Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

Science.gov (United States)

Opila, Elizabeth J.; Serra, Jessica

2009-01-01

Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

Science.gov (United States)

Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

Color-selective photodetection from intermediate colloidal quantum dots buried in amorphous-oxide semiconductors.

Science.gov (United States)

Cho, Kyung-Sang; Heo, Keun; Baik, Chan-Wook; Choi, Jun Young; Jeong, Heejeong; Hwang, Sungwoo; Lee, Sang Yeol

2017-10-10

We report color-selective photodetection from intermediate, monolayered, quantum dots buried in between amorphous-oxide semiconductors. The proposed active channel in phototransistors is a hybrid configuration of oxide-quantum dot-oxide layers, where the gate-tunable electrical property of silicon-doped, indium-zinc-oxide layers is incorporated with the color-selective properties of quantum dots. A remarkably high detectivity (8.1 × 10 13 Jones) is obtained, along with three major findings: fast charge separation in monolayered quantum dots; efficient charge transport through high-mobility oxide layers (20 cm 2  V -1  s -1 ); and gate-tunable drain-current modulation. Particularly, the fast charge separation rate of 3.3 ns -1 measured with time-resolved photoluminescence is attributed to the intermediate quantum dots buried in oxide layers. These results facilitate the realization of efficient color-selective detection exhibiting a photoconductive gain of 10 7 , obtained using a room-temperature deposition of oxide layers and a solution process of quantum dots. This work offers promising opportunities in emerging applications for color detection with sensitivity, transparency, and flexibility.The development of highly sensitive photodetectors is important for image sensing and optical communication applications. Cho et al., report ultra-sensitive photodetectors based on monolayered quantum dots buried in between amorphous-oxide semiconductors and demonstrate color-detecting logic gates.

Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

Science.gov (United States)

Taatjes, Craig A.

2017-05-01

The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

Experimental and simulation analysis of hydrogen production by partial oxidation of methanol

Energy Technology Data Exchange (ETDEWEB)

Sikander, U. [National Univ. of Science and Technology, Islamabad (Pakistan)

2014-10-15

Partial oxidation of methanol is the only self-sustaining process for onboard production of hydrogen. For this a fixed bed catalytic reactor is designed, based on heterogeneous catalytic reaction. To develop an optimized process, simulation is carried out using ASPEN HYSYS v 7.1. Reaction kinetics is developed on the basis of Langmuir Hinshel wood model. 45:55:5 of CuO: ZnO: Al/sub 2/O/sub 3/ is used as a catalyst. Simulation results are studied in detail to understand the phenomenon of partial oxidation of methanol inside the reactor. An experimental rig is developed for hydrogen production through partial oxidation of methanol. Results obtained from process simulation and experimental work; are compared with each other. (author)

The ribosome can prevent aggregation of partially folded protein intermediates: studies using the Escherichia coli ribosome.

Directory of Open Access Journals (Sweden)

Bani Kumar Pathak

Full Text Available BACKGROUND: Molecular chaperones that support de novo folding of proteins under non stress condition are classified as chaperone 'foldases' that are distinct from chaperone' holdases' that provide high affinity binding platform for unfolded proteins and prevent their aggregation specifically under stress conditions. Ribosome, the cellular protein synthesis machine can act as a foldase chaperone that can bind unfolded proteins and release them in folding competent state. The peptidyl transferase center (PTC located in the domain V of the 23S rRNA of Escherichia coli ribosome (bDV RNA is the chaperoning center of the ribosome. It has been proposed that via specific interactions between the RNA and refolding proteins, the chaperone provides information for the correct folding of unfolded polypeptide chains. RESULTS: We demonstrate using Escherichia coli ribosome and variants of its domain V RNA that the ribosome can bind to partially folded intermediates of bovine carbonic anhydrase II (BCAII and lysozyme and suppress aggregation during their refolding. Using mutants of domain V RNA we demonstrate that the time for which the chaperone retains the bound protein is an important factor in determining its ability to suppress aggregation and/or support reactivation of protein. CONCLUSION: The ribosome can behave like a 'holdase' chaperone and has the ability to bind and hold back partially folded intermediate states of proteins from participating in the aggregation process. Since the ribosome is an essential organelle that is present in large numbers in all living cells, this ability of the ribosome provides an energetically inexpensive way to suppress cellular aggregation. Further, this ability of the ribosome might also be crucial in the context that the ribosome is one of the first chaperones to be encountered by a large nascent polypeptide chains that have a tendency to form partially folded intermediates immediately following their synthesis.

Effect of oxygen partial pressure on oxidation of Mo-metal

Science.gov (United States)

Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

2018-05-01

This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel

Science.gov (United States)

Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

2016-01-01

Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially ‘clean’ strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2•- radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO-) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems

Catalytic Partial Oxidation of Biomass/Oil Mixture

Czech Academy of Sciences Publication Activity Database

Veselý, Václav; Hanika, Jiří; Tukač, V.; Lederer, J.; Kovač, D.

2013-01-01

Roč. 7, č. 10 (2013), s. 1940-1945 ISSN 1934-8983 R&D Projects: GA TA ČR TE01020080; GA MPO 2A-2TP1/024 Institutional support: RVO:67985858 Keywords : hydrocarbon oil * biomass * catalytic partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.davidpublishing.com/journals_info.asp?jId=1718#

Electrochemical and partial oxidation of methane

Science.gov (United States)

Singh, Rahul

2008-10-01

negligible coke formation on the novel fabricated anode by electroless plating process. Hydrogen is an environmentally cleaner source of energy. The recent increase in the demand of hydrogen as fuel for all types of fuel cells and petroleum refining process has boosted the need of production of hydrogen. Methane, a major component of natural gas is the major feedstock for production of hydrogen. The route of partial oxidation of methane to produce syngas (CO + H2) offers significant advantages over commercialized steam reforming process for higher efficiency and lower energy requirements. Partial oxidation of methane was studied by pulsing O2 into a CH4 flow over Rh/Al2O3 in a sequence of in situ infrared (IR) cell and fixed bed reactor at 773 K. The results obtained from the sequence of an IR cell followed by a fixed bed reactor show that (i) adsorbed CO produced possesses a long residence time, indicating that adsorbed oxygen leading to the formation of CO is significantly different from those leading to CO2 and (ii) CO2 is not an intermediate species for the formation of CO. In situ IR of pulse reaction coupled with alternating reactor sequence is an effective approach to study the primary and secondary reactions as well as the nature of their adsorbed species. As reported earlier, hydrogen remains to be the most effective fuel for fuel cells, the production of high purity hydrogen from naturally available resources such as coal, petroleum, and natural gas requires a number of energy-intensive steps, making fuel cell processes for stationary electric power generation prohibitively uneconomic. Direct use of coal or coal gas as the feed is a promising approach for low cost electricity generation. Coal gas solid oxide fuel cell was studied by pyrolyzing Ohio #5 coal to coal gas and transporting to a Cu anode solid oxide fuel cell to generate power. The study of coal-gas solid oxide fuel cell is divided into two sections, i.e., (i) understanding the composition of coal gas by

Chemical polishing of partially oxidized T-111 alloy

International Nuclear Information System (INIS)

Teaney, P.E.

1974-01-01

The specimens were pressure-mounted in Bakelite and ground through 600 grit on silicon carbide papers. The specimens were rough-polished on a vibratory polisher for 4 to 6 h, using a water slurry of one micron alumina on Texmet, followed by 0.3-μ alumina on Texmet overnight. Final polishing was accomplished by continuous swabbing with a chemical polish. A chemical polish consisting of ten parts lactic acid, four parts nitric acid, and four parts hydrofluoric acid worked well for the T-111 parent material specimens; however, in the partially oxidized specimens, considerable pitting and staining occurred in the oxygen-affected zone and in the transition zone between the oxygen-affected zone and the parent material. A chemical polish was developed for the partially oxidized specimens by adjusting the ratio of the acids to ten parts lactic acid, two parts nitric acid, and two parts hydrofluoric acid. This slowed the chemical attack on the oxygen-affected zone considerably and, with continuous swabbing, the pitting and stain could be avoided. The specimens were rinsed and checked occasionally on the metallograph to determine when the proper polish had been obtained. Some specimens required intermittent polishing times up to 1 / 2 hour. No relationship could be established between the oxygen content of the specimen and the time required for chemical polishing in the partially oxidized specimens. However, the microstructure of the transition zone was the most difficult to obtain, and specimens with uniform reaction zones across the width of the specimen polished quicker than those with the transition zone

Advances in the Partial Oxidation of Methane to Synthesis Gas

Institute of Scientific and Technical Information of China (English)

Quanli Zhu; Xutao Zhao; Youquan Deng

2004-01-01

The conversion and utilization of natural gas is of significant meaning to the national economy,even to the everyday life of people. However, it has not become a popular industrial process as expected due to the technical obstacles. In the past decades, much investigation into the conversion of methane,predominant component of natural gas, has been carried out. Among the possible routes of methane conversion, the partial oxidation of methane to synthesis gas is considered as an effective and economically feasible one. In this article, a brief review of recent studies on the mechanism of the partial oxidation of methane to synthesis gas together with catalyst development is wherein presented.

Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

KAUST Repository

Zhang, Xuming

2015-01-01

We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight from studying high-temperature and low-pressure conditions with similar reduced field intensities. In the tested range of background temperatures (297 < T < 773 K), we found that the conversion of methane and oxygen depended on both the electron-induced chemistry and the thermo-chemistry, whereas the chemical pathways to the products were overall controlled by the thermo-chemistry at a given temperature. We also found that the thermo-chemistry enhanced the plasma-assisted partial oxidation process. Our findings expand our understanding of the plasma-assisted partial oxidation process and may be helpful in the design of cost-effective plasma reformers. © 2014 The Combustion Institute.

n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine

KAUST Repository

Wang, Zhandong; Chen, Bingjie; Moshammer, Kai; Popolan-Vaida, Denisia M.; Sioud, Salim; Shankar, Vijai; Vuilleumier, David; Tao, Tao; Ruwe, Lena; Brä uer, Eike; Hansen, Nils; Dagaut, Philippe; Kohse-Hö inghaus, Katharina; Raji, Misjudeen; Sarathy, Mani

2017-01-01

-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar

Generation of synthesis gas by partial oxidation of natural gas in a gas turbine

NARCIS (Netherlands)

Cornelissen, R.; Tober, E.; Kok, Jacobus B.W.; van der Meer, Theodorus H.

2006-01-01

The application of partial oxidation in a gas turbine (PO-GT) in the production of synthesis gas for methanol production is explored. In PO-GT, methane is compressed, preheated, partial oxidized and expanded. For the methanol synthesis a 12% gain in thermal efficiency has been calculated for the

The influence of the oxygen partial pressure on the quasi-ternary system Cr-Mn-Ti-oxide

International Nuclear Information System (INIS)

Garcia-Rosales, C.; Schulze, H.A.; Naoumidis, A.; Nickel, H.

1991-05-01

The passivation layers formed by the oxidizing corrosion of high temperature alloys consist primarily of oxides and mixed oxides of the elements chromium, manganese and titanium. For a reproducible formation and characterization of such oxide layers it is necessary to know the phase equilibria of these oxide systems at temperature and oxygen partial pressure conditions which will be relevant during their application. For the investigation of the quasi-ternary system Cr-Mn-Ti-oxide, oxide powders were prepared and annealed at 1000deg C under different oxygen partial pressures ranging from 0.21 bar to 10 -21 bar. Phase identification and determination of lattice parameter using X-ray diffraction analysis as well as the direct measurement of phase boundaries as a function of oxygen partial pressure using the emf-methode were carried out for these investigations. In the quasi-ternary system Cr-Mn-Ti-oxide the spinels play a decisive role in the oxigen partial pressure range examined. The spinel MnCr 2 O 4 may be regarded as the most significant compound. Part of the chronium can be replaced by trivalent manganese at high oxygen partial pressures and by trivalent titanium at low pressures, and the formation of a solid solution with the spinel Mn 2 TiO 4 is possible in all cases. In this way a coherent single-phase spinel region is observed which extends over the entire oxygen partial pressure range form 0.21 bar to 10 -21 bar examined at 1000deg C. (orig.) [de

One-Pot Synthesis of Cu(II Complex with Partially Oxidized TTF Moieties

Directory of Open Access Journals (Sweden)

Hiroki Oshio

2012-07-01

Full Text Available The one-pot synthesis of a Cu(II complex with partially oxidized tetrathiafulvalene (TTF moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF2] [CuICl2] was realized by the simultaneous occurrence of Cu(II complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.

Kinetic studies of isooctane partial oxidation over a nickel-based catalyst

International Nuclear Information System (INIS)

Ibrahim, Hussameldin; Idem, Raphael; Aboudheir, Ahmed

2006-01-01

The production of hydrogen (H 2 ) for fuel cell applications in mobile vehicles by reforming technologies such as partial oxidation of various fossil fuels has gained much attention recently. In this study, the production of H 2 by the catalytic partial oxidation of isooctane ((C 8 H 18 ) used here as a surrogate for gasoline) was investigated over alumina (AI 2 O 3 )supported nickel (Ni) catalyst. The work investigated the kinetics of the partial oxidation of isooctane over a stable Ni/□-AI 2 O 3 catalyst in the range of 863 to 913 K, at atmospheric pressure, W/F i c8 in the range of 1.97 to 8.58 g h mol - 1, and molar feed ratio in the range of 2.0 to 8.0 experiments to obtain kinetic data were performed in a 12.7 mm diameter Inconel micro-reactor housed in an electrically controlled furnace. The chemical reaction was then modeled using rate models developed from the Langmuir-Hinshelwood-hougen-Watson (LHHW) and Eley-Rideal (ER) formulations. The model parameters were estimated using an adaptive Gauss-Newton and Marquardi-Levenberg minimization algorithm. Rival models were screened for their thermodynamic consistency and physicochemical significance of estimated parameters. Langmuir-Hinshelwood-hougen-Watson mechanism requiring the dissociative adsorption of isooctane and oxygen on two different sites appeared to be the most likely pathway for the partial oxidation reaction of isooctane. Reaction order with respect to isooctane indicates the strong coverage of nickel by isooctane. The activation energy of 73±3.1 kJ mol - 1 estimated from the LHHW model is consistent with the trend observed with lower hydrocarbons.(Author)

Oxidative stress and partial migration in brown trout (Salmo trutta)

DEFF Research Database (Denmark)

Birnie-Gauvin, Kim; Peiman, K. S.; Larsen, Martin Hage

2017-01-01

of oxidative status in migration biology, particularly in fish. Semi-anadromous brown trout (Salmo trutta, Linnaeus 1758) exhibit partial migration, where some individuals smoltify and migrate to sea, and others become stream residents, providing us with an excellent model to investigate the link between...... oxidative stress and migration. Using the brown trout, we obtained blood samples from juveniles from a coastal stream in Denmark in the fall prior to peak seaward migration which occurs in the spring, and assayed for antioxidant capacity (oxygen radical absorbance capacity) and oxidative stress levels...

