster, Manfred E; Gibson, Emma K; Gianolio, Diego; Posligua, Victor; Grau-Crespo, Ricardo; Cibin, Giannantonio; Wells, Peter P; Garai, Debi; Solokha, Vladyslav; Krick Calderon, Sandra; Velasco-Velez, Juan J; Ampelli, Claudio; Perathoner, Siglinda; Held, Georg; Centi, Gabriele; Arrigo, Rosa

2018-03-05

The carbon-carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (-0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.

An Approach to the Study of the Interactions between Ellagitannins and Oxygen during Oak Wood Aging.

PubMed

García-Estévez, Ignacio; Alcalde-Eon, Cristina; Martínez-Gil, Ana María; Rivas-Gonzalo, Julián C; Escribano-Bailón, M Teresa; Nevares, Ignacio; Del Alamo-Sanza, María

2017-08-09

During the aging of red wine in oak wood barrels, or in alternative aging systems, interactions between the compounds released from wood, the compounds of the wine, and oxygen can take place. The main objective of the present work was to study oxygen-ellagitannin interactions by monitoring their levels in three model systems, all containing the same amounts of French oak chips and differing only in the oxygen content: total absence, only the oxygen released from the chips, and air-saturated (model systems F, OW, and OS, respectively). This study has highlighted the influence of oxygen in the ellagitannins' evolution and the relevance of the oxygen trapped into the oak chips, reporting for the first time the kinetics of oxygen release to the model wine. Furthermore, the indirect contribution of oxygen to the ellagitannins' disappearance by boosting autoxidative reactions has also been pointed out. Vescalagin seems to be the ellagitannin most affected by the initial oxygen levels.

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qinghua; He, Xu; Shi, Jinan

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE PAGES

Zhang, Qinghua; He, Xu; Shi, Jinan; ...

2017-07-24

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Intercalation of Cobalt into the Interlayer of Birnessite Improves Oxygen Evolution Catalysis

DOE PAGES

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; ...

2016-10-10

Here we show that the activity of cobalt for the oxygen evolution reaction (OER) can be enhanced by confining it in the interlayer region of birnessite (layered manganese oxide). The cobalt intercalation was verified by employing state-of-the-art characterization techniques such as XRD, Raman and electron microscopy. It is demonstrated that the Co 2+/birnessite electrocatalyst can reach 10 mA cm -2 at an overpotential of 360 mV with near unity Faradaic efficiency. This overpotential is lower than that which can be achieved by using a pure cobalt hydroxide electrocatalyst for the OER. Furthermore, the Co 2+/birnessite catalyst shows no degradation aftermore » 1000 electrochemical cycles.« less

Evolution of thiol protective systems in prokaryotes

NASA Technical Reports Server (NTRS)

Fahey, R. C.; Newton, G. L.

1986-01-01

Biological thiols are essential elements in most aspects of cell function but undergo rapid oxidation to disulfides in the presence of oxygen. The evolution of systems to protect against such oxygen toxicity was essential to the emergence of aerobic life. The protection system used by eukaryotes is based upon glutathione (GSH) and GSH-dependent enzymes but many bacteria lack GSH and apparently use other mechanisms. The objective of this research is to elaborate the thiol protective mechanisms employed by prokaryotes of widely divergent evolutionary origin and to understand why GSH became the central thiol employed in essentially all higher organisms. Thiol-selective fluorescent labeling and HPLC analysis has been used to determine key monothiol components.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e– + 4H+ ⇌ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc+/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water frommore » aqueous solution to organic solvent, -0.43 kcal mol–1 for MeCN and -1.47 kcal mol–1 for DMF, and the potential of the H+/H2 couple, – 0.028 V in MeCN and -0.662 V in DMF. The H+/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol–1 for acetonitrile and +0.6 kcal mol–1 for DMF.« less

Interplay between oxygen and Fe-S cluster biogenesis: insights from the Suf pathway.

PubMed

Boyd, Eric S; Thomas, Khaleh M; Dai, Yuyuan; Boyd, Jeff M; Outten, F Wayne

2014-09-23

Iron-sulfur (Fe-S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe-S clusters and the fundamental requirement for Fe-S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth's atmosphere. Intriguingly, Fe-S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe-S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe-S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe-S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB-SufC scaffold complex. This analysis provides a new framework for the study of Fe-S cluster biogenesis pathways and Fe-S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen.

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

PubMed

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.

Tracing the evolution of the Galactic bulge with chemodynamical modelling of alpha-elements

NASA Astrophysics Data System (ADS)

Friaça, A. C. S.; Barbuy, B.

2017-02-01

Context. Galactic bulge abundances can be best understood as indicators of bulge formation and nucleosynthesis processes by comparing them with chemo-dynamical evolution models. Aims: The aim of this work is to study the abundances of alpha-elements in the Galactic bulge, including a revision of the oxygen abundance in a sample of 56 bulge red giants. Methods: Literature abundances for O, Mg, Si, Ca and Ti in Galactic bulge stars are compared with chemical evolution models. For oxygen in particular, we reanalysed high-resolution spectra obtained using FLAMES+UVES on the Very Large Telescope, now taking each star's carbon abundances, derived from CI and C2 lines, into account simultaneously. Results: We present a chemical evolution model of alpha-element enrichment in a massive spheroid that represents a typical classical bulge evolution. The code includes multi-zone chemical evolution coupled with hydrodynamics of the gas. Comparisons between the model predictions and the abundance data suggest a typical bulge formation timescale of 1-2 Gyr. The main constraint on the bulge evolution is provided by the O data from analyses that have taken the C abundance and dissociative equilibrium into account. Mg, Si, Ca and Ti trends are well reproduced, whereas the level of overabundance critically depends on the adopted nucleosynthesis prescriptions. Observations collected both at the European Southern Observatory, Paranal, Chile (ESO programmes 71.B-0617A, 73.B0074A, and GTO 71.B-0196)

Whole-genome de novo sequencing reveals unique genes that contributed to the adaptive evolution of the Mikado pheasant.

PubMed

Lee, Chien-Yueh; Hsieh, Ping-Han; Chiang, Li-Mei; Chattopadhyay, Amrita; Li, Kuan-Yi; Lee, Yi-Fang; Lu, Tzu-Pin; Lai, Liang-Chuan; Lin, En-Chung; Lee, Hsinyu; Ding, Shih-Torng; Tsai, Mong-Hsun; Chen, Chien-Yu; Chuang, Eric Y

2018-05-01

The Mikado pheasant (Syrmaticus mikado) is a nearly endangered species indigenous to high-altitude regions of Taiwan. This pheasant provides an opportunity to investigate evolutionary processes following geographic isolation. Currently, the genetic background and adaptive evolution of the Mikado pheasant remain unclear. We present the draft genome of the Mikado pheasant, which consists of 1.04 Gb of DNA and 15,972 annotated protein-coding genes. The Mikado pheasant displays expansion and positive selection of genes related to features that contribute to its adaptive evolution, such as energy metabolism, oxygen transport, hemoglobin binding, radiation response, immune response, and DNA repair. To investigate the molecular evolution of the major histocompatibility complex (MHC) across several avian species, 39 putative genes spanning 227 kb on a contiguous region were annotated and manually curated. The MHC loci of the pheasant revealed a high level of synteny, several rapidly evolving genes, and inverse regions compared to the same loci in the chicken. The complete mitochondrial genome was also sequenced, assembled, and compared against four long-tailed pheasants. The results from molecular clock analysis suggest that ancestors of the Mikado pheasant migrated from the north to Taiwan about 3.47 million years ago. This study provides a valuable genomic resource for the Mikado pheasant, insights into its adaptation to high altitude, and the evolutionary history of the genus Syrmaticus, which could potentially be useful for future studies that investigate molecular evolution, genomics, ecology, and immunogenetics.

In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

PubMed Central

Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

2013-01-01

In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

The environmental impact of the Virgo Cluster on the evolution of dwarf irregular galaxies

NASA Astrophysics Data System (ADS)

Lee, Henry

Dwarf galaxies are the greatest contributor to the total number of galaxies and most are believed to be systems consisting of matter in a near-primordial state. Containing H I gas and H II regions, dwarf irregular galaxies (dIs) can be used as test bodies to evaluate the impact of the environment on their evolution. Oxygen abundances relative to hydrogen within H II regions are a measure of how far the conversion of gas in the interstellar medium into stars has proceeded as a whole, as abundances do not vary significantly with galactocentric radius in dIs. Measurements of the [O III]λ4363 emission line from H II region spectroscopy provide accurate probes of the electron temperature from which oxygen abundances are directly computed. The impact of the Virgo Cluster environment is investigated by comparing the properties of a set of Virgo dIs with those of a set of dIs in the field. To ensure accurate measures of luminosity and abundance, dIs in the field are chosen to have distance determinations from well-calibrated techniques and oxygen abundances derived from [O III]λ4363 measurements. Spectroscopic data are obtained for H II regions in 11 dIs distributed in the central and outer regions of the Virgo Cluster. There is no systematic difference in oxygen abundance between field dIs and Virgo dIs at a given luminosity, showing that there is no detectable difference in their stellar populations. Oxygen abundances for field dIs are well correlated with the gas fraction in a way which shows definitively that evolution has been isolated, i.e., consistent with the “closed-box” model of chemical evolution. For the gas-poor dI UGC 7636 (VCC 1249), the oxygen abundance of a newly discovered intergalactic H II region is combined with the optical luminosity of the dI and the gas mass of the adjacent H I cloud (STET) to show that STET must have once been the interstellar medium of the dI. Tidal interactions of the dI with the elliptical NGC 4472 combined with ram-pressure stripping by the intracluster medium (ICM) best explain the observed properties of the detached cloud and the dI. A “staged” model is described to examine the chemical evolution of a gas-poor dI in the Virgo Cluster. Motivated by the observations, the model is characterized by three phases: isolated evolution, then sudden stripping which removes most of the gas, followed by a second stage of isolated evolution for the residual gas. The time since a typical stripping event is found to be approximately 1 Gyr or less. The GDIs for Virgo dIs correlate roughly with values of the projected X-ray surface brightness of the intracluster gas at the positions of the dIs. Thus, ram-pressure stripping best explains the observed gas-poor dIs in the Virgo sample. Together with the lack of significant fading, these observations suggest that dIs have recently encountered the ICM for the first time. A faded remnant of a gas-poor dI in Virgo will resemble a bright dE/dSph-like object like those presently seen in the cluster core. (Abstract shortened by UMI.)

Electrochemical performances of graphene nanoribbons interlacing hollow NiCo oxide nanocages

NASA Astrophysics Data System (ADS)

Zhao, Xiyu; Li, Xinlu; Huang, Yanchun; Su, Zelong; Long, Junjun; Zhang, Shilei; Sha, Junwei; Wu, Tianli; Wang, Ronghua

2017-12-01

A hybrid of graphene nanoribbons (GNRs) interlacing hollow NiCoO2 (G-HNCO) nanocages in a size range of 300 500 nm with rough surface is synthesized by a chemical etching Cu2O templates and followed by GNR interlacing process. The G-HNCO showed high electrochemical performance of oxygen evolution reaction (OER), which exhibited small onset potential of 1.50 V and achieved current densities of 10 mA cm-2 at potentials of 1.62 V. Also, the hybrid delivered high capacitance of 937.8 F g-1 at 1 A g-1 in supercapacitor (SC) tests as well as stable cycling performance in both OER and SC measurements. The approach to synthesize the hybrid is simple and scalable for other graphene nanoribbon-based electrocatalysts. [Figure not available: see fulltext.