Hydrogen or Soot?: Partial Oxidation of High-boiling Hydrocarbon Wastes

Czech Academy of Sciences Publication Activity Database

Lederer, J.; Hanika, Jiří; Nečesaný, F.; Poslední, W.; Tukač, V.; Veselý, Václav

2015-01-01

Roč. 29, č. 1 (2015), s. 5-11 ISSN 0352-9568 Institutional support: RVO:67985858 Keywords : partial oxidation * waste * hydrocarbon Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.675, year: 2015

Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

International Nuclear Information System (INIS)

Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

2014-01-01

This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

Palm H-FAME Production through Partially Hydrogenation using Nickel/Carbon Catalyst to Increase Oxidation Stability

Directory of Open Access Journals (Sweden)

Ramayeni Elsa

2018-01-01

Full Text Available One of the methods to improve the oxidation stability of palm biodiesel is through partially hydrogenation. The production using Nickel/Carbon catalyst to speed up the reaction rate. Product is called Palm H-FAME (Hydrogenated FAME. Partial hydrogenation breaks the unsaturated bond on FAME (Fatty Acid Methyl Ester, which is a key component of the determination of oxidative properties. Changes in FAME composition by partial hydrogenation are predicted to change the oxidation stability so it does not cause deposits that can damage the injection system of diesel engine, pump system, and storage tank. Partial hydrogenation is carried out under operating conditions of 120 °C and 6 bar with 100:1, 100:3, 100:5, 100:10 % wt catalyst in the stirred batch autoclave reactor. H-FAME synthesis with 100:5 % wt Ni/C catalyst can decrease the iodine number which is the empirical measure of the number of unsaturated bonds from 91.78 to 82.38 (g-I2/100 g with an increase of oxidation stability from 585 to 602 minutes.

Catalytic partial oxidation of pyrolysis oils

Science.gov (United States)

Rennard, David Carl

2009-12-01

This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

Energy Technology Data Exchange (ETDEWEB)

Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment

1975-11-01

Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.

The chemical energy unit partial oxidation reactor operation simulation modeling

Science.gov (United States)

Mrakin, A. N.; Selivanov, A. A.; Batrakov, P. A.; Sotnikov, D. G.

2018-01-01

The chemical energy unit scheme for synthesis gas, electric and heat energy production which is possible to be used both for the chemical industry on-site facilities and under field conditions is represented in the paper. The partial oxidation reactor gasification process mathematical model is described and reaction products composition and temperature determining algorithm flow diagram is shown. The developed software product verification showed good convergence of the experimental values and calculations according to the other programmes: the temperature determining relative discrepancy amounted from 4 to 5 %, while the absolute composition discrepancy ranged from 1 to 3%. The synthesis gas composition was found out practically not to depend on the supplied into the partial oxidation reactor (POR) water vapour enthalpy and compressor air pressure increase ratio. Moreover, air consumption coefficient α increase from 0.7 to 0.9 was found out to decrease synthesis gas target components (carbon and hydrogen oxides) specific yield by nearly 2 times and synthesis gas target components required ratio was revealed to be seen in the water vapour specific consumption area (from 5 to 6 kg/kg of fuel).

Mechanism of propylene oxidation over bismuth molybdate revealed by transient response method--1. An intermediate in the complete oxidation of C/sub 3/H/sub 6/

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, M.; Futaya, R.

1979-01-01

An intermediate in the complete oxidation of C/sub 3/H/sub 6/ and its nature were deduced from transient response studies of a flow reactor system with a 1:1 bismuth-molybdenum catalyst at temperatures below ordinary operating temperatures. The formation of a stable surface intermediate with a non-allylic structure resembling that of propylene on every site of the catalyst surface occurred at 310/sup 0/C in the presence of propylene/oxygen or acrolein/oxygen; under oxidative conditions at 310/sup 0/C about eight times more intermediate formed directly from propylene than from adsorbed acrolein. The intermediate reacted with weakly adsorbed oxygen from the gas phase, but not with lattice oxygen, to decompose into CO/sub 2/; in temperature programed desorption studies (2.3/sup 0/C/min) it desorbed as CO/sub 2/ into a stream of helium above 220/sup 0/C (peak at 420/sup 0/C), apparently by reaction with oxygen diffused from the bulk to the surface.

Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas

Institute of Scientific and Technical Information of China (English)

魏永刚; 王华; 李孔斋

2010-01-01

The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...

Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

Energy Technology Data Exchange (ETDEWEB)

Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

1998-12-31

A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

Rare earth oxide-doped titania nanocomposites with enhanced photocatalytic activity towards the degradation of partially hydrolysis polyacrylamide

International Nuclear Information System (INIS)

Li Jinhuan; Yang Xia; Yu Xiaodan; Xu, Leilei; Kang Wanli; Yan Wenhua; Gao Hongfeng; Liu Zhonghe; Guo Yihang

2009-01-01

Rare-earth oxide-doped titania nanocomposites (RE 3+ /TiO 2 , where RE = Eu 3+ , Pr 3+ , Gd 3+ , Nd 3+ , and Y 3+ ) were prepared by a one-step sol-gel-solvothermal method. The products exhibited anatase phase structure, mesoporosity, and interesting surface compositions with three oxygen species and two titanium species. The products were used as the photocatalysts to degrade a partially hydrolysis polyacrylamide (HPAM) under UV-light irradiation, a very useful polymer in oil recovery. For comparison, Degussa P25 and as-prepared pure TiO 2 were also tested under the same conditions. The enhanced photocatalytic activity was obtained on as-prepared Eu 3+ (Gd 3+ , Pr 3+ )/TiO 2 composites, and the reasons were explained. Finally, the degradation pathway of HPAM over the RE 3+ /TiO 2 composite was put forward based on the intermediates produced during the photocatalysis procedure.

Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

Science.gov (United States)

Ward, Collin P; Cory, Rose M

2016-04-05

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

Partial Oxidation of High-Boiling Hydrocarbon Mixtures in the Pilot Unit

Czech Academy of Sciences Publication Activity Database

Hanika, Jiří; Lederer, J.; Nečesaný, F.; Poslední, W.; Tukač, V.; Veselý, Václav

2014-01-01

Roč. 68, č. 12 (2014), s. 1701-1706 ISSN 0366-6352 Institutional support: RVO:67985858 Keywords : partial oxidation * high-boiling hydrocarbons * pilot plant Subject RIV: CI - Industrial Chemistry , Chemical Engineering Impact factor: 1.468, year: 2014

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2.

Science.gov (United States)

Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min

2015-09-01

Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH3)2COO with water vapor and with SO2 were directly measured via UV absorption of (CH3)2COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH3)2COO is not fast enough (kH2O SO2 at a near-gas-kinetic-limit rate (kSO2 = 1.3 × 10(-10) cm(3) s(-1)). These observations imply a significant fraction of atmospheric (CH3)2COO may survive under humid conditions and react with SO2, very different from the case of the simplest Criegee intermediate CH2OO, in which the reaction with water dimer predominates in the CH2OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH3)2COO with SO2, suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere.

Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH2Cl2: Fluorescence from intermediate compounds

International Nuclear Information System (INIS)

Alwis, D.D.D.H; Chandrika, U.G.; Jayaweera, P.M.

2015-01-01

Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH 2 Cl 2 solutions via chemical oxidation using anhydrous FeCl 3 . UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S 2 →S 0 (1 1 B u →1 1 A g ) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl 3 in CH 2 Cl 2 shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region

Biological degradation of partially oxidated constituents of stabilized sapropel; Biologischer Abbau teiloxidierter Inhaltsstoffe stabilisierter Faulschlaemme

Energy Technology Data Exchange (ETDEWEB)

Scheminski, A.; Krull, R.; Hempel, D.C. [Technische Univ. Braunschweig (Germany). Inst. fuer Bioverfahrenstechnik

1999-07-01

Partial oxidation of sapropel with ozone destroys the cell walls of microorganisms in sludge and releases the cell constituents. Substances that are not biologically degraded because of the size or structure of their molecules are transformed into smaller, water-soluble and biologically degradable fractions by the reaction with ozone. The experiments aim to render the partially oxidated sewage sludge constituents highly biologically degradable using a minimum of oxidation agents. For the experiments described, stabilized sapropels with low biological activity are used. Hence the ozone is mainly used for the partial oxidation of recalcitrant constituents. (orig.) [German] Durch partielle Oxidation von Faulschlaemmen mit Ozon werden die Zellwaende der Mikroorganismen im Schlamm zerstoert und die Zellinhaltsstoffe freigesetzt. Dabei werden Substanzen, die aufgrund ihrer Molekuelgroesse oder -struktur biologisch nicht abgebaut werden, durch die Reaktion mit Ozon in kleinere, wasserloesliche und biologisch abbaubare Bruchstuecke ueberfuehrt. Ziel der Versuche ist es, durch den Einsatz moeglichst geringer Mengen an Oxidationsmitteln eine hohe biologische Abbaubarkeit der teiloxidierten Klaerschlamminhaltsstoffe zu erreichen. Fuer die hier vorgestellten Experimente wurden stabilisierte Faulschlaemme mit geringer biologischer Aktivitaet eingesetzt. Dadurch wird das Ozon vorwiegend zur Teiloxidation recalcitranter Inhaltsstoffe genutzt. (orig.)

Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

KAUST Repository

Zhang, Tao; Chen, Yin; Leiknes, TorOve

2016-01-01

Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

KAUST Repository

Zhang, Tao

2016-05-04

Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

International Nuclear Information System (INIS)

Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

2012-01-01

Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N 2 -saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO 2 system by changing the reaction atmospheres.

Partial Reduction of Esters to Aldehydes Using a Novel Modified Red-Al Reducing Agent

Energy Technology Data Exchange (ETDEWEB)

Shin, Won Kyu; Kang, Daehoon; An, Duk Keun [Kangwon National Univ., Chunchon (Korea, Republic of)

2014-07-15

We have developed a convenient alternative method for the synthesis of aldehydes from both aromatic and aliphatic esters in very good to excellent yields in the absence of any additives using a modified Red-Al that was easily prepared by reacting commercially available Red-Al with cis-2,6-dimethyl morpholine. The advantages of the present methodology are as follows: simple preparation procedure of the reducing agent, improved product yields, convenient reaction temperature, and short reaction times. Therefore, the new reagent has great potential to be a useful alternative partial reducing agent for the synthesis of aldehydes from esters in organic synthesis. Aldehydes are valuable building blocks and reactive intermediates in organic synthesis. The general and classical syntheses of aldehydes from esters involve reduction-oxidation and partial reduction using efficient partial reducing agents. Obviously, one-step partial reduction methods are more useful than two-step reduction-oxidation methods owing to their simplicity, and generality in organic synthesis.

High temperature oxidation kinetics of dysprosium particles

Energy Technology Data Exchange (ETDEWEB)

Jaques, Brian J.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu

2015-09-25

Highlights: • The oxidation behavior of dysprosium particles was studied from 500 to 1000 °C. • Activation energy in initial region found as 8–25 kJ/mol, depending on atmosphere. • Activation energy in intermediate region found as 80–95 kJ/mol. • The oxide grows at the metal–oxide interface. • Generally, the formed oxide behaved as a p-type semiconductor. - Abstract: Rare earth elements have been recognized as critical materials for the advancement of many strategic and green technologies. Recently, the United States Department of Energy has invested many millions of dollars to enhance, protect, and forecast their production and management. The work presented here attempts to clarify the limited and contradictory literature on the oxidation behavior of the rare earth metal, dysprosium. Dysprosium particles were isothermally oxidized from 500 to 1000 °C in N{sub 2}–(2%, 20%, and 50%) O{sub 2} and Ar–20% O{sub 2} using simultaneous thermal analysis techniques. Two distinct oxidation regions were identified at each isothermal temperature in each oxidizing atmosphere. Initially, the oxidation kinetics are very fast until the reaction enters a slower, intermediate region of oxidation. The two regions are defined and the kinetics of each are assessed to show an apparent activation energy of 8–25 kJ/mol in the initial region and 80–95 kJ/mol in the intermediate oxidation reaction region. The effects of varying the oxygen partial pressure on the reaction rate constant are used to show that dysprosium oxide (Dy{sub 2}O{sub 3}) generally acts as a p-type semiconductor in both regions of oxidation (with an exception above 750 °C in the intermediate region)

Laser-induced partial oxidation of cyclohexane in liquid phase

International Nuclear Information System (INIS)

Oshima, Y.; Wu, X.W.; Koda, S.

1995-01-01

A laser-induced partial oxidation of cyclohexane was studied in the liquid phase. With KrF excimer laser (248 nm) irradiation to neat liquid cyclohexane in which O 2 was dissolved, cyclohexanol and cyclohexanone were obtained with very high selectivities, together with cyclohexane as a minor product. Radical recombination reactions to produce dicyclohexyl ether and bicyclohexyl also took place, while these products were not observed in the gas phase reaction. These experimental results were considered to be due not only to higher concentration of cyclohexane but to the cage effect in the liquid phase oxidation. To clarify the reaction progress including the photoabsorption process, the effects of laser intensity and O 2 pressure on product distribution were studied. (author)

Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

KAUST Repository

Zhang, Xuming; Cha, Min

2015-01-01

We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight

Plasma-assisted partial oxidation of methane at low temperatures: numerical analysis of gas-phase chemical mechanism

Energy Technology Data Exchange (ETDEWEB)

Goujard, Valentin; Nozaki, Tomohiro; Yuzawa, Shuhei; Okazaki, Ken [Department of Mechanical and Control Engineering, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro, 1528552, Tokyo (Japan); Agiral, Anil, E-mail: tnozaki@mech.titech.ac.jp [Mesoscale Chemical Systems, MESA Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, PO Box 217, 7500 AE, Enschede (Netherlands)

2011-07-13

Methane partial oxidation was investigated using a plasma microreactor. The experiments were performed at 5 and 300 deg. C. Microreactor configuration allows an efficient evacuation of the heat generated by methane partial oxidation and dielectric barrier discharges, allowing at the same time a better temperature control. At 5 deg. C, liquid condensation of low vapour pressure compounds, such as formaldehyde and methanol, occurs. {sup 1}H-NMR analysis allowed us to demonstrate significant CH{sub 3}OOH formation during plasma-assisted partial oxidation of methane. Conversion and product selectivity were discussed for both temperatures. In the second part of this work, a numerical simulation was performed and a gas-phase chemical mechanism was proposed and discussed. From the comparison between the experimental results and the simulation it was found that CH{sub 3}OO{center_dot} formation has a determinant role in oxygenated compound production, since its fast formation disfavoured radical recombination. At 5 deg. C the oxidation leads mainly towards oxygenated compound formation, and plasma dissociation was the major phenomenon responsible for CH{sub 4} conversion. At 300 deg. C, higher CH{sub 4} conversion resulted from oxidative reactions induced by {center_dot}OH radicals with a chemistry predominantly oxidative, producing CO, H{sub 2}, CO{sub 2} and H{sub 2}O.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

Science.gov (United States)

Shellnutt, J Gregory

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

Gravity Effects Observed In Partially Premixed Flames

Science.gov (United States)

Puri, Ishwar K.; Aggarwal, Suresh K.; Lock, Andrew J.; Gauguly, Ranjan; Hegde, Uday

2003-01-01

Partially premixed flames (PPFs) contain a rich premixed fuel air mixture in a pocket or stream, and, for complete combustion to occur, they require the transport of oxidizer from an appropriately oxidizer-rich (or fuel-lean) mixture that is present in another pocket or stream. Partial oxidation reactions occur in fuel-rich portions of the mixture and any remaining unburned fuel and/or intermediate species are consumed in the oxidizer-rich portions. Partial premixing, therefore, represents that condition when the equivalence ratio (phi) in one portion of the flowfield is greater than unity, and in another section its value is less than unity. In general, for combustion to occur efficiently, the global equivalence ratio is in the range fuel-lean to stoichiometric. These flames can be established by design by placing a fuel-rich mixture in contact with a fuel-lean mixture, but they also occur otherwise in many practical systems, which include nonpremixed lifted flames, turbulent nonpremixed combustion, spray flames, and unwanted fires. Other practical applications of PPFs are reported elsewhere. Although extensive experimental studies have been conducted on premixed and nonpremixed flames under microgravity, there is a absence of previous experimental work on burner stabilized PPFs in this regard. Previous numerical studies by our group employing a detailed numerical model showed gravity effects to be significant on the PPF structure. We report on the results of microgravity experiments conducted on two-dimensional (established on a Wolfhard-Parker slot burner) and axisymmetric flames (on a coannular burner) that were investigated in a self-contained multipurpose rig. Thermocouple and radiometer data were also used to characterize the thermal transport in the flame.