CoM(M=Fe,Cu,Ni)-embedded nitrogen-enriched porous carbon framework for efficient oxygen and hydrogen evolution reactions

NASA Astrophysics Data System (ADS)

Feng, Xiaogeng; Bo, Xiangjie; Guo, Liping

2018-06-01

Rational synthesis and development of earth-abundant materials with efficient electrocatalytic activity and stability for water splitting is a critical but challenging step for sustainable energy application. Herein, a family of bimetal (CoFe, CoCu, CoNi) embedded nitrogen-doped carbon frameworks is developed through a facile and simple thermal conversion strategy of metal-doped zeolitic imidazolate frameworks. Thanks to collaborative superiorities of abundant M-N-C species, modulation action of secondary metal, cobalt-based electroactive phases, template effect of MOFs and unique porous structure, bimetal embedded nitrogen-doped carbon frameworks materials manifest good oxygen and hydrogen evolution catalytic activity. Especially, after modulating the species and molar ratio of metal sources, optimal Co0.75Fe0.25 nitrogen-doped carbon framework catalyst just requires a low overpotential of 303 mV to achieve 10 mA cm-2 with a low Tafel slope (39.49 mV dec-1) for oxygen evolution reaction, which even surpasses that of commercial RuO2. In addition, the optimal catalyst can function as an efficient bifunctional electrocatalyst for overall water splitting with satisfying activity and stability. This development offers an attractive direction for the rational design and fabrication of porous carbon materials for electrochemical energy applications.

Hydrogen production by nitrogen-starved cultures of Anabaena cylindrica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weissman, J.C.; Benemann, J.R.

Nitrogen-starved cultures of the alga Anabaena cylindrica 629 produced hydrogen and oxygen continuously for 7 to 19 days. Hydrogen production attained a maximum level after 1 to 2 days of starvation and was followed by a slow decline. The maximum rates were 30 ml of H/sub 2/ evolved per liter of culture per h or 32 ..mu..l of H/sub 2/ per mg of dry weight per h. In 5 to 7 days the rate of H/sub 2/ evolution by the more productive cultures fell to one-half its maximum value. The addition of 10/sup -4/ to 5 x 10/sup -4/ Mmore » ammonium increased the rate of oxygen evolution and the total hydrogen production of the cultures. H/sub 2/-O/sub 2/ ratios were 4:1 under conditions of complete nitrogen starvation and about 1.7:1 after the addition of ammonium. Thus, oxygen evolution was affected by the extent of the nitrogen starvation. Thermodynamic efficiencies of converting incident light energy to free energy of hydrogen via algal photosynthesis were 0.4 percent. Possible factors limiting hydrogen production were decline of reductant supply and filament breakage. Hydrogen production by filamentous, heterocystous blue-green algae could be used for development of a biophotolysis system.« less

Dependence of Photochemical Escape of Oxygen at Mars on Solar Radiation and Solar Wind Interaction

NASA Astrophysics Data System (ADS)

Cravens, T.; Rahmati, A.; Lillis, R. J.; Fox, J. L.; Bougher, S. W.; Jakosky, B. M.

2016-12-01

The evolution of the atmosphere of Mars and the loss of volatiles over the life of the solar system is a key topic in planetary science. An important loss process in the ionosphere is photochemical escape. In particular, dissociative recombination of O2+ ions (the major ion species) produces fast oxygen atoms, some of which can escape from the planet. Several theoretical models have been constructed over the years to study hot oxygen and its escape from Mars. These model have a number of uncertainties, particularly for the elastic cross sections of O collisions with target neutral species. Recently, the Mars Atmosphere and Volatile Evolution Mission (MAVEN) mission has been rapidly improving our understanding of the upper atmosphere and ionosphere of Mars and its interaction with the external environment (e.g., the solar wind). The purpose of the current paper is to take a simple analytical approach to the oxygen escape problem in order to: (1) study the role that solar flux and solar wind variations have on escape and (2) isolate the effects of uncertainties in oxygen cross sections on the derived oxygen escape rates. Not surprisingly, we find, in agreement with more elaborate numerical models, that the escape flux is directly proportional to the incident solar extreme ultraviolet irradiance and is inversely proportional to the backscatter elastic cross section. The role for atmospheric loss that ion transport plays in the topside ionosphere and how the solar wind interaction drives this will also be discussed.

Ferredoxin:thioredoxin reductase (FTR) links the regulation of oxygenic photosynthesis to deeply rooted bacteria.

PubMed

Balsera, Monica; Uberegui, Estefania; Susanti, Dwi; Schmitz, Ruth A; Mukhopadhyay, Biswarup; Schürmann, Peter; Buchanan, Bob B

2013-02-01

Uncovered in studies on photosynthesis 35 years ago, redox regulation has been extended to all types of living cells. We understand a great deal about the occurrence, function, and mechanism of action of this mode of regulation, but we know little about its origin and its evolution. To help fill this gap, we have taken advantage of available genome sequences that make it possible to trace the phylogenetic roots of members of the system that was originally described for chloroplasts-ferredoxin, ferredoxin:thioredoxin reductase (FTR), and thioredoxin as well as target enzymes. The results suggest that: (1) the catalytic subunit, FTRc, originated in deeply rooted microaerophilic, chemoautotrophic bacteria where it appears to function in regulating CO(2) fixation by the reverse citric acid cycle; (2) FTRc was incorporated into oxygenic photosynthetic organisms without significant structural change except for addition of a variable subunit (FTRv) seemingly to protect the Fe-S cluster against oxygen; (3) new Trxs and target enzymes were systematically added as evolution proceeded from bacteria through the different types of oxygenic photosynthetic organisms; (4) an oxygenic type of regulation preceded classical light-dark regulation in the regulation of enzymes of CO(2) fixation by the Calvin-Benson cycle; (5) FTR is not universally present in oxygenic photosynthetic organisms, and in certain early representatives is seemingly functionally replaced by NADP-thioredoxin reductase; and (6) FTRc underwent structural diversification to meet the ecological needs of a variety of bacteria and archaea.

Synthesis, Structure, and Electrochemical Performance of High Capacity Li 2Cu 0.5Ni 0.5O 2 Cathodes

DOE PAGES

Ruther, Rose E; Zhou, Hui; Dhital, Chetan; ...

2015-09-08

Orthorhombic Li 2NiO 2, Li 2CuO 2, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li 2Cu 0.5Ni 0.5O 2, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li 2CuO 2 are presented. The cycle life of Li 2Cu 0.5Ni 0.5O 2 is shown to depend critically on the voltage window. The formation of Cu 1+ at low voltage and oxygen evolution at highmore » voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.« less

DR-induced Hot Oxygen and Carbon Coronae of Early Mars

NASA Astrophysics Data System (ADS)

Zhao, J.; Chassefiere, E.; Tian, F.; Chaufray, J. Y.; Leblanc, F.

2017-12-01

The evolution of Martian atmosphere is a key aspect to understand the habitability of Mars in time. The distributions of neutral atoms above the exobase of ancient Mars (corona) is important for understanding the interactions between the corona and the solar wind, which could help improving our understanding of the evolution of Martian atmosphere. In this work, a 3-D Monte Carlo Model is built to simulate Martian corona in different period of Mars history based on thermosphere structure corresponding to 1, 3, 10, and 20 times present solar XUV conditions and dissociative recombination (DR) reaction profiles. DR reactions of O2+, CO2+, and CO+ are considered as the sources of primary O and C. Secondary O and C atoms, which are formed through collisions between primaries and background species. We will discuss the dependence of physical properties of Martian corona as functions of solar XUV flux and DR reactions. We will also discuss the potential importance of CO+ DR as a contributor to Martian corona.

Cobalt Covalent Doping in MoS2 to Induce Bifunctionality of Overall Water Splitting.

PubMed

Xiong, Qizhong; Wang, Yun; Liu, Peng-Fei; Zheng, Li-Rong; Wang, Guozhong; Yang, Hua-Gui; Wong, Po-Keung; Zhang, Haimin; Zhao, Huijun

2018-05-28

The layer-structured MoS 2 is a typical hydrogen evolution reaction (HER) electrocatalyst but it possesses poor activity for the oxygen evolution reaction (OER). In this work, a cobalt covalent doping approach capable of inducing HER and OER bifunctionality into MoS 2 for efficient overall water splitting is reported. The results demonstrate that covalently doping cobalt into MoS 2 can lead to dramatically enhanced HER activity while simultaneously inducing remarkable OER activity. The catalyst with optimal cobalt doping density can readily achieve HER and OER onset potentials of -0.02 and 1.45 V (vs reversible hydrogen electrode (RHE)) in 1.0 m KOH. Importantly, it can deliver high current densities of 10, 100, and 200 mA cm -2 at low HER and OER overpotentials of 48, 132, 165 mV and 260, 350, 390 mV, respectively. The reported catalyst activation approach can be adapted for bifunctionalization of other transition metal dichalcogenides. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temporal and spatial evolution characteristics of water environment quality in Heze

NASA Astrophysics Data System (ADS)

Gao, Qian; Zhao, Qiang; Li, Xiumei

2018-06-01

The evolution of water environment is relatively complicated. The study of its characteristics is helpful to grasp the general direction of spatial and temporal evolution of water environment in Heze city, and to carry out water resources development and water environment protection more rationally. The comprehensive pollution index method for calculation, and the observed data are handled by Excel. In order to facilitate the analysis of the basin, Arcgis is utilized to map the watershed map. In addition, for the spatial evolution, surfer12 is used to analyze the spatial evolution characteristics the spatial evolution, and to draw the pictures of spatial evolution of chemical oxygen demand and water quality evolution. The study shows that: (1) In Heze, the quality of water environment has been improved year by year from 2006 to 2013. In 2014, the water environment has deteriorated. The content of volatile phenol has increased greatly, and the evolution trend of COD is close to the trend of the comprehensive pollution index. (2) In terms of Spatial state of water environment, the water quality of Zhuzhao New River and Wanfu River is poor, and Dongyu River water quality is better. Zhuzhao New River and Wanfu River water qualityis often worse than grade V or V, and Dongyu River water quality is mostly maintained in the grade Ⅳ. Through the analysis on the spatial revolution characteristics of water quality and chemical oxygen demand(COD),as a result, water quality is poor in the northern region,and the water quality in the southern region is better in Heze. Although the water quality has changed in recent years, the overall pattern is relatively stable.

Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

DOEpatents

Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

DOEpatents

Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Where did eukaryotes first evolve? Revisiting Mesoproterozoic habitats in the Torridonian Supergroup, NW Scotland

NASA Astrophysics Data System (ADS)

Stüeken, E.; Bellefroid, E. J.; Prave, T.; Asael, D.; Planavsky, N.; Lyons, T. W.

2016-12-01

Eukaryotic microfossils first appear in the early Mesoproterozoic (1.8-1.6 billion years ago), but their record remains sparse for nearly a billion years. This observation has invited hypotheses about oxygen and nutrient limitation of eukaryotic organisms in a stratified ocean underneath an oxygen-poor atmosphere1,2. One of the most fossiliferous units of Mesoproterozoic age is the Torridonian Supergroup in northwestern Scotland (1.2-1.0 Ga)3, which has been interpreted as lacustrine, based on mild boron enrichments and close associations with fluvial sandstones4. Recent studies have documented unusually large δ34S fractionations and Mo enrichments in the Poll a'Mhuilt Member of the lower Torridonian, which led to the interpretation that non-marine environments became oxygenated earlier than the open ocean and were therefore important niches for early eukaryotes5,6. Here we revisited the Poll a'Mhuilt Member with new geochemical tools. We found δ98/95Mo values up to +1.2‰ in euxinic shales and carbonate-bound 87Sr/86Sr ratios of <0.707-0.710 that agree well with constraints on the composition of Mesoproterozoic seawater. Sedimentological observations revealed herringbone cross-bedding and wave ripples indicative of tidal activity. Collectively, our results are consistent with a marine influence during the time of deposition. The high Mo concentrations and δ34S fractions are most likely the results of evapo-concentration of seawater. These rocks can therefore not be used to make inferences about eukaryotic evolution in freshwater habitats. Instead, it is conceivable that marine margins with active oxygen production and dynamic wave mixing were more hospitable settings for eukaryotic evolution than potentially stagnant mid-Proterozoic lakes. 1. Reinhard, CT, et al.(2016) PNAS doi: 10.1073/pnas.1521544113. 2. Anbar, AD & AH Knoll (2002) Science 297: 1137-1142. 3. Strother, PK, et al.(2011) Nature 473: 505-509. 4. Stewart, AD, in: Memoirs of the Geological Society, ed. G Society. Vol. 24. 2002, Bath, UK: Geological Society. 5. Parnell, J, et al.(2010) Nature 468: 290-293. 6. Parnell, J, et al. (2015) Nature Comm. 6: doi:10.1038/ncomms7996.

The Chemical Evolution Carousel of Spiral Galaxies: Azimuthal Variations of Oxygen Abundance in NGC1365

NASA Astrophysics Data System (ADS)

Ho, I.-Ting; Seibert, Mark; Meidt, Sharon E.; Kudritzki, Rolf-Peter; Kobayashi, Chiaki; Groves, Brent A.; Kewley, Lisa J.; Madore, Barry F.; Rich, Jeffrey A.; Schinnerer, Eva; D’Agostino, Joshua; Poetrodjojo, Henry

2017-09-01

The spatial distribution of oxygen in the interstellar medium of galaxies is the key to understanding how efficiently metals that are synthesized in massive stars can be redistributed across a galaxy. We present here a case study in the nearby spiral galaxy NGC 1365 using 3D optical data obtained in the TYPHOON Program. We find systematic azimuthal variations of the H II region oxygen abundance imprinted on a negative radial gradient. The 0.2 dex azimuthal variations occur over a wide radial range of 0.3–0.7 R 25 and peak at the two spiral arms in NGC 1365. We show that the azimuthal variations can be explained by two physical processes: gas undergoes localized, sub-kiloparsec-scale self-enrichment when orbiting in the inter-arm region, and experiences efficient, kiloparsec-scale mixing-induced dilution when spiral density waves pass through. We construct a simple chemical evolution model to quantitatively test this picture and find that our toy model can reproduce the observations. This result suggests that the observed abundance variations in NGC 1365 are a snapshot of the dynamical local enrichment of oxygen modulated by spiral-driven, periodic mixing and dilution.

The Leoncino Dwarf: The Lowest Metallicity Star-Forming Galaxy in the Nearby Universe

NASA Astrophysics Data System (ADS)

McQuinn, Kristen

2017-08-01

Extremely metal-poor (XMP) galaxies are dwarf irregular galaxies with very low metallicities, traced by their gas-phase oxygen abundance. Galaxy evolution scenarios suggest three pathways to form an XMP: (1) secular evolution at low galaxy masses, (2) slow evolution in voids, or (3) dilution of measured abundances from infall of pristine gas. These scenarios have proven challenging to test because, despite concerted efforts, XMP galaxies in the nearby universe have proven hard to find. A notable exception is the recently discovered dwarf galaxy Leoncino. Leoncino has the lowest gas-phase oxygen abundance ever measured in a galaxy in the local Universe. From optical spectroscopy, the oxygen abundance is 12+log(O/H)=7.02+/-0.03, more than 40% lower than the iconic low-metallicity galaxy I Zw 18 and less than 2% Z_sun. Despite a precision oxygen abundance measurement, the evolutionary context of Leoncino remains uncertain without a secure distance. We propose HST WFC3 high-resolution optical imaging of Leoncino to accurately measure the distance to the galaxy using the tip of the red giant branch (TRGB) method. The distance will determine whether Leoncino is located in a typical field environment or in a void, and whether the galaxy is consistent with the luminosity-metallicity relation at low galaxy masses. The detailed study of Leoncino will provide benchmark results for future XMP discoveries in the nearby Universe, and an exceptionally timely comparison for studies of chemically primitive, high-redshift galaxies that will be observable in the JWST era.

Hollow structured carbon-supported nickel cobaltite nanoparticles as an efficient bifunctional electrocatalyst for the oxygen reduction and evolution reaction

DOE PAGES

Wang, Jie; Han, Lili; Lin, Ruoqian; ...

2016-01-05

Here, the exploration of efficient electrocatalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for fuel cells and metal-air batteries. In this study, we developed 3D hollow-structured NiCo 2O 4/C nanoparticles with interconnected pores as bifunctional electrocatalysts, which are transformed from solid NiCo 2 alloy nanoparticles through the Kirkendall effect. The unique hollow structure of NiCo 2O 4 nanoparticles increases the number of active sites and improves contact with the electrolyte to result in excellent ORR and OER performances. In addition, the hollow-structured NiCo 2O 4/C nanoparticles exhibit superior long-term stability for both themore » ORR and OER compared to commercial Pt/C. The template- and surfactant-free synthetic strategy could be used for the low-cost and large-scale synthesis of hollow-structured materials, which would facilitate the screening of high-efficiency catalysts for energy conversion.« less

The Mn4Ca-cluster of the photosynthetic oxygen evolving centre: its structure, function and evolution.

PubMed

Barber, James

2016-10-05

Photosystem II is the chlorophyll containing enzyme in which the very first chemical energy storing reaction of photosynthesis occurs. It does so by splitting water into molecular oxygen and hydrogen equivalents at a catalytic centre composed of four Mn ions and one Ca2+. All the oxygen in the atmosphere is derived from this reaction and without it the biosphere, as we know it, would not exist. Indeed its appearance about 3 billion years ago gave rise to the "big bang of evolution". Thus understanding the structure and functioning of this metal cluster is a major topic in science and here I discuss it in terms of research over of the last twelve years dating back to when it was first proposed to be a Mn3CaO4 cubane with the fourth Mn attached to cubane by one of its oxo bridging bonds. In so doing a number of novel properties emerge for this metallo-protein with implications for its mechanism and evolutionary origin.

Acoustic Emission Analysis of Damage during Compressive Deformation of Amorphous Zr-Based Foams with Aligned, Elongated Pores

NASA Astrophysics Data System (ADS)

Cox, Marie E.; Dunand, David C.

2013-07-01

Acoustic emission methods are used to investigate the evolution of internal microfractural damage during uniaxial compression of amorphous Zr-based foams with aligned, elongated pores. The foams are fabricated by means of densifying a blend of crystalline W powders and amorphous Zr-based powders with two oxygen contents (0.078 and 0.144 wt pct) by warm equal channel angular extrusion, followed by dissolution of the elongated W phase from the fully densified amorphous matrix. For the high-oxygen foams, prior powder boundaries in the amorphous struts promote damage that accumulates during compression, resulting in energy-absorbing properties comparable with the low-oxygen foams without stress-concentrating powder boundaries. The influence of pore orientation on the evolution of microfracture damage and the ability of the foams to accumulate damage without catastrophic failure is also investigated: pores oriented from 24 to 68 deg to the loading direction promote wall bending, resulting in foams with more diffuse damage and better energy-absorbing properties.

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

Biological modulation of planetary atmospheres: The early Earth scenario

NASA Technical Reports Server (NTRS)

Schidlowski, M.

1985-01-01

The establishment and subsequent evolution of life on Earth had a profound impact on the chemical regime at the planet's surface and its atmosphere. A thermodynamic gradient was imposed on near-surface environments that served as the driving force for a number on important geochemical transformations. An example is the redox imbalance between the modern atmosphere and the material of the Earth's crust. Current photochemical models predict extremely low partial pressures of oxygen in the Earth's prebiological atmosphere. There is widespread consensus that any large-scale oxygenation of the primitive atmosphere was contingent on the advent of biological (autotrophic) carbon fixation. It is suggested that photoautotrophy existed both as a biochemical process and as a geochemical agent since at least 3.8 Ga ago. Combining the stoichiometry of the photosynthesis reaction with a carbon isotope mass balance and current concepts for the evolution of the stationary sedimentary mass as a funion of time, it is possible to quantify, the accumulation of oxygen and its photosynthetic oxidation equivalents through Earth history.

Potential barrier heights at metal on oxygen-terminated diamond interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muret, P., E-mail: pierre.muret@neel.cnrs.fr; Traoré, A.; Maréchal, A.

2015-11-28

Electrical properties of metal-semiconductor (M/SC) and metal/oxide/SC structures built with Zr or ZrO{sub 2} deposited on oxygen-terminated surfaces of (001)-oriented diamond films, comprised of a stack of lightly p-doped diamond on a heavily doped layer itself homoepitaxially grown on an Ib substrate, are investigated experimentally and compared to different models. In Schottky barrier diodes, the interfacial oxide layer evidenced by high resolution transmission electron microscopy and electron energy losses spectroscopy before and after annealing, and barrier height inhomogeneities accounts for the measured electrical characteristics until flat bands are reached, in accordance with a model which generalizes that by Tung [Phys.more » Rev. B 45, 13509 (1992)] and permits to extract physically meaningful parameters of the three kinds of interface: (a) unannealed ones, (b) annealed at 350 °C, (c) annealed at 450 °C with the characteristic barrier heights of 2.2–2.5 V in case (a) while as low as 0.96 V in case (c). Possible models of potential barriers for several metals deposited on well defined oxygen-terminated diamond surfaces are discussed and compared to experimental data. It is concluded that interface dipoles of several kinds present at these compound interfaces and their chemical evolution due to annealing are the suitable ingredients that are able to account for the Mott-Schottky behavior when the effect of the metal work function is ignored, and to justify the reverted slope observed regarding metal work function, in contrast to the trend always reported for all other metal-semiconductor interfaces.« less

Co@Pd core-shell nanoparticles embedded in nitrogen-doped porous carbon as dual functional electrocatalysts for both oxygen reduction and hydrogen evolution reactions.