Hydrogen Production via Synthetic Gas by Biomass/Oil Partial Oxidation

Czech Academy of Sciences Publication Activity Database

Hanika, Jiří; Lederer, J.; Tukač, V.; Veselý, Václav; Kováč, D.

176-177, - (2011), s. 286-290 ISSN 1385-8947. [International Conference on Chemical Reactors CHEMREACTOR-19 /19./. Vienna, 05.09.2010-09.09.2010] R&D Projects: GA MPO 2A-2TP1/024 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrogen * biomass * partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.461, year: 2011

Partial oxidation of TiN coating by hydrothermal treatment and ozone treatment to improve its osteoconductivity

International Nuclear Information System (INIS)

Shi, Xingling; Xu, Lingli; Le, Thi Bang; Zhou, Guanghong; Zheng, Chuanbo; Tsuru, Kanji; Ishikawa, Kunio

2016-01-01

Dental implants made of pure titanium suffer from abrasion and scratch during routine oral hygiene procedures. This results in an irreversible surface damage, facilitates bacteria adhesion and increases risk of peri-implantitis. To overcome these problems, titanium nitride (TiN) coating was introduced to increase surface hardness of pure titanium. However, the osteoconductivity of TiN is considered to be similar or superior to that of titanium and its alloys and therefore surface modification is necessary. In this study, TiN coating prepared through gas nitriding was partially oxidized by hydrothermal (HT) treatment and ozone (O 3 ) treatment in pure water to improve its osteoconductivity. The effects of HT treatment and O 3 treatment on surface properties of TiN were investigated and the osteoconductivity after undergoing treatment was assessed in vitro using osteoblast evaluation. The results showed that the critical temperature for HT treatment was 100 °C since higher temperatures would impair the hardness of TiN coating. By contrast, O 3 treatment was more effective in oxidizing TiN surfaces, improving its wettability while preserving its morphology and hardness. Osteoblast attachment, proliferation, alkaline phosphatase (ALP) expression and mineralization were improved on oxidized specimens, especially on O 3 treated specimens, compared with untreated ones. These effects seemed to be consequences of partial oxidation, as well as improved hydrophilicity and surface decontamination. Finally, it was concluded that, partially oxidized TiN is a promising coating to be used for dental implant. - Highlights: • TiN coating surface was oxidized by hydrothermal or ozone treatment while preserving its hardness. • Improved wettability, decontamination and interstitial N promoted osteoblast responses. • Partial oxidation makes TiN a promising coating for dental implant with good osteoconductivity.

Partial oxidation of TiN coating by hydrothermal treatment and ozone treatment to improve its osteoconductivity

Energy Technology Data Exchange (ETDEWEB)

Shi, Xingling [School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Department of Biomaterials, Faculty of Dental Science, Kyushu University, Fukuoka 812-8582 (Japan); Jiangsu Provincial Key Laboratory for Interventional Medical Devices, Huaiyin Institute of Technology, Huaian 223003 (China); Xu, Lingli, E-mail: linly311@163.com [School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Le, Thi Bang [Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur (Malaysia); Zhou, Guanghong [Jiangsu Provincial Key Laboratory for Interventional Medical Devices, Huaiyin Institute of Technology, Huaian 223003 (China); Zheng, Chuanbo, E-mail: zjust316@163.com [School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Tsuru, Kanji; Ishikawa, Kunio [Department of Biomaterials, Faculty of Dental Science, Kyushu University, Fukuoka 812-8582 (Japan)

2016-02-01

Dental implants made of pure titanium suffer from abrasion and scratch during routine oral hygiene procedures. This results in an irreversible surface damage, facilitates bacteria adhesion and increases risk of peri-implantitis. To overcome these problems, titanium nitride (TiN) coating was introduced to increase surface hardness of pure titanium. However, the osteoconductivity of TiN is considered to be similar or superior to that of titanium and its alloys and therefore surface modification is necessary. In this study, TiN coating prepared through gas nitriding was partially oxidized by hydrothermal (HT) treatment and ozone (O{sub 3}) treatment in pure water to improve its osteoconductivity. The effects of HT treatment and O{sub 3} treatment on surface properties of TiN were investigated and the osteoconductivity after undergoing treatment was assessed in vitro using osteoblast evaluation. The results showed that the critical temperature for HT treatment was 100 °C since higher temperatures would impair the hardness of TiN coating. By contrast, O{sub 3} treatment was more effective in oxidizing TiN surfaces, improving its wettability while preserving its morphology and hardness. Osteoblast attachment, proliferation, alkaline phosphatase (ALP) expression and mineralization were improved on oxidized specimens, especially on O{sub 3} treated specimens, compared with untreated ones. These effects seemed to be consequences of partial oxidation, as well as improved hydrophilicity and surface decontamination. Finally, it was concluded that, partially oxidized TiN is a promising coating to be used for dental implant. - Highlights: • TiN coating surface was oxidized by hydrothermal or ozone treatment while preserving its hardness. • Improved wettability, decontamination and interstitial N promoted osteoblast responses. • Partial oxidation makes TiN a promising coating for dental implant with good osteoconductivity.

Laparoscopic partial nephrectomy for endophytic hilar tumors

DEFF Research Database (Denmark)

Di Pierro, G B; Tartaglia, N; Aresu, L

2014-01-01

To analyze feasibility and outcomes of laparoscopic partial nephrectomy (LPN) for endophytic hilar tumors in low-intermediate (ASA I-II) risk patients.......To analyze feasibility and outcomes of laparoscopic partial nephrectomy (LPN) for endophytic hilar tumors in low-intermediate (ASA I-II) risk patients....

Interaction of dimethylamine with clean and partially oxidized copper surfaces

Science.gov (United States)

Kelber, J. A.; Rogers, J. W.; Banse, B. A.; Koel, B. E.

1990-05-01

The interaction of dimethylamine (DMA) with partially oxidized polycrystalline copper [Cu(poly)] and clean and partially oxidized Cu(110) between 110 and 500 K has been examined using electron stimulated desorption (ESD), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). ESD mass spectra of the DMA adsorbed on O/Cu(poly) between 112 and 230 K consistently display peaks at 44 amu [(CH 3) 2N] + and 46 amu [(CH 3) 2NH-H] +, but no significant parent peak at 45 amu [(CH 3) 2NH] +, even though this last feature is prominent in the gas-phase mass spectrum. OH - is not observed at temperatures below 184 K and the yield at higher temperatures is much less than that of O +. HREELS of DMA on clean and oxygen covered Cu(110) obtained at temperatures between 100 and 320 K show characteristic vibrational spectra for molecular DMA and no OH(a) vibrational modes. TPD results show that the desorption profiles of all the major peaks in the DMA mass spectrum follow that of the parent peak with no evidence for production of H 2O. The ESD, HREELS and TPD results all indicate that DMA is molecularly and reversibly adsorbed, with no significant formation of surface hydroxyl species. The results indicate that preferential adsorption of amines from amine/epoxy mixtures onto metal oxide surfaces could passivate the surface and prevent subsequent bonding to the epoxy resin.

Mechanism of 1, 1-d2 propene oxidation over oxide catalysts

International Nuclear Information System (INIS)

Portefaix, J.L.; Figueras, F.; Forissier, M.

1980-01-01

CD 2 CHCH 3 was oxidized over bismuth molybdate, tin-antimony mixed oxides and supported molybdenum and vanadium oxide catalysts. The deuterium retention is high ( > 90%) in the recovered propene. Percentage retentions of deuterium in the acrolein agree with literature data when bismuth molybdate is used as catalyst. On Sb-Sn-O and supported Mo and V oxides, no isotope effect is noticed for the abstraction of the second hydrogen from the olefin. The slow step of the reaction may therefore be different for the oxidation of propene on Bi-Mo-O and Sb-Sn-O. The ethanal produced by oxidation of CD 2 CHCH 3 contains only minor amounts of deuterium, whatever the catalyst used. It is suggested that partial oxidation of propene to acrolein and C-C bond rupture are parallel reactions which involve different intermediates. Possible mechanisms adapted from organic chemistry are presented to explain these findings. 4 tables

Physical, mechanical and electrochemical characterization of all-perovskite intermediate temperature solid oxide fuel cells

Science.gov (United States)

Mohammadi, Alidad

Strontium- and magnesium-doped lanthanum gallate (LSGM) has been considered as a promising electrolyte for solid oxide fuel cell (SOFC) systems in recent years due to its high ionic conductivity and chemical stability over a wide range of oxygen partial pressures and temperatures. This research describes synthesis, physical and mechanical behavior, electrochemical properties, phase evolution, and microstructure of components of an all-perovskite anode-supported intermediate temperature solid oxide fuel cell (ITSOFC), based on porous La 0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) anode, La0.8Sr0.2Ga0.8Mg0.2O 2.8 (LSGM) electrolyte, and porous La0.6Sr0.4Fe 0.8Co0.2O3 (LSCF) cathode. The phase evolution of synthesized LSGM and LSCM powders has been investigated, and it has been confirmed that there is no reaction between LSGM and LSCM at sintering temperature. Using different amounts of poreformers and binders as well as controlling firing temperature, porosity of the anode was optimized while still retaining good mechanical integrity. The effect of cell operation conditions under dry hydrogen fuel on the SOFC open circuit voltage (OCV) and cell performance were also investigated. Characterization study of the synthesized LSGM indicates that sintering at 1500°C obtains higher electrical conductivity compared to the currently published results, while conductivity of pellets sintered at 1400°C and 1450°C would be slightly lower. The effect of sintering temperature on bulk and grain boundary resistivities was also discussed. The mechanical properties, such as hardness, Young's modulus, fracture toughness and modulus of rupture of the electrolyte were determined and correlated with scanning electron microscopy (SEM) morphological characterization. Linear thermal expansion and thermal expansion coefficient of LSGM were also measured.

Thermoelectric characterization of an intermediate temperature solid oxide fuel cell system directly fed by dry biogas

International Nuclear Information System (INIS)

De Lorenzo, G.; Corigliano, O.; Lo Faro, M.; Frontera, P.; Antonucci, P.; Zignani, S.C.; Trocino, S.; Mirandola, F.A.; Aricò, A.S.; Fragiacomo, P.

2016-01-01

Highlights: • Numerical Model (NM) of SOFC Cogenerative System (SCS) fed by dry biogas is set up. • NM simulates new Ni-Fe/CGO protective layer for direct CH_4 consumption at the anode. • NM simulates the anode carbonation phenomenon and is experimentally validated. • The performance parameters trends of SCS fed by three types of dry biogas are shown. • SEM images after 40 h of operation show that there is no anode carbon deposition. - Abstract: A properly manufactured intermediate temperature Solid Oxide Fuel Cell (SOFC) can be directly fed by dry biogas, considering also the electrochemical partial and total oxidation reactions of methane in the biogas at the anode. In this way the methane in the biogas is electrochemically consumed directly at the fuel cell without the need to mix the biogas with any reforming gas (steam, oxygen or carbon dioxide). In this article, a numerical model of an SOFC system with Ni-Fe/CGO electrocatalyst anode protective layer directly fed by dry biogas, in cogenerative arrangement and with anode exhaust gas recirculation is formulated. The influences of biogas composition, of fuel cell operating current density and of percentage of recirculated anode exhaust gas on the SOFC system performances were evaluated by calculation code. An SOFC test bench was set up to validate the calculation code results experimentally. Furthermore, the numerical model also considers the anode carbonation and evaluates the amount of carbon that can be formed in the anode at chemical equilibrium and quasi-equilibrium conditions associated with the specific anode protective layer used.

Radioactive intermediate products in the photolysis of the system [1-14C] tributyltin oxide cellulose

International Nuclear Information System (INIS)

Kloetzer, D.

1982-01-01

Interactions between matrix and applied biocide in the photochemical degradation of the system [1- 14 C] tributyltin oxide/cellulose have been investigated. The intermediate formation of [1- 14 C] tributylstannyl cellulose ethers was found to be the most important step. The photochemical preparation of bis [8- 14 C] tributylstannyl glucose ether is described. (author)

Benzene oxidation at diamond electrodes: comparison of microcrystalline and nanocrystalline diamonds.

Science.gov (United States)

Pleskov, Yu V; Krotova, M D; Elkin, V V; Varnin, V P; Teremetskaya, I G; Saveliev, A V; Ralchenko, V G

2012-08-27

A comparative study of benzene oxidation at boron-doped diamond (BDD) and nitrogenated nanocrystalline diamond (NCD) anodes in 0.5 M K(2)SO(4) aqueous solution is conducted by using cyclic voltammetry and electrochemical impedance spectroscopy. It is shown by measurements of differential capacitance and anodic current that during the benzene oxidation at the BDD electrode, adsorption of a reaction intermediate occurs, which partially blocks the electrode surface and lowers the anodic current. At the NCD electrode, benzene is oxidized concurrently with oxygen evolution, a (quinoid) intermediate being adsorbed at the electrode. The adsorption and the electrode surface blocking are reflected in the impedance-frequency and impedance-potential complex-plane plots. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH{sub 2}Cl{sub 2}: Fluorescence from intermediate compounds

Energy Technology Data Exchange (ETDEWEB)

Alwis, D.D.D.H [Department of Chemistry, The Open University of Sri Lanka, Nawala (Sri Lanka); Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Chandrika, U.G. [Department of Biochemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Jayaweera, P.M., E-mail: pradeep@sjp.ac.lk [Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka)

2015-02-15

Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH{sub 2}Cl{sub 2} solutions via chemical oxidation using anhydrous FeCl{sub 3}. UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S{sub 2}→S{sub 0} (1{sup 1}B{sub u}→1{sup 1}A{sub g}) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl{sub 3} in CH{sub 2}Cl{sub 2} shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

KAUST Repository

Wang, Zhandong

2017-11-28

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

KAUST Repository

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Hö inghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani

2017-01-01

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

NARCIS (Netherlands)

Deshmukh, S.A.R.K.; Sint Annaland, van M.; Kuipers, J.A.M.

2005-01-01

The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230–260 °C, over a wide range of methanol and oxygen concentrations. The principal

Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

NARCIS (Netherlands)

Deshmukh, S.A.R.K.; van Sint Annaland, M.; Kuipers, J.A.M.

2005-01-01

The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal

Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

Science.gov (United States)

Cuba Torres, Christian Martin

On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

Partial oxidation of methane over Ni/Mg/Al/La mixed oxides prepared from layered double hydrotalcites

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jun [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Zhao, Ning; Wei, Wei [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Sun, Yuhan [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China)

2010-11-15

A series of Ni/Mg/Al/La mixed oxides prepared by thermal decomposition of layered double hydrotalcites (HT) were characterized by XRD, ICP, EXAFS, TGA, TPR-H{sub 2}, SEM, and N{sub 2} adsorption/desorption technique. The results revealed the formation of periclase-type catalysts with mesoporous structure, and the addition of La{sup 3+} lowered the phase crystallization with the formation of small oxide particles. Such catalysts had both high activities and stabilities toward partial oxidation of methane (POM). The catalyst containing 6.5 mol.% La{sup 3+} showed the highest performance at 1053 K with CH{sub 4} conversion of 99%, CO selectivity of 93% and H{sub 2} selectivity of 96%, which could be attributed to the presence of highly dispersed nickel and then the resistance to coke formation due to the promotion effect of lanthanum. (author)

Composite cathode materials development for intermediate temperature solid oxide fuel cell systems

Science.gov (United States)

Qin, Ya

Solid oxide fuel cell (SOFC) systems are of particular interest as electrochemical power systems that can operate on various hydrocarbon fuels with high fuel-to-electrical energy conversion efficiency. Within the SOFC stack, La0.8Sr 0.2Ga0.8Mg0.115Co0.085O3-delta (LSGMC) has been reported as an optimized composition of lanthanum gallate based electrolytes to achieve higher oxygen ionic conductivity at intermediate temperatures, i.e., 500-700°C. The electrocatalytic properties of interfaces between LSGMC electrolytes and various candidate intermediate-temperature SOFC cathodes have been investigated. Sm0.5Sr0.5CoO 3-delta (SSC), and La0.6Sr0.4Co0.2Fe 0.8O3-delta (LSCF), in both pure and composite forms with LSGMC, were investigated with regards to both oxygen reduction and evolution, A range of composite cathode compositions, having ratios of SSC (in wt.%) with LSGMC (wt.%) spanning the compositions 9:1, 8:2, 7:3, 6:4 and 5:5, were investigated to determine the optimal cathode-electrolyte interface performance at intermediate temperatures. All LSGMC electrolyte and cathode powders were synthesized using the glycine-nitrate process (GNP). Symmetrical electrochemical cells were investigated with three-electrode linear dc polarization and ac impedance spectroscopy to characterize the kinetics of the interfacial reactions in detail. Composite cathodes were found to perform better than the single phase cathodes due to significantly reduced polarization resistances. Among those composite SSC-LSGMC cathodes, the 7:3 composition has demonstrated the highest current density at the equivalent overpotential values, indicating that 7:3 is an optimal mixing ratio of the composite cathode materials to achieve the best performance. For the composite SC-LSGMC cathode/LSGMC interface, the cathodic overpotential under 1 A/cm2 current density was as low as 0.085 V at 700°C, 0.062V at 750°C and 0.051V at 800°C in air. Composite LSCF-LSGMC cathode/LSGMC interfaces were found to have

Comparison of partial and full nitrification processes applied for treating high-strength nitrogen wastewaters: microbial ecology through nitrous oxide production.

Science.gov (United States)

Ahn, Joon Ho; Kwan, Tiffany; Chandran, Kartik

2011-04-01

The goal of this study was to compare the microbial ecology, gene expression, biokinetics, and N2O emissions from a lab-scale bioreactor operated sequentially in full-nitrification and partial-nitrification modes. Based on sequencing of 16S rRNA and ammonia monooxygenase subunit A (amoA) genes, ammonia oxidizing bacteria (AOB) populations during full- and partial-nitrification modes were distinct from one another. The concentrations of AOB (XAOB) and their respiration rates during full- and partial-nitrification modes were statistically similar, whereas the concentrations of nitrite oxidizing bacteria (XNOB) and their respiration rates declined significantly after the switch from full- to partial-nitrification. The transition from full-nitrification to partial nitrification resulted in a protracted transient spike of nitrous oxide (N2O) and nitric oxide (NO) emissions, which later stabilized. The trends in N2O and NO emissions correlated well with trends in the expression of nirK and norB genes that code for the production of these gases in AOB. Both the transient and stabilized N2O and NO emissions during partial nitrification were statistically higher than those during steady-state full-nitrification. Based on these results, partial nitrification strategies for biological nitrogen removal, although attractive for their reduced operating costs and energy demand, may need to be optimized against the higher carbon foot-print attributed to their N2O emissions.

Partial oxidation of n-hexadecane through decomposition of hydrogen peroxide in supercritical water

KAUST Repository

Alshammari, Y.M.

2015-01-01

© 2014 The Institution of Chemical Engineers. This work reports the experimental analysis of partial oxidation of n-hexadecane under supercritical water conditions. A novel reactor flow system was developed which allows for total decomposition of hydrogen peroxide in a separate reactor followed partial oxidation of n-hexadecane in a gasification reactor instead of having both reactions in one reactor. The kinetics of hydrothermal decomposition of hydrogen peroxide was studied in order to confirm its full conversion into water and oxygen under the desired partial oxidation conditions, and the kinetic data were found in a good agreement with previously reported literature. The gas yield and gasification efficiency were investigated under different operating parameters. Furthermore, the profile of C-C/C=C ratio was studied which showed the favourable conditions for maximising yields of n-alkanes via hydrogenation of their corresponding 1-alkenes. Enhanced hydrogenation of 1-alkenes was observed at higher O/C ratios and higher residence times, shown by the increase in the C-C/C=C ratio to more than unity, while increasing the temperature has shown much less effect on the C-C/C=C ratio at the current experimental conditions. In addition, GC-MS analysis of liquid samples revealed the formation of heavy oxygenated compounds which may suggest a new addition reaction to account for their formation under the current experimental conditions. Results show new promising routes for hydrogen production with in situ hydrogenation of heavy hydrocarbons in a supercritical water reactor.

RuO4-mediated oxidation of secondary amines: Part 1. Are hydroxylamines main intermediates?

Directory of Open Access Journals (Sweden)

Florea Cristina A.

2016-01-01

Full Text Available The RuO4-catalyzed oxidation of secondary amines Bn-NH-CH2R (1a-b; R=H, Me gave mainly amides, but minute amounts of nitrones PhCH=N(O-CH2R (9a-b and traces of Bn-N(OH-CH2R (R=H, 4a were also detected. In the presence of cyanide, up to 22 reaction products were identified, but mainly α-aminonitriles. Comparison of the oxidation products of 1a-b with those of 4a-b, 9a-b, and Bn-N(O=CHR (10a-b showed that 4a-b cannot be main reaction intermediates formed from 1a-b.

Optimizing solid oxide fuel cell cathode processing route for intermediate temperature operation

DEFF Research Database (Denmark)

Ortiz-Vitoriano, N.; Bernuy-Lopez, Carlos; Ruiz de Larramendi, I.

2013-01-01

-priced raw material and cost-effective production techniques.In this work the perovskite-type La0.6Ca0.4Fe0.8Ni0.2O3 (LCFN) oxide has been used in order to optimize intermediate temperature SOFC cathode processing route. The advantages this material presents arise from the low temperature powder calcination......For Solid Oxide Fuel Cells (SOFCs) to become an economically attractive energy conversion technology suitable materials which allow operation at lower temperatures, while retaining cell performance, must be developed. At the same time, the cell components must be inexpensive - requiring both low...... (∼600°C) and electrode sintering (∼800°C) of LCFN electrodes, making them a cheaper alternative to conventional SOFC cathodes. An electrode polarization resistance as low as 0.10Ωcm2 at 800°C is reported, as determined by impedance spectroscopy studies of symmetrical cells sintered at a range...

Acetylene and oxygen as inhibitors of nitrous oxide production in Nitrosomonas europaea and Nitrosospira briensis: a cautionary tale

NARCIS (Netherlands)

Wrage, N.; Velthof, G.L.; Oenema, O.; Laanbroek, H.J.

2004-01-01

Autotrophic ammonia-oxidizing bacteria produce nitrous oxide (N2O) as a by-product of nitrification or as an intermediate of nitrifier denitrification. In soil incubations, acetylene (C2H2) and large partial pressures of oxygen (O2) are used to distinguish between these sources. C2H2 inhibits

Evidence of an Intermediate Phase in bulk alloy oxide glass sysem

Science.gov (United States)

Chakraborty, S.; Boolchand, P.

2011-03-01

Reversibility windows have been observed in modified oxides (alkali-silicates and -germanates) and identified with Intermediate Phases(IPs). Here we find preliminary evidence of an IP in a ternary oxide glass, (B2 O3)5 (Te O2)95-x (V2O5)x , which is composed of network formers. Bulk glasses are synthesized across the 18% x 35 % composition range, and examined in Raman scattering, modulated DSC and molar volume experiments. Glass transition temperatures Tg (x) steadily decrease with V2O5 content x, and reveal the enthalpy of relaxation at Tg to show a global minimum in the 24% x < 27 range, the reversibility window (IP). Molar volumes reveal a minimum in this window. Raman scattering reveals a Boson mode, and at least six other vibrational bands in the 100cm-1 < ν < 1700cm-1 range. Compositional trends in vibrational mode strengths and frequency are established. These results will be presented in relation to glass structure evolution with vanadia content and the underlying elastic phases. Supported by NSF grant DMR 08-53957.

Mechanisms of deterioration of intermediate moisture food systems

Science.gov (United States)

Labuza, T. P.

1972-01-01

A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

International Nuclear Information System (INIS)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

2015-01-01

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY H2 , TRE and CR could exhibit up to 14.32 mmol·gTOC −1 , 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H 2 yield (GY H2 ), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY H2 , CR and TRE were established with Box–Behnken design. GY H2 , CR and TRE reached up to 14.32 mmol·gTOC −1 , 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO 2 and H 2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH 3 has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient

Modeling of termokinetic oscillations at partial oxidation of methane

Science.gov (United States)

Arutyunov, A. V.; Belyaev, A. A.; Inovenkov, I. N.; Nefedov, V. V.

2017-12-01

Partial oxidation of natural gas at moderate temperatures below 1500 K has significant interest for a number of industrial applications. But such processes can proceed at different unstable regimes including oscillating modes. Nonlinear phenomena at partial oxidation of methane were observed at different conditions. The investigation of the complex nonlinear system of equations that describes this process is a real method to insure its stability at industrial conditions and, at the same time, is an effective tool for its further enhancement. Numerical analysis of methane oxidation kinetics in the continuous stirred-tank reactor, with the use of detailed kinetic model has shown the possibility of the appearance of oscillating modes in the appropriate range of reaction parameters that characterize the composition, pressure, reagents flow, thermophysical features of the system, and geometry of the reactor. The appearance of oscillating modes is connected both with the reaction kinetics, heat release and sink and reagents introduction and removing. At that, oscillations appear only at a limited range of parameters, but can be accompanied by significant change in the yield of products. We have determined the range of initial temperature and pressure at which oscillations can be observed, if all other parameters remained fixed. The boundaries of existence of oscillations on the phase plane were calculated. It was shown that depending on the position inside the oscillation region the oscillations have different frequency and amplitude. It was reviled the role of heat exchange with the environment: at the absence of heat exchange the oscillating modes are impossible. In the vicinity of the boundary of phase range, where oscillations exist, significant change of concentration of some products were observed, for example, that of CO2, which in this case one of the principal products is. At that, insignificant increase in pressure not only change the character of CO2 behaving

Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures.

Science.gov (United States)

Vavilin, V A; Rytov, S V

2015-09-01

A kinetic analysis of nitrate denitrification by a single or two species of denitrifying bacteria with glucose or ethanol as a carbon source and nitrite or nitrous oxide as intermediate products was performed using experimental data published earlier (Menyailo and Hungate, 2006; Vidal-Gavilan et al., 2013). Modified Monod kinetics was used in the dynamic biological model. The special equations were added to the common dynamic biological model to describe how isotopic fractionation between N species changes. In contrast to the generally assumed first-order kinetics, in this paper, the traditional Rayleigh equation describing stable nitrogen and oxygen isotope fractionation in nitrate was derived from the dynamic isotopic equations for any type of kinetics. In accordance with the model, in Vidal-Gavilan's experiments, the maximum specific rate of nitrate reduction was proved to be less for ethanol compared to glucose. Conversely, the maximum specific rate of nitrite reduction was proved to be much less for glucose compared to ethanol. Thus, the intermediate nitrite concentration was negligible for the ethanol experiment, while it was significant for the glucose experiment. In Menyailo's and Hungate's experiments, the low value of maximum specific rate of nitrous oxide reduction gives high intermediate value of nitrous oxide concentration. The model showed that the dynamics of nitrogen and oxygen isotope signatures are responding to the biological dynamics. Two microbial species instead of single denitrifying bacteria are proved to be more adequate to describe the total process of nitrate denitrification to dinitrogen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

Energy Technology Data Exchange (ETDEWEB)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

2015-09-15

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.

The influence of partial oxidation mechanisms on tar destruction in TwoStage biomass gasification

DEFF Research Database (Denmark)

Ahrenfeldt, Jesper; Egsgaard, Helge; Stelte, Wolfgang

2013-01-01

adsorption and determined by stable isotope dilution analysis. The results have shown that partial oxidation reduces and converts primary tars into low molecular weight, polycyclic aromatic hydrocarbons (PAHs), primarily naphthalene. At temperatures above 950°C practically all phenol is converted...

Mobile communication and intermediality

DEFF Research Database (Denmark)

Helles, Rasmus

2013-01-01

communicative affordances of mobile devices in order to understand how people choose between them for different purposes. It is argued that mobile communication makes intermediality especially central, as the choice of medium is detached from the location of stationary media and begins to follow the user across......The article argues the importance of intermediality as a concept for research in mobile communication and media. The constant availability of several, partially overlapping channels for communication (texting, calls, email, Facebook, etc.) requires that we adopt an integrated view of the various...

Oxygen partial pressure: a key to alloying and discovery in metal oxide--metal eutectic systems

International Nuclear Information System (INIS)

Holder, J.D.; Clark, G.W.; Oliver, B.F.

1978-01-01

Control of oxygen partial pressure is essential in the directional solidification of oxide--metal eutectic composites by techniques involving gas-solid and gas-liquid interactions. The existence of end components in the eutectic composite is Po 2 sensitive as are melt stoichiometry, solid phase compositions, and vapor losses due to oxidation-volatilization. Simple criteria are postulated which can aid the experimentalist in selecting the proper gas mixture for oxide--metal eutectic composite growth. The Cr 2 O 3 --Mo--Cr systems was used to verify certain aspects of the proposed criteria

Partial oxidation process for producing a stream of hot purified gas

Science.gov (United States)

Leininger, T.F.; Robin, A.M.; Wolfenbarger, J.K.; Suggitt, R.M.