PubMed

Yang, Hongyu; Tang, Zhenghua; Wang, Kai; Wu, Wen; Chen, Yinghuan; Ding, Zhaoqing; Liu, Zhen; Chen, Shaowei

2018-05-21

Developing efficient bi-functional electrocatalysts for both oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for producing hydrogen and utilizing hydrogen effectively to promote electrochemical energy storage in proton membrane exchange fuel cells (PEMFCs). Herein, we report Co@Pd core-shell nanoparticles encapsulated in porous carbon derived from zeolitic imidazolate framework 67 (ZIF-67) for both ORR and HER. The controlled pyrolysis of ZIF-67 can lead to the formation of Co nanoparticles encapsulated in nitrogen-doped porous carbon (Co NC), which subsequently underwent galvanic replacement with Na 2 PdCl 4 to form Co@Pd core-shell nanoparticles embedded in nitrogen-doped porous carbon (Co@Pd NC). The Co@Pd NC exhibited outperformance in ORR and HER than commercial Pd/C, as manifested by more positive onset potential and larger diffusion-limited current density in ORR tests, as well as a small overpotential to drive a current density of 10 mA cm -2 , and much lower Tafel slope in HER tests. It also demonstrated more robust long-term stability than commercial Pd/C for both ORR and HER. Multiple techniques inter-confirmed that the Pd loading in the sample was very low. The findings can pave a path for fabricating a core-shell structured nanocomposite with ultralow noble metal usage as a bifunctional catalyst for electrochemical energy storage and conversion with high-efficiency and remarkable longevity. Copyright © 2018 Elsevier Inc. All rights reserved.

NiFe layered double hydroxide/reduced graphene oxide nanohybrid as an efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions

NASA Astrophysics Data System (ADS)

Zhan, Tianrong; Zhang, Yumei; Liu, Xiaolin; Lu, SiSi; Hou, Wanguo

2016-11-01

Highly active and low-cost bifunctional electrocatalysts for oxygen evolution and reduction reactions (OER and ORR) hold a heart position for the renewable energy technologies such as metal-air batteries and fuel cells. Here, we reported the synthesis of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanohybrid via the facile solvothermal method followed by chemical reduction. The template role of surfactant and the hybridization of rGO supplied the NiFe-LDH/rGO catalyst with a porous nanostructure and an enhanced conductivity, favoring both mass transport and charge communication of electrocatalytic reactions. The NiFe-LDH/rGO composite not only displayed highly efficient OER activity in alkaline solution with a low onset overpotential of 240 mV, but also only needed an overpotential of 250 mV to reach the 10 mA cm-2 current density. The NiFe-LDH/rGO nanohybrid also offered excellent ORR catalytic activity with onset potential at 0.796 V in alkaline media. The rotating-disk and rotating-ring-disk electrodes both revealed that the ORR on NiFe-LDH/rGO mainly involved a direct four-electron reaction pathways accompanying part of the two-electron process. The excellent bifunctional activity of the NiFe-LDH/rGO nanohybrid could be attributed to the synergistic effects of rGO and NiFe-LDH components due to the strongly coupled interactions.

Facile sonochemical synthesis of amorphous NiFe-(oxy)hydroxide nanoparticles as superior electrocatalysts for oxygen evolution reaction.

PubMed

Lee, Eunjik; Park, Ah-Hyeon; Park, Hyun-Uk; Kwon, Young-Uk

2018-01-01

In this work, we present facile synthesis of amorphous Ni/Fe mixed (oxy)hydroxide (NiFe(H)) nanoparticles (NPs) and their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media. a-NiFe(H) NPs have received lots of attention as OER electrocatalysts with many desirable properties. By using a simple sonochemical route, we prepared amorphous Ni and Fe-alkoxide (NiFe(A)) NPs whose composition can be controlled in the entire composition range (Ni 100-x Fe x , 0≤x≤1). These samples are composed of extremely small NiFe(A) NPs with Ni and Fe atoms homogeneously distributed. NiFe(A) NPs are readily converted into corresponding electrocatalytically active NiFe(H) NP by a simple electrochemical treatment. Electrochemical analysis data show that the OER activity of amorphous NiFe(H) samples follows the volcano-type trend when plotted against the Fe content. Ni 70 Fe 30 (H) sample showed the lowest overpotential of 292mV at 10mAcm -2 geo and the lowest Tafel slope of 30.4mVdec -1 , outperforming IrO x /C (326mV, 41.7mVdec -1 ). Our samples are highly durable based on the chronopotentiometry data at the current density of 10mAcm -2 geo for 2h which show that Ni 70 Fe 30 sample maintains the steady-state potential, contrary to the time-varying IrO x /C. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2018-02-01

Metal selenides have great potential for electrochemical energy storage, but are relatively scarce investigated. Herein, a novel hollow core-branch CoSe 2 nanoarray on carbon cloth is designed by a facile selenization reaction of predesigned CoO nanocones. And the electrochemical reaction mechanism of CoSe 2 in supercapacitor is studied in detail for the first time. Compared with CoO, the hollow core-branch CoSe 2 has both larger specific surface area and higher electrical conductivity. When tested as a supercapacitor positive electrode, the CoSe 2 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 CoSe 2 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 CoSe 2 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 CoSe 2 electrode also exhibits better oxygen evolution reaction activity than that of CoO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba0.5Sr0.5Co0.8Fe0.2O3−δ nanofilms with tunable oxidation state

PubMed Central

Chen, Gao; Zhou, Wei; Guan, Daqin; Sunarso, Jaka; Zhu, Yanping; Hu, Xuefeng; Zhang, Wei; Shao, Zongping

2017-01-01

Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal–based catalysts. We report the enhanced performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering. The surface nickel oxide layer of the Ni substrate and the thickness of the BSCF film were further used to tune the intrinsic OER activity and stability of the BSCF catalyst by optimizing the electronic configuration of the transition metal cations in BSCF via the interaction between the nanofilm and the surface nickel oxide, which enables up to 315-fold enhanced mass-specific activity compared to the crystalline BSCF bulk phase. Moreover, the amorphous BSCF–Ni foam anode coupled with the Pt–Ni foam cathode demonstrated an attractive small overpotential of 0.34 V at 10 mA cm−2 for water electrolysis, with a BSCF loading as low as 154.8 μg cm−2. PMID:28691090

Trends in reactivity of electrodeposited 3d transition metals on gold revealed by operando soft x-ray absorption spectroscopy during water splitting

NASA Astrophysics Data System (ADS)

Velasco-Vélez, J. J.; Jones, Travis E.; Pfeifer, Verena; Dong, Chung-Li; Chen, Yu-Xun; Chen, Chieh-Ming; Chen, Hsin-Yu; Lu, Ying-Rui; Chen, Jin-Ming; Schlögl, R.; Knop-Gericke, A.; Chuang, C.-H.

2017-01-01

We activated gold electrodes for their use as electrocatalyst for water splitting by electrodepositing Cu, Ni and Co. A combination of operando x-ray absorption spectroscopy and potentiometric control under aqueous conditions revealed the trends in reactivity yielded by these electrodes, which are directly associated with the cross- and overpotentials as well as the occupancy of the 3d orbitals. It was found that under anodic polarization the materials electrodeposited on gold suffer from a lack of stability, while under cathodic polarization they exhibit stable behavior. The observed activity is strongly related to the lack of stability shown by these composites under anodic polarization revealing a dynamic process ruled by corrosion. By operando x-ray absorption, we established that the overall enhancement of the activity for the oxygen evolution reaction is directly attributable to the cross-potential and corrosion process of the electrodeposited materials. It is associated with the high potential deposition, which is the origin of the incipient oxidation-corrosion resistance of the lattice. We conclude that the observed trends in the total current are directly associated with the loss of oxygen in the metal-oxide lattice and the subsequent dissolution of metallic ions in the electrolyte under anodic polarization.

Metal availability and the expanding network of microbial metabolisms in the Archaean eon

NASA Astrophysics Data System (ADS)

Moore, Eli K.; Jelen, Benjamin I.; Giovannelli, Donato; Raanan, Hagai; Falkowski, Paul G.

2017-09-01

Life is based on energy gained by electron-transfer processes; these processes rely on oxidoreductase enzymes, which often contain transition metals in their structures. The availability of different metals and substrates has changed over the course of Earth's history as a result of secular changes in redox conditions, particularly global oxygenation. New metabolic pathways using different transition metals co-evolved alongside changing redox conditions. Sulfur reduction, sulfate reduction, methanogenesis and anoxygenic photosynthesis appeared between about 3.8 and 3.4 billion years ago. The oxidoreductases responsible for these metabolisms incorporated metals that were readily available in Archaean oceans, chiefly iron and iron-sulfur clusters. Oxygenic photosynthesis appeared between 3.2 and 2.5 billion years ago, as did methane oxidation, nitrogen fixation, nitrification and denitrification. These metabolisms rely on an expanded range of transition metals presumably made available by the build-up of molecular oxygen in soil crusts and marine microbial mats. The appropriation of copper in enzymes before the Great Oxidation Event is particularly important, as copper is key to nitrogen and methane cycling and was later incorporated into numerous aerobic metabolisms. We find that the diversity of metals used in oxidoreductases has increased through time, suggesting that surface redox potential and metal incorporation influenced the evolution of metabolism, biological electron transfer and microbial ecology.

Boron oxynitride nanoclusters on tungsten trioxide as a metal-free cocatalyst for photocatalytic oxygen evolution from water splitting

NASA Astrophysics Data System (ADS)

Xie, Ying Peng; Liu, Gang; Lu, Gao Qing (Max); Cheng, Hui-Ming

2012-02-01

Here we show that B2O3-xNx nanoclusters can be formed on the surface of WO3 particles by a combination of thermal oxidation of tungsten boride (WB) in air and the subsequent nitriding process in gaseous ammonia. The resultant nanoclusters are found to play an apparent role in improving the photocatalytic oxygen evolution of WO3 by promoting the surface separation of photoexcited charge-carriers.Here we show that B2O3-xNx nanoclusters can be formed on the surface of WO3 particles by a combination of thermal oxidation of tungsten boride (WB) in air and the subsequent nitriding process in gaseous ammonia. The resultant nanoclusters are found to play an apparent role in improving the photocatalytic oxygen evolution of WO3 by promoting the surface separation of photoexcited charge-carriers. Electronic supplementary information (ESI) available: (1) Experimental section. (2) XRD patterns, FT-IR and Raman spectra of B2O3@WO3 and B2O3-xNx@WO3. (3) Time course of O2 evolution from water splitting using B2O3@WO3 and B2O3-xNx@WO3. (4) XRD pattern and SEM image of pure WO3, UV-visible absorption spectra of pure WO3 and N-WO3. (5) UV-visible absorption spectra of bulk B2O3 and schematic of band edges of WO3, bulk B2O3, and B2O3-xNx nanocluster. See DOI: 10.1039/c2nr11846g

Rising levels of atmospheric oxygen and evolution of Nrf2

PubMed Central

Gacesa, Ranko; Dunlap, Walter C.; Barlow, David J.; Laskowski, Roman A.; Long, Paul F.

2016-01-01

In mammals, the master transcription regulator of antioxidant defences is provided by the Nrf2 protein. Phylogenetic analyses of Nrf2 sequences are used here to derive a molecular clock that manifests persuasive evidence that Nrf2 orthologues emerged, and then diverged, at two time points that correlate with well-established geochemical and palaeobiological chronologies during progression of the ‘Great Oxygenation Event’. We demonstrate that orthologues of Nrf2 first appeared in fungi around 1.5 Ga during the Paleoproterozoic when photosynthetic oxygen was being absorbed into the oceans. A subsequent significant divergence in Nrf2 is seen during the split between fungi and the Metazoa approximately 1.0–1.2 Ga, at a time when oceanic ventilation released free oxygen to the atmosphere, but with most being absorbed by methane oxidation and oxidative weathering of land surfaces until approximately 800 Ma. Atmospheric oxygen levels thereafter accumulated giving rise to metazoan success known as the Cambrian explosion commencing at ~541 Ma. Atmospheric O2 levels then rose in the mid Paleozoic (359–252 Ma), and Nrf2 diverged once again at the division between mammals and non-mammalian vertebrates during the Permian-Triassic boundary (~252 Ma). Understanding Nrf2 evolution as an effective antioxidant response may have repercussions for improved human health. PMID:27297177

Chemical production on Mars using in situ propellant production technology

NASA Technical Reports Server (NTRS)

Ash, Robert L.