1995-03-28

A partial oxidation process is described for the production of a stream of hot clean gas substantially free from particulate matter, ammonia, alkali metal compounds, halides and sulfur-containing gas for use as synthesis gas, reducing gas, or fuel gas. A hydrocarbonaceous fuel comprising a solid carbonaceous fuel with or without liquid hydrocarbonaceous fuel or gaseous hydrocarbon fuel, wherein said hydrocarbonaceous fuel contains halides, alkali metal compounds, sulfur, nitrogen and inorganic ash containing components, is reacted in a gasifier by partial oxidation to produce a hot raw gas stream comprising H{sub 2}, CO, CO{sub 2}, H{sub 2}O, CH{sub 4}, NH{sub 3}, HCl, HF, H{sub 2}S, COS, N{sub 2}, Ar, particulate matter, vapor phase alkali metal compounds, and molten slag. The hot raw gas stream from the gasifier is split into two streams which are separately deslagged, cleaned and recombined. Ammonia in the gas mixture is catalytically disproportionated into N{sub 2} and H{sub 2}. The ammonia-free gas stream is then cooled and halides in the gas stream are reacted with a supplementary alkali metal compound to remove HCl and HF. Alkali metal halides, vaporized alkali metal compounds and residual fine particulate matter are removed from the gas stream by further cooling and filtering. The sulfur-containing gases in the process gas stream are then reacted at high temperature with a regenerable sulfur-reactive mixed metal oxide sulfur sorbent material to produce a sulfided sorbent material which is then separated from the hot clean purified gas stream having a temperature of at least 1000 F. 1 figure.

Thermodynamic Study on the Catalytic Partial Oxidation of Methane to Syngas

Institute of Scientific and Technical Information of China (English)

XUJian; WEIWeisheng; 等

2002-01-01

The catalytic partial oxidation of methane to syngas (CO+H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.

YSZ thin films deposited on NiO-CSZ anodes by pulsed injection MOCVD for intermediate temperature-SOFC applications

International Nuclear Information System (INIS)

Garcia, G.; Pardo, J.A.; Santiso, J.; Merino, R.I.; Orera, V.M.; Larrea, A.; Pena, J.I.; Laguna-Bercero, M.A.; Figueras, A.

2004-01-01

Yttria-stabilized zirconia (YSZ) films are prepared on NiO-CaSZ by PIMOCVD (pulsed injection metal organic chemical vapor deposition). High quality, 5 to 10 μm thick, totally dense YSZ layers are prepared by controlling the oxygen partial pressure during the deposition. YSZ solid electrolyte deposition onto Ni-YSZ eutectic substrate is found to be a promising combination with regard to intermediate-temperature solid-oxide fuel cell applications. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Wael Ahmed Abou Taleb Sayed

2011-01-13

This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

KAUST Repository

Moshammer, Kai

2016-09-17

This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015, 119, 7361–7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450–1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

Science.gov (United States)

Opila, Elizabeth J.; Boyd, Meredith

2010-01-01

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Review Of Plutonium Oxidation Literature

International Nuclear Information System (INIS)

Korinko, P.

2009-01-01

A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

Development of a novel reactor concept for the partial oxidation of methane to syngas

NARCIS (Netherlands)

Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

2004-01-01

The gas-to-liquid process, consisting of the partial oxidation of methane (POM) followed by the Fischer-Tropsch reaction, is a promising alternative to conventional oil processing for the production of liquid fuels. The cost of a conventional POM process is mainly determined by cryogenic air

Modelling of a reverse flow catalytic membrane reactor for the partial oxidation of methane

NARCIS (Netherlands)

Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

2003-01-01

Gas-To-Liquid (GTL) processes have great potential as alternative to conventional oil and coal processing for the production of liquid fuels. In GTL-processes the partial oxidation of methane (POM) is combined with the Fischer-Tropsch reaction. An important part of the investment costs of a

Positron scattering by atomic hydrogen at intermediate energies

International Nuclear Information System (INIS)

Higgins, K.; Burke, P.G.; Walters, H.R.J.

1990-01-01

Results of an accurate calculation based upon the intermediate energy R-matrix theory are reported for elastic scattering of positrons by atomic hydrogen. T-matrix elements for both low and intermediate energy scattering are evaluated for the S e , P o , D e and F o partial wave symmetries. The low-energy elastic phaseshifts are found to be in good agreement with previous accurate variational calculations. Using an optical potential approach to include the effect of the higher partial waves, elastic and total cross sections are presented for energies ranging from near threshold to 3.7 Rydbergs. (author)

Glutamate availability is important in intramuscular amino acid metabolism and TCA cycle intermediates but does not affect peak oxidative metabolism

DEFF Research Database (Denmark)

Mourtzakis, M.; Graham, T.E.; Gonzalez-Alonso, J.

2008-01-01

Muscle glutamate is central to reactions producing 2-oxoglutarate, a tricarboxylic acid (TCA) cycle intermediate that essentially expands the TCA cycle intermediate pool during exercise. Paradoxically, muscle glutamate drops approximately 40-80% with the onset of exercise and 2-oxoglutarate...... declines in early exercise. To investigate the physiological relationship between glutamate, oxidative metabolism, and TCA cycle intermediates (i.e., fumarate, malate, 2-oxoglutarate), healthy subjects trained (T) the quadriceps of one thigh on the single-legged knee extensor ergometer (1 h/day at 70......% maximum workload for 5 days/wk), while their contralateral quadriceps remained untrained (UT). After 5 wk of training, peak oxygen consumption (VO2peak) in the T thigh was greater than that in the UT thigh (Pglutamate infusion. Peak...

Glutamate availability is important in intramuscular amino acid metabolism and TCA cycle intermediates but does not affect peak oxidative metabolism.

Science.gov (United States)

Mourtzakis, M; Graham, T E; González-Alonso, J; Saltin, B

2008-08-01

Muscle glutamate is central to reactions producing 2-oxoglutarate, a tricarboxylic acid (TCA) cycle intermediate that essentially expands the TCA cycle intermediate pool during exercise. Paradoxically, muscle glutamate drops approximately 40-80% with the onset of exercise and 2-oxoglutarate declines in early exercise. To investigate the physiological relationship between glutamate, oxidative metabolism, and TCA cycle intermediates (i.e., fumarate, malate, 2-oxoglutarate), healthy subjects trained (T) the quadriceps of one thigh on the single-legged knee extensor ergometer (1 h/day at 70% maximum workload for 5 days/wk), while their contralateral quadriceps remained untrained (UT). After 5 wk of training, peak oxygen consumption (VO2peak) in the T thigh was greater than that in the UT thigh (PTCA cycle intermediates. In the UT thigh, peak exercise (vs. rest) induced an increase in fumarate (0.33+/-0.07 vs. 0.02+/-0.01 mmol/kg dry wt (dw), PTCA cycle, glutamate and TCA cycle intermediates do not directly affect VO2peak in either trained or untrained muscle.

Microgravity Processing of Oxide Superconductors

Science.gov (United States)

Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus; McCallum, William; Peters, Palmer (Technical Monitor)

2000-01-01

The primary goal is to understand the microstructures which develop under the nonequilibrium solidification conditions achieved by melt processing in copper oxide superconductor systems. More specifically, to define the liquidus at the Y- 1:2:3 composition, the Nd-1:2:3 composition, and several intermediate partial substitution points between pure Y-1:2:3 and Nd-1:2:3. A secondary goal has been to understand resultant solidification morphologies and pathways under a variety of experimental conditions and to use this knowledge to better characterize solidification phenomena in these systems.

Reaction scheme of partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia

NARCIS (Netherlands)

Zhu, J.J.; van Ommen, J.G.; Lefferts, Leonardus

2004-01-01

The partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia (YSZ) was studied with in situ FTIR and both steady-state and transient experiments. The four major products, CO, H2, CO2, and H2O, are primary products of CPOM over YSZ. Besides these major products and traces of

Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

DEFF Research Database (Denmark)

Kimmerle, B.; Baiker, A.; Grunwaldt, Jan-Dierk

2010-01-01

Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

Antiferromagnetic iridium-manganese intermediate layers for perpendicular recording media (invited)

Science.gov (United States)

Srinivasan, Kumar; Piramanayagam, S. N.; Sbiaa, Rachid; Kay, Yew Seng; Tan, Hang Khume; Wong, Seng Kai

2009-04-01

Current generation of cobalt-oxide-based perpendicular magnetic recording media uses single or dual ruthenium intermediate layers in order to grow crystallographically textured, and magnetically isolated granular media. In this work, the potential advantages of an antiferromagnetic iridium-manganese intermediate layer directly under the recording layer are highlighted. Owing to its close lattice matching with hexagonal cobalt, iridium-manganese which has the L12, or AuCu3-type crystal structure, can support the heteroepitaxial growth of the cobalt-based recording layer. In one of the media schemes described here, (111) textured iridium-manganese thin film was grown on 7.5 nm thick ruthenium layer. On the iridium-manganese as segregation layer, the Co-oxide-based magnetic recording layer showed perpendicular texture with Δθ50 below 4°, coercivity of over 4000 Oe alongside magnetic exchange decoupling, average grain sizes of 6 nm with distributions under 14%, and improved thermal stability. Measurements of the anisotropy constant did not show any significant change and even an IrMn capping layer was observed to improve the thermal stability. The possible mechanisms through which the IrMn layer could affect the thermal stability are hypothesized. The initial layers of the magnetic recording layer on IrMn segregation layers also showed exchange-decoupled and segregated grains, which is unlike that observed on Ru segregation layers. In a second media scheme, (111) textured iridium-manganese thin film was grown on a crystalline soft magnetic underlayer belonging on top of amorphous soft underlayers. In this scheme, partial pinning of the soft underlayer due to exchange-bias interaction with the IrMn layer was observed. This scheme offers the possibility to reduce the intermediate layer thickness, thus improve media writability, and with further optimization, could potentially facilitate the approach toward 1 Tbits/in.2.

Reactions of stabilized Criegee Intermediates

Science.gov (United States)

Vereecken, Luc; Harder, Hartwig; Novelli, Anna

2014-05-01

Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

Energy Technology Data Exchange (ETDEWEB)

Rajagopalan, S., E-mail: rajagopalan78@hotmail.com [Indira Gandhi Centre for Atomic Research, Materials Science Group (India); Asthalter, T., E-mail: t.asthalter@web.de [Universität Stuttgart, Institute of Physical Chemistry (Germany); Rabe, V.; Laschat, S. [Universität Stuttgart, Institute of Organic Chemistry (Germany)

2016-12-15

Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe{sub 3}(μ{sub 3}-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe{sub 3}(μ{sub 3}-O) in pyridine solution, Fe{sub 3}(μ{sub 3}-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe{sub 3}(μ{sub 3}-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe{sup (III)}(C{sub 5}H{sub 5}N){sub 2}(O{sub 2}CCH{sub 3}){sub 2}]{sup +} and Fe{sup (II)}(C{sub 5}H{sub 5}N){sub 4}(O{sub 2}CCH{sub 3}){sub 2}, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

Krebs Cycle Intermediates Protective against Oxidative Stress by Modulating the Level of Reactive Oxygen Species in Neuronal HT22 Cells

Directory of Open Access Journals (Sweden)

Kenta Sawa

2017-03-01

Full Text Available Krebs cycle intermediates (KCIs are reported to function as energy substrates in mitochondria and to exert antioxidants effects on the brain. The present study was designed to identify which KCIs are effective neuroprotective compounds against oxidative stress in neuronal cells. Here we found that pyruvate, oxaloacetate, and α-ketoglutarate, but not lactate, citrate, iso-citrate, succinate, fumarate, or malate, protected HT22 cells against hydrogen peroxide-mediated toxicity. These three intermediates reduced the production of hydrogen peroxide-activated reactive oxygen species, measured in terms of 2′,7′-dichlorofluorescein diacetate fluorescence. In contrast, none of the KCIs—used at 1 mM—protected against cell death induced by high concentrations of glutamate—another type of oxidative stress-induced neuronal cell death. Because these protective KCIs did not have any toxic effects (at least up to 10 mM, they have potential use for therapeutic intervention against chronic neurodegenerative diseases.

A novel technique for hydrogen production from hog-manure in supercritical partial oxidation (SCWPO)

Energy Technology Data Exchange (ETDEWEB)

Youssef, Emhemmed A.; Charpentier, Paul [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Nakhla, George [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering; Elbeshbishy, Elsayed; Hafez, Hisham [Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering

2010-07-01

In this study, the catalytic hydrogen production from hog manure using supercritical water partial oxidation was investigated in a batch reactor at a temperature of 500 C, and pressure of 28 MPa using several metallic catalysts. Hog manure was characterized by a total and soluble chemical oxygen demand (TCOD, SCOD) of 57000 and 28000 mg/L, total and volatile suspended solids (TSS, VSS) of 25000, 19000, and ammonia of 2400 mg/L, respectively. The order of H{sub 2} production was the following: Pd/AC > Ru/Al{sub 2}O{sub 3} > Ru/AC > AC > NaOH. The order of COD reduction efficiency was as follows: NaOH > Ru/AC > AC > Ru/Al{sub 2}O{sub 3} > Pd/AC. The behaviour of the volatile fatty acids (VFA's), ethanol, methanol, ammonia, H{sub 2}S, and Sulfate was investigated experimentally and discussed. A 35 % reduction in the H{sub 2} and CH{sub 4} yields was observed in the sequential gasification partial oxidation (oxidant at an 80 % of theoretical requirement) experiments compared to the gasification experiments (catalyst only). Moreover, this reduction in gas yields was coincided with a 45 % reduction in the liquid effluent chemical oxygen demand (COD), 60 % reduction of the ammonia concentration in the liquid effluent, and 20 % reduction in the H{sub 2}S concentration in the effluent gas. (orig.)

Oxidative Stress in Patients with Drug Resistant Partial Complex Seizure

Directory of Open Access Journals (Sweden)

Lourdes Lorigados Pedre

2018-06-01

Full Text Available Oxidative stress (OS has been implicated as a pathophysiological mechanism of drug-resistant epilepsy, but little is known about the relationship between OS markers and clinical parameters, such as the number of drugs, age onset of seizure and frequency of seizures per month. The current study’s aim was to evaluate several oxidative stress markers and antioxidants in 18 drug-resistant partial complex seizure (DRPCS patients compared to a control group (age and sex matched, and the results were related to clinical variables. We examined malondialdehyde (MDA, advanced oxidation protein products (AOPP, advanced glycation end products (AGEs, nitric oxide (NO, uric acid, superoxide dismutase (SOD, glutathione, vitamin C, 4-hydroxy-2-nonenal (4-HNE and nitrotyrosine (3-NT. All markers except 4-HNE and 3-NT were studied by spectrophotometry. The expressions of 4-HNE and 3-NT were evaluated by Western blot analysis. MDA levels in patients were significantly increased (p ≤ 0.0001 while AOPP levels were similar to the control group. AGEs, NO and uric acid concentrations were significantly decreased (p ≤ 0.004, p ≤ 0.005, p ≤ 0.0001, respectively. Expressions of 3-NT and 4-HNE were increased (p ≤ 0.005 similarly to SOD activity (p = 0.0001, whereas vitamin C was considerably diminished (p = 0.0001. Glutathione levels were similar to the control group. There was a positive correlation between NO and MDA with the number of drugs. The expression of 3-NT was positively related with the frequency of seizures per month. There was a negative relationship between MDA and age at onset of seizures, as well as vitamin C with seizure frequency/month. We detected an imbalance in the redox state in patients with DRCPS, supporting oxidative stress as a relevant mechanism in this pathology. Thus, it is apparent that some oxidant and antioxidant parameters are closely linked with clinical variables.