1986-01-01

In situ propellant production (ISPP) was examined in terms of its applicability to a manned Mars mission. Production of oxygen from Martian atmosphere was used as the baseline system for ISPP technology assessment. It was concluded that production of oxygen was an important element in a manned Mars mission which could be developed in terrestrial laboratories. Expert system methodology will be required to enable reliable, autonomous production of oxygen. Furthermore, while no major technical breakthroughs are required, this research requires a long lead time to permit its systematic evolution.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

PubMed Central

Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

2017-01-01

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

Bimetallic NiFe2O4 synthesized via confined carburization in NiFe-MOFs for efficient oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Fang, Zhiqiang; Hao, Zhaomin; Dong, Qingsong; Cui, Yong

2018-04-01

Transition metal oxides that derived from metal-organic framework (MOF) precursor have intensively received attention because of their numerous electrochemical applications. Bimetallic Ni-Fe oxides have been rarely reported on the basis of MOF-related strategy. Herein, a bimetallic NiFe2O4 was successfully synthesized via confined carburization in NiFe-MOF precursors and characterized by XRD, XPS, SEM, and TEM. After conducting an investigation of oxygen evolution reaction (OER), the as-synthesized NiFe2O4 material exhibited good catalytic efficiency and high stability and durability in alkaline media. The as-synthesized NiFe2O4 material would promote the development of MOFs in non-noble-metal OER catalyst.

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

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

PubMed

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

2018-07-13

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

Spring Blooms Observed with Biochemical Profiling Floats from a Chemical and Biological Perspective

NASA Astrophysics Data System (ADS)

Plant, J. N.; Johnson, K. S.; Sakamoto, C.; Jannasch, H. W.; Coletti, L. J.; Elrod, V.

2015-12-01

Recently there has been renewed interest in the mechanisms which control the seasonal increases in plankton biomass (spring blooms). Changes in physical and chemical forcing (light, wind, heat and nutrients) may increase the specific growth rate of phytoplankton. These changes may also shift the predator - prey relationships within the food web structure, which can alter the balance between plankton growth and loss rates. Biogeochemical profiling floats provide a means to observe the seasonal evolution of spring blooms from a physical, chemical and biological perspective in near real time. Floats equipped with optical sensors to measure nitrate, oxygen, chlorophyll fluorescence, and optical backscatter now have a presence in many ocean regions including the North Pacific, Subarctic Pacific, North Atlantic, South Atlantic and the Southern Ocean. Data from these regions are used to compare and contrast the evolution of spring blooms. The evolution of the bloom is examined using both chemical (oxygen, nitrate) and biooptical (phytoplankton from chlorophyll fluorescence and particulate organic carbon from optical backscatter) sensors under vastly different environmental conditions.

Maximal Predictability Approach for Identifying the Right Descriptors for Electrocatalytic Reactions.

PubMed

Krishnamurthy, Dilip; Sumaria, Vaidish; Viswanathan, Venkatasubramanian

2018-02-01

Density functional theory (DFT) calculations are being routinely used to identify new material candidates that approach activity near fundamental limits imposed by thermodynamics or scaling relations. DFT calculations are associated with inherent uncertainty, which limits the ability to delineate materials (distinguishability) that possess high activity. Development of error-estimation capabilities in DFT has enabled uncertainty propagation through activity-prediction models. In this work, we demonstrate an approach to propagating uncertainty through thermodynamic activity models leading to a probability distribution of the computed activity and thereby its expectation value. A new metric, prediction efficiency, is defined, which provides a quantitative measure of the ability to distinguish activity of materials and can be used to identify the optimal descriptor(s) ΔG opt . We demonstrate the framework for four important electrochemical reactions: hydrogen evolution, chlorine evolution, oxygen reduction and oxygen evolution. Future studies could utilize expected activity and prediction efficiency to significantly improve the prediction accuracy of highly active material candidates.

Accreting CO material onto ONe white dwarfs towards accretion-induced collapse

NASA Astrophysics Data System (ADS)

Wu, Cheng-Yuan; Wang, Bo

2018-03-01

The final outcomes of accreting ONe white dwarfs (ONe WDs) have been studied for several decades, but there are still some issues that are not resolved. Recently, some studies suggested that the deflagration of oxygen would occur for accreting ONe WDs with Chandrasekhar masses. In this paper, we aim to investigate whether ONe WDs can experience accretion-induced collapse (AIC) or explosions when their masses approach the Chandrasekhar limit. Employing the stellar evolution code Modules for Experiments in Stellar Astrophysics (MESA), we simulate the long-term evolution of ONe WDs with accreting CO material. The ONe WDs undergo weak multicycle carbon flashes during the mass-accretion process, leading to mass increase of the WDs. We found that different initial WD masses and mass-accretion rates influence the evolution of central density and temperature. However, the central temperature cannot reach the explosive oxygen ignition temperature due to neutrino cooling. This work implies that the final outcome of accreting ONe WDs is electron-capture induced collapse rather than thermonuclear explosion.

Hydrogen production by photoelectrolytic decomposition of H2O using solar energy

NASA Technical Reports Server (NTRS)

Rauh, R. D.; Alkaitis, S. A.; Buzby, J. M.; Schiff, R.

1980-01-01

Photoelectrochemical systems for the efficient decomposition of water are discussed. Semiconducting d band oxides which would yield the combination of stability, low electron affinity, and moderate band gap essential for an efficient photoanode are sought. The materials PdO and Fe-xRhxO3 appear most likely. Oxygen evolution yields may also be improved by mediation of high energy oxidizing agents, such as CO3(-). Examination of several p type semiconductors as photocathodes revealed remarkable stability for p-GaAs, and also indicated p-CdTe as a stable H2 photoelectrode. Several potentially economical schemes for photoelectrochemical decomposition of water were examined, including photoelectrochemical diodes and two stage, four photon processes.

Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

PubMed

Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

2013-01-01

In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

Fuel cell applied research: Electrocatalysis and materials

NASA Astrophysics Data System (ADS)

Srinivasan, S.; Isaacs, H.; McBreen, J.; Ogrady, W. E.; Olender, H.; Olmer, L. J.; Schouler, E. J. L.; Adzic, R. R.

1980-03-01

The effect of underpotential deposited metal layers on the electrocatalysis of fuel cell reactions is studied. The potential for developing organic compound/air fuel cells using underpotential deposited Pb adatoms to enhance the electrocatalysis of the fuel electrode is explored. The effects of adsorbed layers of Pb, Tl and Bi on formic acid and methanol oxidation on platinum in 85 percent H3PO4 were investigated. The effect of crystal orientation on formic acid oxidation on platinum in 1 M CHlO2 was investigated. The kinetics of the oxygen reduction and evolution reactions at the electrode (metal or oxide) solid electrolyte (yttria stabilized zirconia) interface were investigated using ac and dc techniques.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

In situ grown Ni9S8 nanorod/O-MoS2 nanosheet nanocomposite on carbon cloth as a free binder supercapacitor electrode and hydrogen evolution catalyst

NASA Astrophysics Data System (ADS)

Li, Songzhan; Chen, Tian; Wen, Jian; Gui, Pengbin; Fang, Guojia

2017-11-01

Transition metal sulfide nanostructure composites have received significant attention as energy conversion and storage devices. In this work, we report a three-dimension (3D) nanostructure with the Ni9S8 nanorods embedded in oxygen-incorporated MoS2 (O-MoS2) nanosheets for supercapacitors and hydrogen evolution catalysts. The in situ grown Ni9S8/O-MoS2 nanocomposite on carbon cloth can be used as a free binder supercapacitor electrode and hydrogen evolution catalyst. The Ni9S8/O-MoS2 nanocomposite exhibits electrochemical behaviors with a specific capacitance of 907 F g-1 (at 2 A g-1) and good cycle stability after 1200 cycles due to its unique mutual embedding 3D nanostructure. Furthermore, the Ni9S8/O-MoS2 nanocomposite also shows highly electrocatalytic features for hydrogen production with an onset overpotential of ˜150 mV and a low Tafel slope of ˜81 mV dec-1. The oxygen incorporation of MoS2 provides more active sites to participate in the catalytic process for the hydrogen evolution reaction.

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Genetic adaptations of the plateau zokor in high-elevation burrows.

PubMed

Shao, Yong; Li, Jin-Xiu; Ge, Ri-Li; Zhong, Li; Irwin, David M; Murphy, Robert W; Zhang, Ya-Ping

2015-11-25

The plateau zokor (Myospalax baileyi) spends its entire life underground in sealed burrows. Confronting limited oxygen and high carbon dioxide concentrations, and complete darkness, they epitomize a successful physiological adaptation. Here, we employ transcriptome sequencing to explore the genetic underpinnings of their adaptations to this unique habitat. Compared to Rattus norvegicus, genes belonging to GO categories related to energy metabolism (e.g. mitochondrion and fatty acid beta-oxidation) underwent accelerated evolution in the plateau zokor. Furthermore, the numbers of positively selected genes were significantly enriched in the gene categories involved in ATPase activity, blood vessel development and respiratory gaseous exchange, functional categories that are relevant to adaptation to high altitudes. Among the 787 genes with evidence of parallel evolution, and thus identified as candidate genes, several GO categories (e.g. response to hypoxia, oxygen homeostasis and erythrocyte homeostasis) are significantly enriched, are two genes, EPAS1 and AJUBA, involved in the response to hypoxia, where the parallel evolved sites are at positions that are highly conserved in sequence alignments from multiple species. Thus, accelerated evolution of GO categories, positive selection and parallel evolution at the molecular level provide evidences to parse the genetic adaptations of the plateau zokor for living in high-elevation burrows.

Space Station evolution study oxygen loop closure

NASA Technical Reports Server (NTRS)

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.

Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

DOE PAGES

Barron, Sara C.; Lee, Ho Nyung; Petrie, Jonathan R.; ...

2016-05-27

Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoO x) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this importantmore » reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.« less

Uniting sex and eukaryote origins in an emerging oxygenic world.

PubMed

Gross, Jeferson; Bhattacharya, Debashish

2010-08-23

Theories about eukaryote origins (eukaryogenesis) need to provide unified explanations for the emergence of diverse complex features that define this lineage. Models that propose a prokaryote-to-eukaryote transition are gridlocked between the opposing "phagocytosis first" and "mitochondria as seed" paradigms, neither of which fully explain the origins of eukaryote cell complexity. Sex (outcrossing with meiosis) is an example of an elaborate trait not yet satisfactorily addressed in theories about eukaryogenesis. The ancestral nature of meiosis and its dependence on eukaryote cell biology suggest that the emergence of sex and eukaryogenesis were simultaneous and synergic and may be explained by a common selective pressure. We propose that a local rise in oxygen levels, due to cyanobacterial photosynthesis in ancient Archean microenvironments, was highly toxic to the surrounding biota. This selective pressure drove the transformation of an archaeal (archaebacterial) lineage into the first eukaryotes. Key is that oxygen might have acted in synergy with environmental stresses such as ultraviolet (UV) radiation and/or desiccation that resulted in the accumulation of reactive oxygen species (ROS). The emergence of eukaryote features such as the endomembrane system and acquisition of the mitochondrion are posited as strategies to cope with a metabolic crisis in the cell plasma membrane and the accumulation of ROS, respectively. Selective pressure for efficient repair of ROS/UV-damaged DNA drove the evolution of sex, which required cell-cell fusions, cytoskeleton-mediated chromosome movement, and emergence of the nuclear envelope. Our model implies that evolution of sex and eukaryogenesis were inseparable processes. Several types of data can be used to test our hypothesis. These include paleontological predictions, simulation of ancient oxygenic microenvironments, and cell biological experiments with Archaea exposed to ROS and UV stresses. Studies of archaeal conjugation, prokaryotic DNA recombination, and the universality of nuclear-mediated meiotic activities might corroborate the hypothesis that sex and the nucleus evolved to support DNA repair. Oxygen tolerance emerges as an important principle to investigate eukaryogenesis. The evolution of eukaryotic complexity might be best understood as a synergic process between key evolutionary innovations, of which meiosis (sex) played a central role. This manuscript was reviewed by Eugene V. Koonin, Anthony M. Poole, and Gáspár Jékely.

Insight into the structure and functional application of the Sr0.95Ce0.05CoO3-δ cathode for solid oxide fuel cells.

PubMed

Yang, Wei; Zhang, Huairuo; Sun, Chunwen; Liu, Lilu; Alonso, J A; Fernández-Díaz, M T; Chen, Liquan

2015-04-06

A new perovskite cathode, Sr0.95Ce0.05CoO3-δ, performs well for oxygen-reduction reactions in solid oxide fuel cells (SOFCs). We gain insight into the crystal structure of Sr1-xCexCoO3-δ (x = 0.05, 0.1) and temperature-dependent structural evolution of Sr0.95Ce0.05CoO3-δ by X-ray diffraction, neutron powder diffraction, and scanning transmission electron microscopy experiments. Sr0.9Ce0.1CoO3-δ shows a perfectly cubic structure (a = a0), with a large oxygen deficiency in a single oxygen site; however, Sr0.95Ce0.05CoO3-δ exhibits a tetragonal perovskite superstructure with a double c axis, defined in the P4/mmm space group, that contains two crystallographically different cobalt positions, with distinct oxygen environments. The structural evolution of Sr0.95Ce0.05CoO3-δ at high temperatures was further studied by in situ temperature-dependent NPD experiments. At 1100 K, the oxygen atoms in Sr0.95Ce0.05CoO3-δ show large and highly anisotropic displacement factors, suggesting a significant ionic mobility. The test cell with a La0.8Sr0.2Ga0.83Mg0.17O3-δ-electrolyte-supported (∼300 μm thickness) configuration yields peak power densities of 0.25 and 0.48 W cm(-2) at temperatures of 1023 and 1073 K, respectively, with pure H2 as the fuel and ambient air as the oxidant. The electrochemical impedance spectra evolution with time of the symmetric cathode fuel cell measured at 1073 K shows that the Sr0.95Ce0.05CoO3-δ cathode possesses superior ORR catalytic activity and long-term stability. Mixed ionic-electronic conduction properties of Sr0.95Ce0.05CoO3-δ account for its good performance as an oxygen-reduction catalyst.

A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.

PubMed

Poisson, Lionel; Nandi, Dhananjay; Soep, Benoît; Hochlaf, Majdi; Boggio-Pasqua, Martial; Mestdagh, Jean-Michel

2014-01-14

How much time does it take for a wavepacket to roam on a multidimensional potential energy surface? This combined theoretical and pump-probe femtosecond time experiment on 2-hydroxypyridine proposes an answer. Bypassing the well-established transition state and conical intersection relaxation pathways, this molecular system undergoes relaxation into the S1 excited state: the central ring is destabilized by the electronic excitation, within ~100 fs after absorption of the pump photon, then the H-atom bound to oxygen undergoes a roaming behavior when it couples to other degrees of freedom of the molecule. The timescale of the latter process is measured to be ~1.3 ps. Further evolution of the wavepacket is either an oscillation onto the S1 potential or a conversion into the triplet state for timescale larger than ~110 ps. Our work introduces a new tool for the understanding of time-resolved relaxation dynamics applied to large molecules through the roaming dynamics characterized by its strongly delocalized wavepacket on flat molecular potential energy surfaces.

Microstructure evolution characteristics induced by oxygen vacancy generation in anatase TiO2 based resistive switching devices

NASA Astrophysics Data System (ADS)

Liu, Chen; Gao, Bin; Huang, Peng; Kang, Jinfeng

2017-03-01

In this work, first principle calculations are employed to study the microstructure characteristics of the anatase TiO2 resistive switching material associated with the generation of oxygen vacancy (V o) based nanofilaments during the switching process. The calculations indicate that both the magnéli phase Ti4O7 and V o-defect phase of anatase TiO2 may be formed with the generation of oxygen vacancies during the forming and SET processes. Based on the calculations, a new physical insight is proposed to clarify the microstructure evolution characteristics of the anatase TiO2 resistive switching material and the correlation with resistive switching behaviors. During the forming or SET process, the anatase TiO2 is first excited to a transition state with the generation of oxygen vacancies, then fully relaxes to a stable V o-defect state. This V o-defect state may either recover to the original state with the recombination of the oxygen vacancies, which causes the reversible resistive switching behavior, or further transform to a much more stable state—the magnéli phase Ti4O7, through a phase transition process with the generation of many more oxygen vacancies. The phase transition from V o- defective anatase phase to magnéli phase Ti4O7 causes the failure of the resistive switching due to the significantly reduced possibility of the reversible phase transition from the magnéli phase to the anatase phase, compared with the possibility of the recombination from the V o-defective anatase.

Hot oxygen escape from Mars: Simple scaling with solar EUV irradiance

NASA Astrophysics Data System (ADS)

Cravens, T. E.; Rahmati, A.; Fox, Jane L.; Lillis, R.; Bougher, S.; Luhmann, J.; Sakai, S.; Deighan, J.; Lee, Yuni; Combi, M.; Jakosky, B.

2017-01-01

The evolution of the atmosphere of Mars and the loss of volatiles over the lifetime of the solar system is a key topic in planetary science. An important loss process for atomic species, such as oxygen, is ionospheric photochemical escape. Dissociative recombination of O2+ ions (the major ion species) produces fast oxygen atoms, some of which can escape from the planet. Many theoretical hot O models have been constructed over the years, although a number of uncertainties are present in these models, particularly concerning the elastic cross sections of O atoms with CO2. Recently, the Mars Atmosphere and Volatile Evolution mission has been rapidly improving our understanding of the upper atmosphere and ionosphere of Mars and its interaction with the external environment (e.g., solar wind), allowing a new assessment of this important loss process. The purpose of the current paper is to take a simple analytical approach to the oxygen escape problem in order to (1) study the role that variations in solar radiation or solar wind fluxes could have on escape in a transparent fashion and (2) isolate the effects of uncertainties in oxygen cross sections on the derived oxygen escape rates. In agreement with several more elaborate numerical models, we find that the escape flux is directly proportional to the incident solar extreme ultraviolet irradiance and is inversely proportional to the backscatter elastic cross section. The amount of O lost due to ion transport in the topside ionosphere is found to be about 5-10% of the total.

Oxygen potential of uranium--plutonium oxide as determined by controlled- atmosphere thermogravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swanson, Gerald C.

1975-10-01

The oxygen-to-metal atom ratio, or O/M, of solid solution uranium- plutonium oxide reactor fuel is a measure of the concentration of crystal defects in the oxide which affect many fuel properties, particularly, fuel oxygen potential. Fabrication of a high-temperature oxygen electrode, employing an electro-active tip of oxygen-deficient solid-state electrolyte, intended to confirm gaseous oxygen potentials is described. Uranium oxide and plutonium oxide O/M reference materials were prepared by in situ oxidation of high purity metals in the thermobalance. A solid solution uranium-plutonium oxide O/M reference material was prepared by alloying the uranium and plutonium metals in a yttrium oxide cruciblemore » at 1200°C and oxidizing with moist He at 250°C. The individual and solid solution oxides were isothermally equilibrated with controlled oxygen potentials between 800 and 1300°C and the equilibrated O/ M ratios calculated with corrections for impurities and buoyancy effects. Use of a reference oxygen potential of -100 kcal/mol to produce an O/M of 2.000 is confirmed by these results. However, because of the lengthy equilibration times required for all oxides, use of the O/M reference materials rather than a reference oxygen potential is recommended for O/M analysis methods calibrations.« less

Oxygen stable isotope ratios from British oak tree-rings provide a strong and consistent record of past changes in summer rainfall

NASA Astrophysics Data System (ADS)

Young, Giles H. F.; Loader, Neil J.; McCarroll, Danny; Bale, Roderick J.; Demmler, Joanne C.; Miles, Daniel; Nayling, Nigel T.; Rinne, Katja T.; Robertson, Iain; Watts, Camilla; Whitney, Matthew

2015-12-01

United Kingdom (UK) summers dominated by anti-cyclonic circulation patterns are characterised by clear skies, warm temperatures, low precipitation totals, low air humidity and more enriched oxygen isotope ratios (δ18O) in precipitation. Such conditions usually result in relatively more positive (enriched) oxygen isotope ratios in tree leaf sugars and ultimately in the tree-ring cellulose formed in that year, the converse being true in cooler, wet summers dominated by westerly air flow and cyclonic conditions. There should therefore be a strong link between tree-ring δ18O and the amount of summer precipitation. Stable oxygen isotope ratios from the latewood cellulose of 40 oak trees sampled at eight locations across Great Britain produce a mean δ18O chronology that correlates strongly and significantly with summer indices of total shear vorticity, surface air pressure, and the amount of summer precipitation across the England and Wales region of the United Kingdom. The isotope-based rainfall signal is stronger and much more stable over time than reconstructions based upon oak ring widths. Using recently developed methods that are precise, efficient and highly cost-effective it is possible to measure both carbon (δ13C) and oxygen (δ18O) isotope ratios simultaneously from the same tree-ring cellulose. In our study region, these two measurements from multiple trees can be used to reconstruct summer temperature (δ13C) and summer precipitation (δ18O) with sufficient independence to allow the evolution of these climate parameters to be reconstructed with high levels of confidence. The existence of long, well-replicated oak tree-ring chronologies across the British Isles mean that it should now be possible to reconstruct both summer temperature and precipitation over many centuries and potentially millennia.