Partial oxidation of dimethyl ether using the structured catalyst Rh/Al2O3/Al prepared through the anodic oxidation of aluminum.

Science.gov (United States)

Yu, B Y; Lee, K H; Kim, K; Byun, D J; Ha, H P; Byun, J Y

2011-07-01

The partial oxidation of dimethyl ether (DME) was investigated using the structured catalyst Rh/Al2O3/Al. The porous Al2O3 layer was synthesized on the aluminum plate through anodic oxidation in an oxalic-acid solution. It was observed that about 20 nm nanopores were well developed in the Al2O3 layer. The thickness of Al2O3 layer can be adjusted by controlling the anodizing time and current density. After pore-widening and hot-water treatment, the Al2O3/Al plate was calcined at 500 degrees C for 3 h. The obtained delta-Al2O3 had a specific surface area of 160 m2/g, making it fit to be used as a catalyst support. A microchannel reactor was designed and fabricated to evaluate the catalytic activity of Rh/Al2O3/Al in the partial oxidation of DME. The structured catalyst showed an 86% maximum hydrogen yield at 450 degrees C. On the other hand, the maximum syngas yield by a pack-bed-type catalyst could be attained by using a more than fivefold Rh amount compared to that used in the structured Rh/Al2O3/Al catalyst.

Self-Driven Bioelectrochemical Mineralization of Azobenzene by Coupling Cathodic Reduction with Anodic Intermediate Oxidation

International Nuclear Information System (INIS)

Liu, Rong-Hua; Li, Wen-Wei; Sheng, Guo-Ping; Tong, Zhong-Hua; Lam, Michael Hon-Wah; Yu, Han-Qing

2015-01-01

Highlights: • Azobenzene was reduced to aniline at the cathode of an acetate-fueled MFC. • Aniline was degraded at the bioanode of a single-chamber MFC. • Cathodic reduction of azobenzene was coupled with anodic oxidation of aniline. • Self-driven, complete mineralization of azobenzene in an MFC was accomplished. - Abstract: Bioelectrochemical systems have been intensively studied as a promising technology for wastewater treatment and environment remediation. Coupling of the anodic and cathodic electrochemical reactions allows an enhanced degradation of recalcitrant organics, but external power supply is usually needed to overcome the thermodynamic barrier. In this work, we report a self-driven degradation of azobenzene in a microbial fuel cell (MFC), where the cathodic reduction of azobenzene was effectively coupled with the anodic oxidation of its reduction degradation intermediate (i.e., aniline). The anodic degradation rate of aniline, as the sole carbon source, was significantly higher than that under open-circuit conditions, suggesting a considerable bioelectrochemical oxidation of aniline. Output voltages up to 8 mV were obtained in the MFC. However, a shift of cathodic electron acceptor from oxygen to azobenzene resulted in a decreased aniline degradation rate and output voltage. The present work may provide valuable implications for development of sustainable bioelectrochemical technologies for environmental remediation

Isoporphyrin Intermediate in Heme Oxygenase Catalysis

Science.gov (United States)

Evans, John P.; Niemevz, Fernando; Buldain, Graciela; de Montellano, Paul Ortiz

2008-01-01

Human heme oxygenase-1 (hHO-1) catalyzes the O2- and NADPH-dependent oxidation of heme to biliverdin, CO, and free iron. The first step involves regiospecific insertion of an oxygen atom at the α-meso carbon by a ferric hydroperoxide and is predicted to proceed via an isoporphyrin π-cation intermediate. Here we report spectroscopic detection of a transient intermediate during oxidation by hHO-1 of α-meso-phenylheme-IX, α-meso-(p-methylphenyl)-mesoheme-III, and α-meso-(p-trifluoromethylphenyl)-mesoheme-III. In agreement with previous experiments (Wang, J., Niemevz, F., Lad, L., Huang, L., Alvarez, D. E., Buldain, G., Poulos, T. L., and Ortiz de Montellano, P. R. (2004) J. Biol. Chem. 279, 42593–42604), only the α-biliverdin isomer is produced with concomitant formation of the corresponding benzoic acid. The transient intermediate observed in the NADPH-P450 reductase-catalyzed reaction accumulated when the reaction was supported by H2O2 and exhibited the absorption maxima at 435 and 930 nm characteristic of an isoporphyrin. Product analysis by reversed phase high performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry of the product generated with H2O2 identified it as an isoporphyrin that, on quenching, decayed to benzoylbiliverdin. In the presence of H218O2, one labeled oxygen atom was incorporated into these products. The hHO-1-isoporphyrin complexes were found to have half-lives of 1.7 and 2.4 h for the p-trifluoromethyl- and p-methyl-substituted phenylhemes, respectively. The addition of NADPH-P450 reductase to the H2O2-generated hHO-1-isoporphyrin complex produced α-biliverdin, confirming its role as a reaction intermediate. Identification of an isoporphyrin intermediate in the catalytic sequence of hHO-1, the first such intermediate observed in hemoprotein catalysis, completes our understanding of the critical first step of heme oxidation. PMID:18487208

Production of reduction gases: partial oxidation of hydrocarbons and coal

Energy Technology Data Exchange (ETDEWEB)

Tippmer, K

1976-04-01

After some general remarks on reduction gas and quality demands, the Texaco process of partial oxidation with scrubbing is dealt with. A comparison of current iron-sponge techniques shows that a heat demand below 3 M kcal/t Fe should be envisaged, which means that heavy fuel oil or coal should be used. The special features of oxygen generation, coal processing, demands made on fuel oil, gasoline, and natural gas, gas generation, soot recovery, hydrogen sulphide-carbon dioxide scrubbing, system Benfield HP process, recycle-carbon dioxide scrubbing, auxiliary steam system, gas preheating, recycle gas cooling and compression, process data and heat balances for natural gas (one-heat system) and heating fuel oil or naphtha (two-heat system) are given.

Oxidative degradation of atenolol by heat-activated persulfate: Kinetics, degradation pathways and distribution of transformation intermediates.

Science.gov (United States)

Miao, Dong; Peng, Jianbiao; Zhou, Xiaohuan; Qian, Li; Wang, Mengjie; Zhai, Li; Gao, Shixiang

2018-05-17

Atenolol (ATL) has been widely detected in wastewater and aquatic environment. Although satisfactory removal of ATL from wastewater could be achieved, the mineralization ratio is usually low, which may result in the accumulation of its transformation products in the effluent and cause additional ecological risk to the environment. The aim of this study is to explore the effectiveness of heat activated persulfate (PS) in the removal of ATL from wastewater. Influencing factors including temperature, PS dosage, solution pH, existence of NO 3 - , Cl - , HCO 3 - and Suwannee river fulvic acid (SRFA) were examined. Complete removal of ATL was achieved within 40 min at pH 7.0 and 70 °C by using 0.5 mM PS. Inhibitive effects of HCO 3 - and FA had been observed on ATL oxidation, which was increased with the increase of their concentration. Sulfate radical (SO 4 - ) was determined as the main reactive species by quenching experiment. Eight intermediates produced in ATL degradation were identified, and four degradation pathways were proposed based on the analysis of mass spectrum and frontier electron densities. The distribution of major intermediates was influenced by reaction temperature. Hydroxylation intermediates and deamidation intermediate were the most prominent at 50 °C and 60 °C, respectively. All intermediates were completely degraded in 40 min except P134 at 70 °C. Effective removal of TOC (74.12%) was achieved with 0.5 mM PS, pH 7.0 and 70 °C after 240 min. The results proved that heat activation of PS is a promising method to remove organic pollutants in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

DEFF Research Database (Denmark)

Forster, M.; Hester, R. E.; Cartling, B.

1982-01-01

An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...... in the (alpha, beta) and the Soret optical absorption band. The spectra of the intermediate state are more like those of the stable reduced form than those of the stable oxidized form. For excitation of 514.5 nm, the most prominent indication of an intermediate state is the wave-number shift of one RR band from...... 1,562 cm-1 in the stable oxidized state through 1,535 cm-1 in the intermediate state to 1,544 cm-1 in the stable reduced state. For excitation at 413.1 nm, a band, present at 1,542 cm-1 in the stable reduced state but not present in the stable oxidized state, is absent in the intermediate state. We...

Partial twisting for scalar mesons

International Nuclear Information System (INIS)

Agadjanov, Dimitri; Meißner, Ulf-G.; Rusetsky, Akaki

2014-01-01

The possibility of imposing partially twisted boundary conditions is investigated for the scalar sector of lattice QCD. According to the commonly shared belief, the presence of quark-antiquark annihilation diagrams in the intermediate state generally hinders the use of the partial twisting. Using effective field theory techniques in a finite volume, and studying the scalar sector of QCD with total isospin I=1, we however demonstrate that partial twisting can still be performed, despite the fact that annihilation diagrams are present. The reason for this are delicate cancellations, which emerge due to the graded symmetry in partially quenched QCD with valence, sea and ghost quarks. The modified Lüscher equation in case of partial twisting is given

Surface intermediates on metal electrodes at high temperatures

DEFF Research Database (Denmark)

Zachau-Christiansen, Birgit; Jacobsen, Torben; Bay, Lasse

1998-01-01

The mechanisms widely conceived for the O(2)-reduction or H(2)-oxidation reactions in SOFC's involve intermediate O/H species adsorbed on the electrode surface. The presence of these intermediates is investigated by linear sweep voltammetry. In air at moderate temperatures (500 degrees C) Pt...

Adiabatic Gasification and Pyrolysis of Coffee Husk Using Air-Steam for Partial Oxidation

OpenAIRE

Catalina Rodriguez; Gerardo Gordillo

2011-01-01

Colombian coffee industry produces about 0.6 million tons of husk (CH) per year which could serve as feedstock for thermal gasification to produce gaseous and liquid fuels. The current paper deals with: (i) CH adiabatic gasification modeling using air-steam blends for partial oxidation and (ii) experimental thermogravimetric analysis to determine the CH activation energy (E). The Chemical Equilibrium with Applications Program (CEA), developed by NASA, was used to estimate the effect of equiva...

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Science.gov (United States)

Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru; Akbay, Taner; Hosoi, Kei

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 °C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 °C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system.

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Toru; Nishiwaki, Futoshi; Yamasaki, Satoru [The Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-choume, Amagasaki, Hyogo 661-0974 (Japan); Akbay, Taner; Hosoi, Kei [Mitsubishi Materials Corporation, Corporate Technology and Development Division, 1002-14 Mukohyama, Naka, Ibaraki 311-0102 (Japan)

2008-07-01

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 C. There are some significant features in IT-SOFC of KEPCO-MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system. (author)

Effect of surface composition of yttrium-stabilized zirconia on partial oxidation of methane to synthesis gas.

NARCIS (Netherlands)

Zhu, J.J.; van Ommen, J.G.; Knoester, A.; Lefferts, Leonardus

2005-01-01

Catalytic partial oxidation of methane to synthesis gas (CPOM) over yttrium-stabilized zirconia (YSZ) was studied within a wide temperature window (500¿1100 °C). The catalysts were characterized by X-ray fluorescence (XRF) and low-energy ion scattering (LEIS). The influence of calcination

Development of a simultaneous partial nitrification and anaerobic ammonia oxidation process in a single reactor.

Science.gov (United States)

Cho, Sunja; Fujii, Naoki; Lee, Taeho; Okabe, Satoshi

2011-01-01

Up-flow oxygen-controlled biofilm reactors equipped with a non-woven fabric support were used as a single reactor system for autotrophic nitrogen removal based on a combined partial nitrification and anaerobic ammonium oxidation (anammox) reaction. The up-flow biofilm reactors were initiated as either a partial nitrifying reactor or an anammox reactor, respectively, and simultaneous partial nitrification and anammox was established by careful control of the aeration rate. The combined partial nitrification and anammox reaction was successfully developed in both biofilm reactors without additional biomass inoculation. The reactor initiated as the anammox reactor gave a slightly higher and more stable mean nitrogen removal rate of 0.35 (±0.19) kg-N m(-3) d(-1) than the reactor initiated as the partial nitrifying reactor (0.23 (±0.16) kg-N m(-3) d(-1)). FISH analysis revealed that the biofilm in the reactor started as the anammox reactor were composed of anammox bacteria located in inner anoxic layers that were surrounded by surface aerobic AOB layers, whereas AOB and anammox bacteria were mixed without a distinguishable niche in the biofilm in the reactor started as the partial nitrifying reactor. However, it was difficult to efficiently maintain the stable partial nitrification owing to inefficient aeration in the reactor, which is a key to development of the combined partial nitrification and anammox reaction in a single biofilm reactor. Copyright © 2010 Elsevier Ltd. All rights reserved.

Effects of Oxygen Partial Pressure on Oxidation Behavior of CMnSi TRIP Steel in an Oxidation-Reduction Scheme

Energy Technology Data Exchange (ETDEWEB)

Kim, Seong-Hwan; Huh, Joo-Youl [Korea University, Seoul (Korea, Republic of); Kim, Myung-Soo; Kim, Jong-Sang [POSCO Technical Research Laboratories, Gwangyang (Korea, Republic of)

2017-02-15

An oxidation-reduction scheme is an alternative approach for improving the galvanizability of advanced high-strength steel in the continuous hot-dip galvanizing process. Here, we investigated the effect of oxygen partial pressure (Po{sub 2}) on the oxidation behavior of a transformation-induced plasticity steel containing 1.5 wt% Si and 1.6 wt% Mn during heating to and holding for 60 s at 700 ℃ under atmospheres with various Po{sub 2} values. Irrespective of Po{sub 2}, a thin amorphous Si-rich layer of Si-Mn-O was formed underneath the Fe oxide scale (a Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} bilayer) in the heating stage. In contrast to Si, Mn tended to segregate at the scale surface as (Fe,Mn){sub 2}O{sub 3}. The multilayered structure of (Fe,Mn){sub 2}O{sub 3}/Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4}/amorphous Si-Mn-O remained even after extended oxidizing at 700 ℃ for 60 s. Fe{sub 2}O{sub 3} was the dominantly growing oxide phase in the scale. The enhanced growth rate of Fe{sub 2}O{sub 3} with increasing Po{sub 2} resulted in the formation of more Kirkendall voids in the amorphous Si-rich layer and a less Mn segregation at the scale surface. The mechanisms underlying the absence of FeO and the formation of Kirkendall voids are discussed.

Surface Intermediates on Metal Electrodes at High Temperature

DEFF Research Database (Denmark)

Zachau-Christiansen, Birgit; Jacobsen, Torben; Bay, Lasse

1997-01-01

The mechanisms widely suggested for the O2-reduc-tion or H2-oxidation SOFC reactions involve inter-mediate O/H species adsorbed on the electrode surface. The presence of these intermediates is investigated by linear sweep voltammetry. In airat moderate temperatures (500øC) Pt in contact with YSZ...

Partial oxidation of methane to syngas on Rh/Al{sub 2}O{sub 3} and Rh/Ce-ZrO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Raquel L.; Bitencourt, Isabela G.; Passos, Fabio B., E-mail: fbpassos@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e Petroleo

2013-01-15

The partial oxidation of methane with {gamma}-Al{sub 2}O{sub 3}-, CeO{sub 2}-, ZrO{sub 2}- and Ce-ZrO{sub 2}-supported rhodium catalysts was investigated. DRIFTS (diffuse reflectance infrared spectroscopy) measurements of adsorbed CO showed the formation of different rhodium species on different supports, which influenced the dispersion of the metal. The effects of the metal dispersion, oxygen storage capacity on the activity of these catalysts for the partial oxidation of methane are discussed. (author)

Identification of key nitrous oxide production pathways in aerobic partial nitrifying granules.