Macroscale cobalt-MOFs derived metallic Co nanoparticles embedded in N-doped porous carbon layers as efficient oxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Lu, Hai-Sheng; Zhang, Haimin; Liu, Rongrong; Zhang, Xian; Zhao, Huijun; Wang, Guozhong

2017-01-01

Metal-organic frameworks (MOFs) materials have aroused great research interest in different areas owing to their unique properties, such as high surface area, various composition, well-organized framework and controllable porous structure. Controllable fabrication of MOFs materials at macro-scale may be more promising for their large-scale practical applications. Here we report the synthesis of macro-scale Co-MOFs crystals using 1,3,5-benzenetricarboxylic acid (H3BTC) linker in the presence of Co2+, triethylamine (TEA) and nonanoic acid by a facile solvothermal reaction. Further, the as-fabricated Co-MOFs as precursor was pyrolytically treated at different temperatures in N2 atmosphere to obtain metallic Co nanoparticles embedded in N-doped porous carbon layers (denoted as Co@NPC). The results demonstrate that the Co-MOFs derived sample obtained at 900 °C (Co@NPC-900) shows a porous structure (including micropore and mesopore) with a surface area of 110.8 m2 g-1 and an N doping level of 1.62 at.% resulted from TEA in the pyrolysis process. As electrocatalyst, the Co@NPC-900 exhibits bifunctional electrocatalytic activities toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media which are key reactions in some renewable energy technologies such as fuel cells and rechargeable metal-air batteries. The results indicate that the Co@NPC-900 can afford an onset potential of 1.50 V (vs. RHE) and a potential value of 1.61 V (vs. RHE) at a current density of 10 mA cm-2 for ORR and OER with high applicable stability, respectively. The efficient catalytic activity of Co@NPC-900 as bifunctional oxygen electrocatalyst can be ascribed to N doping and embedded metallic Co nanoparticles in carbon structure providing catalytic active sites and porous structure favourable for electrocatalysis-related mass transport.

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

Iron Tolerant Cyanobacteria as an Effective Tool to Study Early Evolution of Life and the Development of Biosignatures

NASA Technical Reports Server (NTRS)

Brown, Igor; Mummey, Daniel; Sarkisova, Svetlana; Allen, Carlton; McKay, David S.

2006-01-01

We are currently conducting preliminary studies on the diversity of iron-tolerant cyanobacteria (CB) isolated from iron-depositing hot springs in and around Yellowstone National Park (WY, USA). In conclusion, there is no consensus on the divergence of cyanobacteria from a common ancestor for either anoxygenic or oxygenic phototrophs. Anoxygenic photosynthesis may have provided energy for the common ancestor, but it is unclear what environmental pressure induced the evolving of oxygenic phototrophs. It is supposed, however, that predecessors of contemporary CB were capable of oxidizing various substrates other than water , and it is likely that Fe2+ could be one of those substrates . If that were the case, the work of entire photosystems in Precambrian cyanobacteria and/or in their predecessors could follow three scenarios (at least): 1) ferrous iron may have been oxidized in PS II but without significant effects on oxygen evolution, and environmental iron could have been oxidized either enzymatically or chemically; 2) ferrous iron may have been oxidized only enzymatically by PS II, accompanied by the repression of O2 evolution; or 3) ferrous iron may have been oxidized by PS I upon the prevalence of anoxygenic photosynthesis or without any effect on PS II. All of these scenarios will be the subject of our future studies with the aim to understand which line-ages of CB could be typical for Precambrian time.

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

PubMed

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.

Redox Evolution in Magma Oceans Due to Ferric/Ferrous Iron Partitioning

NASA Astrophysics Data System (ADS)

Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

2017-12-01

A long-standing puzzle in the evolution of the Earth is that while the present day upper mantle has an oxygen fugacity close to the QFM buffer, core formation during accretion would have occurred at much lower oxygen fugacities close to IW. We present a new model based on experimental evidence that normal solidification and differentiation processes in the terrestrial magma ocean may explain both core formation and the current oxygen fugacity of the mantle without resorting to a change in source material or process. A commonly made assumption is that ferric iron (Fe3+) is negligible at such low oxygen fugacities [1]. However, recent work on Fe3+/Fe2+ ratios in molten silicates [2-4] suggests that the Fe3+ content should increase at high pressure for a given oxygen fugacity. While disproportionation was not observed in these experiments, it may nonetheless be occurring in the melt at high pressure [5]. Therefore, there may be non-negligible amounts of Fe3+ formed through metal-silicate equilibration at high pressures within the magma ocean. Homogenization of the mantle and further partitioning of Fe2+/Fe3+ as the magma ocean crystallizes may explain the oxygen fugacity of the Earth's mantle without requiring additional oxidation mechanisms. We present here models using different parameterizations for the Fe2+/Fe3+ thermodynamic relationships in silicate melts to constrain the evolution of the redox state of the magma ocean as it crystallizes. The model begins with metal-silicate partitioning at high pressure to form the core and set the initial Fe3+ abundance. Combined with previous work on oxygen absorption by magma oceans due to escape of H from H2O [6], we show that the upper layers of solidifying magma oceans should be more oxidized than the lower mantle. This model also suggests that large terrestrial planets should have more oxidized mantles than small planets. From a redox perspective, no change in the composition of the Earth's accreting material needs to be invoked to explain mantle oxygen fugacity, although implications for trace elements in the Earth's core and mantle are still being explored. [1] Ringwood, AE (1979) [2] Armstrong, K et al (2016) LPSC, 2580 [3] Armstrong, K et al (2017) ACCRETE workshop [4] Zhang, HL et al (2017) GCA, 204, 83 [5] Frost, DJ et al (2004) Nature, 428, 409 [6] Schaefer, L et al (2016) ApJ, 829, 63

Trace elements at the intersection of marine biological and geochemical evolution

USGS Publications Warehouse

Robbins, Leslie J.; Lalonde, Stefan V.; Planavsky, Noah J.; Partin, Camille A.; Reinhard, Christopher T.; Kendall, Brian; Scott, Clinton T.; Hardisty, Dalton S.; Gill, Benjamin C.; Alessi, Daniel S.; Dupont, Christopher L.; Saito, Mak A.; Crowe, Sean A.; Poulton, Simon W.; Bekker, Andrey; Lyons, Timothy W.; Konhauser, Kurt O.

2016-01-01

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.

Effects of oxygen concentration on atmospheric pressure dielectric barrier discharge in Argon-Oxygen Mixture

NASA Astrophysics Data System (ADS)

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).

Evolution of Electron Transport Chains During the Anaerobic to Aerobic Transition on Early Earth

NASA Astrophysics Data System (ADS)

Sepúlveda, R.; Ortiz, R.; Holmes, D. S.

2015-12-01

Sepulveda, R., Ortiz R. and Holmes DS. Center for Bioinformatics and Genome Biology, Fundacion Ciencia y Vida, and Facultad de Ciencias Biologicas, Universidad Andres Bello, Santiago, Chile.According to several models, life emerged on earth in an anoxic environment where oxygen was not available as a terminal electron acceptor for energy generating reactions. After the Great Oxidation Event (GOE) about 2.4 billion years ago, or perhaps even before the GOE, oxygen became the most widespread and efficient terminal electron acceptor and was accompanied by the evolution of a number of redox proteins that could deliver electrons to reduce oxygen to water. Where did these proteins come from? One hypothesis is that they evolved by the neofunctionalization of previously existing redox proteins that had been used in anaerobic conditions as terminal electron donors to reduce compounds such as perchlorate, nitric oxide or iron. We have used a number of bioinformatic tools to explore a large number of genomes looking for discernable signals of such redeployment of function. A Perl pipeline was designed to detect sequence similarity, conserved gene context, remote homology detection, identification of domains and functional evolution of electron carrier proteins from extreme acidophiles, including the small blue copper protein rusticyanin (involved in FeII oxidation), cytochrome oxidase subunit II and quinol-dependent nitric oxide reductase (qNOR). The protein folds and copper binding sites of rusticyanin are conserved in cytochrome oxidase aa3 subunit II, a protein complex that is responsible for the final passage of electrons to reduce oxygen. Therefore, we hypothesize that rusticyanin, cytochrome oxidase II and qNOR are evolutionarily related. Acknowledgments: Fondecyt 1130683.

On the subduction of oxygenated surface water in submesoscale cold filaments off Peru.

NASA Astrophysics Data System (ADS)

Thomsen, Soeren; Kanzow, Torsten; Colas, Francois; Echevin, Vincent; Krahmann, Gerd

2015-04-01

The Peruvian upwelling regime is characterized by pronounced submesoscale variability including filaments and sharp density fronts. Submesoscale frontal processes can drive large vertical velocities and enhance vertical tracer fluxes in the upper ocean. The associated high temporal and spatial variability poses a large challenge to observational approaches targeting submesoscale processes. In this study the role of submesoscale processes for both the ventilation of the near-coastal oxygen minimum zone off Peru and the physical-biogeochemical coupling at these scales is investigated. For our study we use satellite based sea surface temperature measurements in combination with multiple high-resolution glider observations of temperature, salinity, oxygen and chlorophyll fluorescence carried out in January and February 2013 off Peru near 14°S during active upwelling. Additionally, high-resolution regional ocean circulation model outputs (ROMS) are analysed. At the beginning of our observations a previously upwelled, productive and highly oxygenated body of water is found within the mixed layer. Subsequently, a cold filament forms and the waters are moved offshore. After the decay of the filament and the relaxation of the upwelling front, the oxygen enriched surface water is found within the previously less oxygenated thermocline suggesting the occurrence of frontal subduction. A numerical model simulation is used to analyse the evolution of passive tracers and Lagrangian floats within several upwelling filaments, whose vertical structure and hydrographic properties agree well with the observations. The simulated temporal evolution of the tracers and floats support our interpretation that the subduction of previously upwelled water indeed occurs within cold filaments off Peru. Filaments are common features within eastern boundary upwelling systems, which all encompass large oxygen minimum zones. However, most state of-the-art large and regional scale physical-biogeochemical ocean models do not resolve submesoscale filaments and the associated downward transport of oxygen and other solutes. Even if the observed subduction event only reaches into the still oxygenated thermocline the associated ventilation mechanism likely influences the shape and depth of the upper boundary of oxygen minimum zones, which would probably be even shallower without this process.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Thermal and chemical evolution in the early Solar System as recorded by FUN CAIs: Part II - Laboratory evaporation of potential CMS-1 precursor material

NASA Astrophysics Data System (ADS)

Mendybaev, Ruslan A.; Williams, Curtis D.; Spicuzza, Michael J.; Richter, Frank M.; Valley, John W.; Fedkin, Alexei V.; Wadhwa, Meenakshi

2017-03-01

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [α2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium (α25,24 for 25Mg/24Mg), silicon (α29,28 for 29Si/28Si) and oxygen (α18,16 for 18O/16O) from the forsterite-rich melt at 1900 °C. The values of α25,24 = 0.98383 ± 0.00033 and α29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α25,24 and α29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1.

Low temperature formation of electrode having electrically conductive metal oxide surface

DOEpatents

Anders, Simone; Anders, Andre; Brown, Ian G.; McLarnon, Frank R.; Kong, Fanping

1998-01-01

A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang; ...

2017-08-25

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

New Views on the Early Evolution of Oxygen in the Galaxy

NASA Astrophysics Data System (ADS)

Rebolo, R.; Israelian, G.; García López, R. J.

We have performed a detailed oxygen abundance analysis of 23 metal-poor (-3.0 < [Fe/H] < -0.3) unevolved halo stars and one giant through the OH bands in the near UV, using high-resolution echelle spectra. Oxygen is found to be overabundant with respect to iron in these stars, with the [O/Fe] ratio increasing from 0.6 to 1 between [Fe/H] = -1.5 and -3.0. The behavior of the oxygen overabundance with respect to [Fe/H] is similar to that seen in previous works based on the OI IR triplet data (Abia & Rebolo 1989; Tomkin et al. 1992; Cavallo, Pilachowski, & Rebolo 1997). Contrary to the previously accepted picture, our oxygen abundances, derived from low-excitation OH lines, agree well with those derived from high-excitation lines of the triplet. For nine stars in common with Tomkin et al. we obtain a mean difference of 0.00 plus or minus 0.11dex with respect to the abundances determined from the triplet using the same stellar parameters and model photospheres. Our new results show a smooth extension of the Edvardsson et al.'s (1993) [O/Fe] versus metallicity curve to much lower abundances. The oxygen abundances of unevolved stars when compared with values in the literature for giants of similar metallicity imply that the latter may have suffered a process of oxygen depletion. It appears that unevolved metal-poor stars are better tracers of the early chemical evolution of the Galaxy. The extrapolation of our results to very low metallicities indicates that the ratio of oxygen to iron emerging from the first Type II SNe in the early Galaxy was indeed close to unity. The higher [O/Fe] ratios we find in dwarfs has an impact on the age determination of globular clusters, and suggest that current age estimates have to be reduced by about 1-2 Gyr.