Science.gov (United States)

Ishii, Satoshi; Song, Yanjun; Rathnayake, Lashitha; Tumendelger, Azzaya; Satoh, Hisashi; Toyoda, Sakae; Yoshida, Naohiro; Okabe, Satoshi

2014-10-01

The identification of the key nitrous oxide (N2O) production pathways is important to establish a strategy to mitigate N2O emission. In this study, we combined real-time gas-monitoring analysis, (15)N stable isotope analysis, denitrification functional gene transcriptome analysis and microscale N2O concentration measurements to identify the main N2O producers in a partial nitrification (PN) aerobic granule reactor, which was fed with ammonium and acetate. Our results suggest that heterotrophic denitrification was the main contributor to N2O production in our PN aerobic granule reactor. The heterotrophic denitrifiers were probably related to Rhodocyclales bacteria, although different types of bacteria were active in the initial and latter stages of the PN reaction cycles, most likely in response to the presence of acetate. Hydroxylamine oxidation and nitrifier denitrification occurred, but their contribution to N2O emission was relatively small (20-30%) compared with heterotrophic denitrification. Our approach can be useful to quantitatively examine the relative contributions of the three pathways (hydroxylamine oxidation, nitrifier denitrification and heterotrophic denitrification) to N2O emission in mixed microbial populations. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

Directory of Open Access Journals (Sweden)

Yuni Krisyuningsih Krisnandi

2015-11-01

Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

In situ photoemission spectroscopy using synchrotron radiation for O2 translational kinetic energy induced oxidation processes of partially-oxidized Si(001) surfaces

International Nuclear Information System (INIS)

Teraoka, Yuden; Yoshigoe, Akitaka

2001-01-01

The influence of translational kinetic energy of incident O 2 molecules for the passive oxidation process of partially-oxidized Si(001) surfaces has been studied by photoemission spectroscopy. The translational kinetic energy of O 2 molecules was controlled up to 3 eV by a supersonic seed beam technique using a high temperature nozzle. Two translational kinetic energy thresholds (1.0 eV and 2.6 eV) were found out in accordance with the first-principles calculation for the oxidation of clean surfaces. Si-2p photoemission spectra measured in representative translational kinetic energies revealed that the translational kinetic energy dependent oxidation of dimers and the second layer (subsurface) backbonds were caused by the direct dissociative chemisorption of O 2 molecules. Moreover, the difference in chemical bonds for oxygen atoms was found out to be as low and high binding energy components in O-1s photoemission spectra. Especially, the low binding energy component increased with increasing the translational kinetic energy that indicates the translational kinetic energy induced oxidation in backbonds. (author)

Catalytic partial oxidation of methane over porous silica supported VO{sub x} catalysts

Energy Technology Data Exchange (ETDEWEB)

Pirovano, C.; Schoenborn, E.; Kalevaru, V.N.; Wohlrab, S.; Luecke, B.; Martin, A. [University Rostock e.V., Rostock (Germany). Leibniz Inst. for Catalysis

2011-07-01

High surface area mesoporous siliceous MCM-41 and SBA-15 materials have been used as supports to disperse vanadium oxide species using wet impregnation and incipient wetness impregnation methods. These materials were used as catalysts for the partial oxidation of methane (POM) to formaldehyde. The physico-chemical properties of the solids were studied by means of BET, DR-UV/Vis spectroscopy, Py-FTIR and TEM. The influence of support and the preparation method on the dispersion of VOx is also investigated. The catalytic properties of the catalysts were examined in a fixed bed stainless steel reactor at 923 K. So far a maximum production of formaldehyde can be detected on SBA-15 supported VOx-catalysts prepared by incipient wetness impregnation. On this V/SBA-15 material a covalent attachment of catalytic active molecular vanadium species dominates, which in turn leads to a lower activation temperature and thereby reduced over-oxidation. From the best case, the space time yield of HCHO could be reached close to 775 g{sub HCHO} Kg{sub cat}{sup -1} h{sup -1}. (orig.)

Oxidative demethylation of lanosterol in cholesterol biosynthesis: accumulation of sterol intermediates

International Nuclear Information System (INIS)

Shafiee, A.; Trzaskos, J.M.; Paik, Y.K.; Gaylor, J.L.

1986-01-01

With [ 3 H-24,25]-dihydrolanosterol as substrate, large-scale metabolic formation of intermediates of lanosterol demethylation was carried out to identify all compounds in the metabolic process. Utilizing knowledge of electron transport of lanosterol demethylation, we interrupted the demethylation reaction allowing accumulation and confirmation of the structure of the oxygenated intermediates lanost-8-en-3 beta,32-diol and 3 beta-hydroxylanost-8-en-32-al, as well as the demethylation product 4,4-dimethyl-cholesta-8,14-dien-3 beta-ol. Further metabolism of the delta 8.14-diene intermediate to a single product 4,4-dimethyl-cholest-8-en-3 beta-ol occurs under interruption conditions in the presence of 0.5 mM CN-1. With authentic compounds, each intermediate has been rigorously characterized by high performance liquid chromatography and gas-liquid chromatography plus mass spectral analysis of isolated and derivatized sterols. Intermediates that accumulated in greater abundance were further characterized by ultraviolet, 1 H-NMR, and infrared spectroscopy of the isolated sterols

Identification of the intermediates of in vivo oxidation of 1 ,4-dioxane by monooxygenase-containing bacteria.

Science.gov (United States)

Mahendra, Shaily; Petzold, Christopher J; Baidoo, Edward E; Keasling, Jay D; Alvarez-Cohen, Lisa

2007-11-01

1,4-dioxane is a probable human carcinogen and an emerging water contaminant. Monooxygenase-expressing bacteria have been shown to degrade dioxane via growth-supporting as well as cometabolic mechanisms. In this study, the intermediates of dioxane degradation by monooxygenase-expressing bacteria were determined by triple quadrupole-mass spectrometry and Fourier transform ion cyclotron resonance-mass spectrometry. The major intermediates were identified as 2-hydroxyethoxyacetic acid (HEAA), ethylene glycol, glycolate, and oxalate. Studies with uniformly labeled 14C dioxane showed that over 50% of the dioxane was mineralized to CO2 by CB1190, while 5% became biomass-associated after 48 h. Volatile organic acids and non-volatiles, respectively, accounted for 20 and 11% of the radiolabeled carbon. Although strains cometabolizing dioxane exhibited limited transformation capacities, nearly half of the initial dioxane was recovered as CO2. On the basis of these analytical results, we propose a pathway for dioxane oxidation by monooxygenase-expressing cells in which dioxane is first converted to 2-hydroxy-1,4-dioxane, which is spontaneously oxidized to HEAA. During a second monooxygenation step, HEAA is further hydroxylated, resulting in a mixture of dihydroxyethoxyacetic acids with a hydroxyl group at the ortho or para position. After cleavage of the second ether bond, small organic molecules such as ethylene glycol, glycolate, glyoxalate, and oxalate are progressively formed, which are then mineralized to CO2 via common cellular metabolic pathways. Bioremediation of dioxane via this pathway is not expected to cause an accumulation of toxic compounds in the environment.

Co-free, iron perovskites as cathode materials for intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Hou, Shu-en [Engineering Research Center of Nano-Geo Materials of Ministry of Education, China University of Geosciences, Wuhan, 430074 (China); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Alonso, Jose Antonio [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, E-28049 Madrid (Spain); Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States); Goodenough, John B. [Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, TX 78712 (United States)

2010-01-01

We have developed a Co-free solid oxide fuel cell (SOFC) based upon Fe mixed oxides that gives an extraordinary performance in test-cells with H{sub 2} as fuel. As cathode material, the perovskite Sr{sub 0.9}K{sub 0.1}FeO{sub 3-{delta}} (SKFO) has been selected since it has an excellent ionic and electronic conductivity and long-term stability under oxidizing conditions; the characterization of this material included X-ray diffraction (XRD), thermal analysis, scanning microscopy and conductivity measurements. The electrodes were supported on a 300-{mu}m thick pellet of the electrolyte La{sub 0.8}Sr{sub 0.2}Ga{sub 0.83}Mg{sub 0.17}O{sub 3-{delta}} (LSGM) with Sr{sub 2}MgMoO{sub 6} as the anode and SKFO as the cathode. The test cells gave a maximum power density of 680 mW cm{sup -2} at 800 C and 850 mW cm{sup -2} at 850 C, with pure H{sub 2} as fuel. The electronic conductivity shows a change of regime at T {approx} 350 C that could correspond to the phase transition from tetragonal to cubic symmetry. The high-temperature regime is characterized by a metallic-like behavior. At 800 C the crystal structure contains 0.20(1) oxygen vacancies per formula unit randomly distributed over the oxygen sites (if a cubic symmetry is assumed). The presence of disordered vacancies could account, by itself, for the oxide-ion conductivity that is required for the mass transport across the cathode. The result is a competitive cathode material containing no cobalt that meets the target for the intermediate-temperature SOFC. (author)

Synthesis and characterization of novel electrolyte materials for intermediate temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Chaubey, Nityanand; Chattopadhyaya, M.C.; Wani, B.N.; Bharadwaj, S.R.

2008-01-01

The high operating temperature of SOFCs using zirconia based electrolyte have several restrictions on materials used as interconnect and sealing and also requires use of expensive ceramics. Lowering the operating temperature of SOFCs to 600-800 deg C will enable to use cheaper materials and reduce the cost of fabrication while keeping the high power density. Lanthanide gallates are considered to be very promising solid electrolytes for intermediate temperature (600-800 deg C) solid oxide fuel cells (IT-SOFCs) due to their high ionic conductivity at lower temperatures. Phase purity of this material is a concern for the researchers for a long time. These materials are prepared at very high temperature (∼1400 deg C), since it is known that at around 1100 deg C, solubilities of Sr and Mg in LaGaO 3 were close to zero. Hence in the present work perovskite oxides of Ln 1-x Sr x Ga 1-y Mg y O 3-δ (Ln= Sm, Gd and x = 0.10, y=0.20) have been prepared by different methods i.e. solid state reaction, gel combustion and co-precipitation methods

Effects of dissolved oxygen and pH on nitrous oxide production rates in autotrophic partial nitrification granules.

Science.gov (United States)

Rathnayake, Rathnayake M L D; Oshiki, Mamoru; Ishii, Satoshi; Segawa, Takahiro; Satoh, Hisashi; Okabe, Satoshi

2015-12-01

The effects of dissolved oxygen (DO) and pH on nitrous oxide (N2O) production rates and pathways in autotrophic partial nitrification (PN) granules were investigated at the granular level. N2O was primarily produced by betaproteobacterial ammonia-oxidizing bacteria, mainly Nitrosomonas europaea, in the oxic surface layer (production increased with increasing bulk DO concentration owing to activation of the ammonia (i.e., hydroxylamine) oxidation in this layer. The highest N2O emissions were observed at pH 7.5, although the ammonia oxidation rate was unchanged between pH 6.5 and 8.5. Overall, the results of this study suggest that in situ analyses of PN granules are essential to gaining insight into N2O emission mechanisms in a granule. Copyright © 2015 Elsevier Ltd. All rights reserved.

Steam and partial oxidation reforming options for hydrogen production from fossil fuels for PEM fuel cells

Directory of Open Access Journals (Sweden)

Yousri M.A. Welaya

2012-06-01

Full Text Available Proton exchange membrane fuel cell (PEM generates electrical power from air and from hydrogen or hydrogen rich gas mixtures. Therefore, there is an increasing interest in converting current hydrocarbon based marine fuels such as natural gas, gasoline, and diesel into hydrogen rich gases acceptable to the PEM fuel cells on board ships. Using chemical flow sheeting software, the total system efficiency has been calculated. Natural gas appears to be the best fuel for hydrogen rich gas production due to its favorable composition of lower molecular weight compounds. This paper presents a study for a 250 kW net electrical power PEM fuel cell system utilizing a partial oxidation in one case study and steam reformers in the second. This study has shown that steam-reforming process is the most competitive fuel processing option in terms of fuel processing efficiency. Partial oxidation process has proved to posses the lowest fuel processing efficiency. Among the options studied, the highest fuel processing efficiency is achieved with natural gas steam reforming system.

Structure of replicating intermediates of human herpesvirus type 6

International Nuclear Information System (INIS)

Severini, Alberto; Sevenhuysen, Claire; Garbutt, Michael; Tipples, Graham A.

2003-01-01

We have studied the structure of the replicative intermediates of human herpesvirus 6 (HHV-6) using pulsed-field gel electrophoresis, partial digestion, two-dimensional gel electrophoresis, and sedimentation centrifugation. The results show that DNA replication of HHV-6 produces head-to-tail concatemeric intermediates as well as approximately equal amounts of circular monomers or oligomers. Unlike the situation in herpes simplex virus, the intermediates of human herpesvirus 6 replication are not highly branched, suggesting a difference in the mechanism of replication or a lower frequency of homologous recombination in human herpesvirus 6 compared to herpes simplex virus

Statistical distribution of partial widths in the microscopic theory of nuclear reactions

International Nuclear Information System (INIS)

Bunakov, V.E.; Ogloblin, S.G.

1978-01-01

Using the microscopic theory of nuclear reaction the distribution function of neutron reduced partial widths is obtained. It is shown that the distribution of reduced partial widths of a radiative transition is of the same form. The distribution obtained differs from the Porter-Thomas law for neutron widths only in the presence of intermediate structures. It is noteworthy that the presence of an intermediate structure leads to a greater dispersion

Investigation of partial oxidation of hydrogen sulfide for dry desulfurisation of fuel gases; Untersuchung der Partialoxidation von Schwefelwasserstoff zur Trockenentschwefelung von Brenngasen

Energy Technology Data Exchange (ETDEWEB)

Kliemczak, U.