Interplay between Oxygen and Fe–S Cluster Biogenesis: Insights from the Suf Pathway

PubMed Central

2015-01-01

Iron–sulfur (Fe–S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe–S clusters and the fundamental requirement for Fe–S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth’s atmosphere. Intriguingly, Fe–S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe–S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe–S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe–S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB–SufC scaffold complex. This analysis provides a new framework for the study of Fe–S cluster biogenesis pathways and Fe–S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen. PMID:25153801

Perovskite-nitrogen-doped carbon nanotube composite as bifunctional catalysts for rechargeable lithium-air batteries.

PubMed

Park, Hey Woong; Lee, Dong Un; Park, Moon Gyu; Ahmed, Raihan; Seo, Min Ho; Nazar, Linda F; Chen, Zhongwei

2015-03-01

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ecology and evolution of viruses infecting uncultivated SUP05 bacteria as revealed by single-cell- and meta-genomics

DOE PAGES

Roux, Simon; Hawley, Alyse K.; Torres Beltran, Monica; ...

2014-08-29

Viruses modulate microbial communities and alter ecosystem functions. However, due to cultivation bottlenecks, specific virus–host interaction dynamics remain cryptic. In this study, we examined 127 single-cell amplified genomes (SAGs) from uncultivated SUP05 bacteria isolated from a model marine oxygen minimum zone (OMZ) to identify 69 viral contigs representing five new genera within dsDNA Caudovirales and ssDNA Microviridae. Infection frequencies suggest that ∼1/3 of SUP05 bacteria is viral-infected, with higher infection frequency where oxygen-deficiency was most severe. Observed Microviridae clonality suggests recovery of bloom-terminating viruses, while systematic co-infection between dsDNA and ssDNA viruses posits previously unrecognized cooperation modes. Analyses of 186more » microbial and viral metagenomes revealed that SUP05 viruses persisted for years, but remained endemic to the OMZ. Finally, identification of virus-encoded dissimilatory sulfite reductase suggests SUP05 viruses reprogram their host's energy metabolism. Together, these results demonstrate closely coupled SUP05 virus–host co-evolutionary dynamics with the potential to modulate biogeochemical cycling in climate-critical and expanding OMZs.« less

Testing the 'free radical theory of aging' hypothesis: physiological differences in long-lived and short-lived colubrid snakes.

PubMed

Robert, Kylie A; Brunet-Rossinni, Anja; Bronikowski, Anne M

2007-06-01

We test the 'free radical theory of aging' using six species of colubrid snakes (numerous, widely distributed, non-venomous snakes of the family Colubridae) that exhibit long (> 15 years) or short (< 10 years) lifespans. Because the 'rate of living theory' predicts metabolic rates to be correlated with rates of aging and oxidative damage results from normal metabolic processes we sought to answer whether physiological parameters and locomotor performance (which is a good predictor of survival in juvenile snakes) mirrored the evolution of lifespans in these colubrid snakes. We measured whole animal metabolic rate (oxygen consumption Vo2), locomotor performance, cellular metabolic rate (mitochondrial oxygen consumption), and oxidative stress potential (hydrogen peroxide production by mitochondria). Longer-lived colubrid snakes have greater locomotor performance and reduced hydrogen peroxide production than short-lived species, while whole animal metabolic rates and mitochondrial efficiency did not differ with lifespan. We present the first measures testing the 'free radical theory of aging' using reptilian species as model organisms. Using reptiles with different lifespans as model organisms should provide greater insight into mechanisms of aging.

Oxygen isotopes of marine mollusc shells record Eocene elevation change in the Pyrenees

NASA Astrophysics Data System (ADS)

Huyghe, Damien; Mouthereau, Frédéric; Emmanuel, Laurent

2012-09-01

Constraining paleoaltimetry of collisional orogens is critical to understand the dynamics of topographic evolution and climate/tectonics retroactions. Here, we use oxygen stable-isotope record on oyster shells, preserved in marine foreland deposits, to examine the past elevation of the Pyrenees during the Eocene. Our approach is based on the comparison with the Paris basin, an intracratonic basin not influenced by orogenic growth. The finding of a shift of 1.5‰ between 49 and 41 Ma, indicating more negative δ18Oc in the south Pyrenean foreland, is interpreted to reflect the inflow of river water sourced from higher elevation in the Pyrenees. To test this and provide paleoelevation estimate, we adopt a morphologic-hydrological model accounting for the hypsometry of drainage basin. Our best fitting model shows that the Pyrenees rose up to 2000 m. This indicates that the Pyrenees reached high elevation in the Eocene, thus providing new critical constraints on their long-term orogenic development. δ18O of marine mollusc shells are proved potentially attractive for paleoelevation studies, especially for mountain belts where elevated continental surfaces have not been preserved.

Highly oxidising fluids generated during serpentinite breakdown in subduction zones.

PubMed

Debret, B; Sverjensky, D A

2017-09-04

Subduction zones facilitate chemical exchanges between Earth's deep interior and volcanism that affects habitability of the surface environment. Lavas erupted at subduction zones are oxidized and release volatile species. These features may reflect a modification of the oxidation state of the sub-arc mantle by hydrous, oxidizing sulfate and/or carbonate-bearing fluids derived from subducting slabs. But the reason that the fluids are oxidizing has been unclear. Here we use theoretical chemical mass transfer calculations to predict the redox state of fluids generated during serpentinite dehydration. Specifically, the breakdown of antigorite to olivine, enstatite, and chlorite generates fluids with high oxygen fugacities, close to the hematite-magnetite buffer, that can contain significant amounts of sulfate. The migration of these fluids from the slab to the mantle wedge could therefore provide the oxidized source for the genesis of primary arc magmas that release gases to the atmosphere during volcanism. Our results also show that the evolution of oxygen fugacity in serpentinite during subduction is sensitive to the amount of sulfides and potentially metal alloys in bulk rock, possibly producing redox heterogeneities in subducting slabs.

Ni xWO 2.72 nanorods as an efficient electrocatalyst for oxygen evolution reaction

DOE PAGES

Xi, Zheng; Mendoza-Garcia, Adriana; Zhu, Huiyuan; ...

2017-01-13

Ni xWO 2.72 nanorods (NRs) are synthesized by a one-pot reaction of Ni(acac) 2 and WCl 4. In the rod structure, Ni(II) intercalates in the defective perovskite-type WO 2.72 and is stabilized. The Ni xWO 2.72 NRs show the x-dependent electrocatalysis for the oxygen evolution reaction (OER) in 0.1M KOH with Ni 0.78WO 2.72 being the most efficient, even outperforming the commercial Ir-catalyst. Lastly, the synthesis is not limited to Ni xWO 2.72 but can be extended to M xWO 2.72 (M = Co, Fe) as well, providing a new class of oxide-based catalysts for efficient OER and other energymore » conversion reactions.« less

Highly-active oxygen evolution electrocatalyzed by an Fe-doped NiCr2O4 nanoparticle film.

PubMed

Zhao, Jinxiu; Li, Xianghong; Cui, Guanwei; Sun, Xuping

2018-05-11

Alkaline water splitting offers a simple method for the mass production of hydrogen but suffers from the sluggish kinetics of the anodic oxygen evolution reaction (OER). Here, we report on the development of an Fe-doped NiCr2O4 nanoparticle film on Ni foam (Fe-NiCr2O4/NF) as a non-noble-metal OER electrocatalyst with superior catalytic activity at alkaline pH. Such Fe-NiCr2O4/NF demands overpotentials as low as 228 and 318 mV to drive current densities of 20 and 500 mA cm-2, respectively, in 1.0 M KOH. Notably, it also shows strong long-term electrochemical durability with its activity being retained for at least 60 h.

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance.

PubMed

Song, Fang; Bai, Lichen; Moysiadou, Aliki; Lee, Seunghwa; Hu, Chao; Liardet, Laurent; Hu, Xile

2018-06-27

Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.

Reducing Iridium Loading in Oxygen Evolution Reaction Electrocatalysts Using Core–Shell Particles with Nitride Cores

DOE PAGES

Tackett, Brian M.; Sheng, Wenchao; Kattel, Shyam; ...

2018-02-16

Here, the oxygen evolution reaction (OER) has broad applications in electrochemical devices, but it often requires expensive and scarce Ir-based catalysts in acid electrolyte. Presented here is a framework to reduce Ir loading by combining core–shell iridium/metal nitride morphologies using in situ experiments and density functional theory (DFT) calculations. Several group VIII transition metal (Fe, Co, and Ni) nitrides are studied as core materials, with Ir/Fe 4N core–shell particles showing enhancement in both OER activity and stability. In situ X-ray absorption fine structure measurements are used to determine the structure and stability of the core–shell catalysts under OER conditions. DFTmore » calculations are used to demonstrate adsorbate binding energies as descriptors of the observed activity trends.« less

A theoretical stochastic control framework for adapting radiotherapy to hypoxia

NASA Astrophysics Data System (ADS)

Saberian, Fatemeh; Ghate, Archis; Kim, Minsun

2016-10-01

Hypoxia, that is, insufficient oxygen partial pressure, is a known cause of reduced radiosensitivity in solid tumors, and especially in head-and-neck tumors. It is thus believed to adversely affect the outcome of fractionated radiotherapy. Oxygen partial pressure varies spatially and temporally over the treatment course and exhibits inter-patient and intra-tumor variation. Emerging advances in non-invasive functional imaging offer the future possibility of adapting radiotherapy plans to this uncertain spatiotemporal evolution of hypoxia over the treatment course. We study the potential benefits of such adaptive planning via a theoretical stochastic control framework using computer-simulated evolution of hypoxia on computer-generated test cases in head-and-neck cancer. The exact solution of the resulting control problem is computationally intractable. We develop an approximation algorithm, called certainty equivalent control, that calls for the solution of a sequence of convex programs over the treatment course; dose-volume constraints are handled using a simple constraint generation method. These convex programs are solved using an interior point algorithm with a logarithmic barrier via Newton’s method and backtracking line search. Convexity of various formulations in this paper is guaranteed by a sufficient condition on radiobiological tumor-response parameters. This condition is expected to hold for head-and-neck tumors and for other similarly responding tumors where the linear dose-response parameter is larger than the quadratic dose-response parameter. We perform numerical experiments on four test cases by using a first-order vector autoregressive process with exponential and rational-quadratic covariance functions from the spatiotemporal statistics literature to simulate the evolution of hypoxia. Our results suggest that dynamic planning could lead to a considerable improvement in the number of tumor cells remaining at the end of the treatment course. Through these simulations, we also gain insights into when and why dynamic planning is likely to yield the largest benefits.