2002-07-01

Three process variants for direct desulfurisation in the dry state of coal gasification gases by partial oxidation of H{sub 2}S were investigated in Prenflo conditions: 1. Heterogeneously catalyzed partial oxidation of H{sub 2}S on fly dust followed by sulfur deposition on the dust; 2. Non-catalyzed partial oxidation of H{sub 2}S in a homogeneous gaseous phase followed by sulfur deposition in a spray separator; 3. Heterogeneously catalyzed partial oxidation of H{sub 2}S in a fixed bed. The experiments were carried out in conditions similar to the crude gas conditions of slag bath gasification at SVZ Schwarze Pumpe. The fixed bed materials investigated were hearth furnace coke, Berl saddles, and an activated carbon developed specially for the investigations, Oxorbon CJ. The focus of the investigations was on the envisaged continuous operation of the process. [German] Im Rahmen der vorliegenden Arbeit wurde an einer zu diesem Zweck modifizierten Technikumsanlage die trockene Direktentschwefelung von Brenngasen aus der Kohlevergasung durch partielle Oxidation von H{sub 2}S untersucht. Im Vordergrund standen zwei Verfahrensvarianten, deren Eignung fuer die Bedingungen der Prenflo-Vergasung ueberprueft werden sollte: Variante 1: die heterogen katalysierte Partialoxidation von H{sub 2}S an Flugstaub mit anschliessender Schwefelabscheidung auf dem Staub und, Variante 2: die nichtkatalysierte Partialoxidation von H{sub 2}S in homogener Gasphase mit anschliessender Schwefelabscheidung in einem Spruehabscheider. Ausgehend von den Versuchsergebnissen der Verfahrensvarianten 1 und 2 wurde zusaetzlich als Verfahrensvariante 3 die heterogen katalysierte Partialoxidation von H{sub 2}S am Festbett untersucht. Diese Versuche orientierten sich an den Rohgasbedingungen der Schlackebadvergasung des SVZ Schwarze Pumpe. Als Festbettmaterialien kamen Herdofenkoks, Berlsaettel und eine, speziell fuer diese Verfahrensvariante entwickelte Aktivkohle Oxorbon CJ, zum Einsatz. Die Eignung des

A novel partial SOI LDMOSFET with periodic buried oxide for breakdown voltage and self heating effect enhancement

Science.gov (United States)

Jamali Mahabadi, S. E.; Rajabi, Saba; Loiacono, Julian

2015-09-01

In this paper a partial silicon on insulator (PSOI) lateral double diffused metal oxide semiconductor field effect transistor (LDMOSFET) with periodic buried oxide layer (PBO) for enhancing breakdown voltage (BV) and self-heating effects (SHEs) is proposed for the first time. This new structure is called periodic buried oxide partial silicon on insulator (PBO-PSOI). In this structure, periodic small pieces of SiO2 were used as the buried oxide (BOX) layer in PSOI to modulate the electric field in the structure. It was demonstrated that the electric field is distributed more evenly by producing additional electric field peaks, which decrease the common peaks near the drain and gate junctions in the PBO-PSOI structure. Hence, the area underneath the electric field curve increases which leads to higher breakdown voltage. Also a p-type Si window was introduced in the source side to force the substrate to share the vertical voltage drop, leading to a higher vertical BV. Furthermore, the Si window under the source and those between periodic pieces of SiO2 create parallel conduction paths between the active layer and substrate thereby alleviating the SHEs. Simulations with the two dimensional ATLAS device simulator from the Silvaco suite of simulation tools show that the BV of PBO-PSOI is 100% higher than that of the conventional partial SOI (C-PSOI) structure. Furthermore the PBO-PSOI structure alleviates SHEs to a greater extent than its C-PSOI counterpart. The achieved drain current for the PBO-PSOI structure (100 μA), at drain-source voltage of VDS = 100 V and gate-source voltage of VGS = 25 V, is shown to be significantly larger than that in C-PSOI and fully depleted SOI (FD-SOI) structures (87 μA and 51 μA respectively). Drain current can be further improved at the expense of BV by increasing the doping of the drift region.

Present status of intermediate band solar cell research

International Nuclear Information System (INIS)

Cuadra, L.; Marti, A.; Luque, A.

2004-01-01

The intermediate band solar cell is a theoretical concept with the potential for exceeding the performance of conventional single-gap solar cells. This novel photovoltaic converter bases its superior theoretical efficiency over single-gap solar cells by enhancing its photogenerated current, via the two-step absorption of sub-band gap photons, without reducing its output voltage. This is achieved through a material with an electrically isolated and partially filled intermediate band located within a higher forbidden gap. This material is commonly named intermediate band material. This paper centres on summarising the present status of intermediate band solar cell research. A number of attempts, which aim to implement the intermediate band concept, are being followed: the direct engineering of the intermediate band material, its implementation by means of quantum dots and the highly porous material approach. Among other sub-band gap absorbing proposals, there is a renewed interest on the impurity photovoltaic effect, the quantum well solar cells and the particularly promising proposal for the use of up- and down-converters

Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

Science.gov (United States)

Mahmoodlu, Mojtaba G.; Hassanizadeh, S. Majid; Hartog, Niels; Raoof, Amir

2014-08-01

The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw = 0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

Nitrogen removal from sludge digester liquids by nitrification/denitrification or partial nitritation/anammox: environmental and economical considerations.

Science.gov (United States)

Fux, C; Siegrist, H

2004-01-01

In wastewater treatment plants with anaerobic sludge digestion, 15-20% of the nitrogen load is recirculated to the main stream with the return liquors from dewatering. Separate treatment of this ammonium-rich digester supernatant significantly reduces the nitrogen load of the activated sludge system. Two biological applications are considered for nitrogen elimination: (i) classical autotrophic nitrification/heterotrophic denitrification and (ii) partial nitritation/autotrophic anaerobic ammonium oxidation (anammox). With both applications 85-90% nitrogen removal can be achieved, but there are considerable differences in terms of sustainability and costs. The final gaseous products for heterotrophic denitrification are generally not measured and are assumed to be nitrogen gas (N2). However, significant nitrous oxide (N2O) production can occur at elevated nitrite concentrations in the reactor. Denitrification via nitrite instead of nitrate has been promoted in recent years in order to reduce the oxygen and the organic carbon requirements. Obviously this "achievement" turns out to be rather disadvantageous from an overall environmental point of view. On the other hand no unfavorable intermediates are emitted during anaerobic ammonium oxidation. A cost estimate for both applications demonstrates that partial nitritation/anammox is also more economical than classical nitrification/denitrification. Therefore autotrophic nitrogen elimination should be used in future to treat ammonium-rich sludge liquors.

Ammonia oxidation at high pressure and intermediate temperatures

DEFF Research Database (Denmark)

Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

2016-01-01

Ammonia oxidation experiments were conducted at high pressure (30 bar and 100 bar) under oxidizing and stoichiometric conditions, respectively, and temperatures ranging from 450 to 925 K. The oxidation of ammonia was slow under stoichiometric conditions in the temperature range investigated. Under...... oxidizing conditions the onset temperature for reaction was 850–875 K at 30 bar, while at 100 bar it was about 800 K, with complete consumption of NH3 at 875 K. The products of reaction were N2 and N2O, while NO and NO2 concentrations were below the detection limit even under oxidizing conditions. The data...... was satisfactory. The main oxidation path for NH3 at high pressure under oxidizing conditions is NH3⟶+OH NH2⟶+HO2,NO2 H2NO⟶+O2 HNO⟶+O2 NO ⟶+NH2 N2. The modeling predictions are most sensitive to the reactions NH2 + NO = NNH + OH and NH2 + HO2 = H2NO + OH, which promote the ammonia consumption by forming OH...

A DRIFTS study of the partial oxidation of ethanol on Rh catalysts; Estudo da oxidacao parcial do etanol em catalisadores de Rh por DRIFTS

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Raquel Lima; Passos, Fabio Barboza, E-mail: fbpassos@vm.uff.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Departamento de Engenharia Quimica e de Petroleo

2013-09-01

The partial oxidation of ethanol on {gamma}-Al{sub 2}O{sub 3}, CeO{sub 2}, ZrO{sub 2} and Ce{sub x}Zr{sub 1-x}O{sub 2} supported rhodium catalysts was investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The catalysts were characterized by temperature-programmed reduction (TPR) and cyclohexane dehydrogenation. DRIFTS studies on the partial oxidation of ethanol showed that ethanol is adsorbed dissociatively, through O-H bond breaking, with the formation of ethoxy species, followed by successive dehydrogenation to acetaldehyde and acetyl species. Further oxidation to acetate and carbonate species lead to the formation of CO, CH{sub 4} and H{sub 2} by decomposition. The presence of CeO{sub 2} in the catalysts favored the oxidation steps due to its oxygen storage capacity. (author)

Characterization of porous stainless steel 430 for low and intermediate temperature solid oxide fuel cell substrates

Energy Technology Data Exchange (ETDEWEB)

Rose, L. [National Research Council of Canada, Vancouver, BC (Canada). Inst. for Fuel Cell Innovation; British Columbia Univ., Vancouver, BC (Canada). Dept. of Materials Engineering; Deces-Petit, C.; Sobolyeva, T.; Maric, R. [National Research Council of Canada, Vancouver, BC (Canada). Inst. for Fuel Cell Innovation; Troczynski, T. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Materials Engineering; Kesler, O. [Toronto Univ., ON (Canada). Dept. of Mechanical and Industrial Engineering

2009-07-01

In order to lower the cost of solid oxide fuel cells (SOFCs), the operating temperatures could be lowered below 1073 K to allow the use of robust and comparatively inexpensive stainless steels not only for interconnects but also for SOFC support structures. To facilitate gas flow towards the reactive sites in the electrodes, the metal supports must be adequately porous. Gas flow and electrical conductivity must remain adequate during any oxidation that occurs during operation. This paper discussed a series of gas permeation and surface profilometry experiments that were conducted to determine the permeability and surface roughness of porous steels having different pore structures. The purpose of the study was to identify microstructures most suitable for use as SOFC supports. The materials were also characterized by a variety of porosity measurement methods, each yielding complementary information on the three dimensional structures. The paper described the experimental methods as well as the results and discussion of results in terms of surface profilometry, porosity analyses, pore morphology and gas permeability. It was concluded that a material with more than 20 per cent total porosity that does not close during oxidation and with a surface roughness of less than 8 micrometres appears to be a good candidate structure for intermediate temperature SOFCs. 8 refs., 8 figs.

Layered perovskite PrBa0.5Sr0.5CoCuO5+δ as a cathode for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Wang, Biao; Long, Guohui; Ji, Yuan; Pang, Mingjun; Meng, Xiangwei

2014-01-01

Highlights: • A single-phase layered-perovskite PrBa 0.5 Sr 0.5 CoCuO 5+δ (PBSCCu) is prepared by the EDTA–citrate complexing method. • PBSCCu cathode has a good chemical compatible with GDC electrolyte. • Partial substitution of Cu for Co can efficiently lower the thermal expansion coefficient. • Performances of PrBa 0.5 Sr 0.5 CoCuO 5+δ cathode based on Gd 0.1 Ce 0.9 O 1.95 electrolyte is reported firstly. - Abstract: Layered perovskite PrBa 0.5 Sr 0.5 CoCuO 5+δ (PBSCCo) oxide is synthesized by EDTA–citrate complexing method and investigated as a novel cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). X-ray diffraction results show that PBSCCo is chemical compatible with Gd 0.1 Ce 0.9 O 1.95 (GDC) electrolyte below 950 °C. The thermal expansion coefficient of PBSCCo is 17.58 × 10 −6 K −1 between 30 °C and 900 °C. The maximum electrical conductivity of PBSCCo is 483 S cm −1 at 325 °C. The polarization resistance of PBSCCo cathode on GDC electrolyte is as low as 0.06 Ω cm 2 at 800 °C. The maximum power density of the electrolyte-supported single cell with PBSCCo cathode achieves 521 mW cm −2 at 800 °C. Preliminary results indicate that PBSCCo is a potential cathode material for application in IT-SOFCs

Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

DEFF Research Database (Denmark)

Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram

2012-01-01

oxidation of methane, the catalyst reduced from the end to the beginning of the catalyst bed and oxidized again toward the end as soon as the entire catalyst bed was reduced. On an entirely oxidized catalyst bed, only total oxidation of methane was observed and consumed the oxygen until the conditions...... of the Pd particles at increasing age of the catalyst was observed, which leads to a lower oscillation frequency. Effects of particle size, oven temperature, and oxygen/methane ratio on the oscillation behavior were studied in detail. The deactivation period (reoxidation of Pd) was much less influenced...... by the oven temperature than the ignition behavior of the catalytic partial oxidation of methane. This indicates that deactivation is caused by an autoreduction of the palladium at the beginning of the catalyst bed due to the high temperature achieved by total oxidation of methane....

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

Science.gov (United States)

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Development of a membrane-assisted fluidized bed reactor - 2 - Experimental demonstration and modeling for the partial oxidation of methanol

NARCIS (Netherlands)

Deshmukh, S.A.R.K.; Laverman, J.A.; van Sint Annaland, M.; Kuipers, J.A.M.

2005-01-01

A small laboratory-scale membrane-assisted fluidized bed reactor (MAFBR) was constructed in order to experimentally demonstrate the reactor concept for the partial oxidation of methanol to formaldehyde. Methanol conversion and product selectivities were measured at various overall fluidization

n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine

KAUST Repository

Wang, Zhandong

2017-10-03

This work identifies classes of cool flame intermediates from n-heptane low-temperature oxidation in a jet-stirred reactor (JSR) and a motored cooperative fuel research (CFR) engine. The sampled species from the JSR oxidation of a mixture of n-heptane/O2/Ar (0.01/0.11/0.88) were analyzed using a synchrotron vacuum ultraviolet radiation photoionization (SVUV-PI) time-of-flight molecular-beam mass spectrometer (MBMS) and an atmospheric pressure chemical ionization (APCI) Orbitrap mass spectrometer (OTMS). The OTMS was also used to analyze the sampled species from a CFR engine exhaust. Approximately 70 intermediates were detected by the SVUV-PI-MBMS, and their assigned molecular formulae are in good agreement with those detected by the APCI-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar to those produced in an ideal reactor, i.e., a JSR.The products can be classified by species with molecular formulae of C7H14Ox (x = 0–5), C7H12Ox (x = 0–4), C7H10Ox (x = 0–4), CnH2n (n = 2–6), CnH2n−2 (n = 4–6), CnH2n+2O (n = 1–4), CnH2nO (n = 1–6), CnH2n−2O (n = 2–6), CnH2n−4O (n = 4–6), CnH2n+2O2 (n = 0–4, 7), CnH2nO2 (n = 1–6), CnH2n−2O2 (n = 2–6), CnH2n−4O2 (n = 4–6), and CnH2nO3 (n = 3–6). The identified intermediate species include alkenes, dienes, aldehyde/keto compounds, olefinic aldehyde/keto compounds, diones, cyclic ethers, peroxides, acids, and alcohols/ethers. Reaction pathways forming these intermediates are proposed and discussed herein. These experimental results are important in the development of more accurate kinetic models for n-heptane and longer-chain alkanes.

Characteristics of hydrogen produced by partial oxidation and auto-thermal reforming in a small methanol reformer

Science.gov (United States)

Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te

This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.

Effect of PEEP and inhaled nitric oxide on pulmonary gas exchange during gaseous and partial liquid ventilation with small volumes of perfluorocarbon.

Science.gov (United States)

Max, M; Kuhlen, R; Falter, F; Reyle-Hahn, M; Dembinski, R; Rossaint, R

2000-04-01

Partial liquid ventilation, positive end-expiratory pressure (PEEP) and inhaled nitric oxide (NO) can improve ventilation/perfusion mismatch in acute lung injury (ALI). The aim of the present study was to compare gas exchange and hemodynamics in experimental ALI during gaseous and partial liquid ventilation at two different levels of PEEP, with and without the inhalation of nitric oxide. Seven pigs (24+/-2 kg BW) were surfactant-depleted by repeated lung lavage with saline. Gas exchange and hemodynamic parameters were assessed in all animals during gaseous and subsequent partial liquid ventilation at two levels of PEEP (5 and 15 cmH2O) and intermittent inhalation of 10 ppm NO. Arterial oxygenation increased significantly with a simultaneous decrease in cardiac output when PEEP 15 cmH2O was applied during gaseous and partial liquid ventilation. All other hemodynamic parameters revealed no relevant changes. Inhalation of NO and instillation of perfluorocarbon had no additive effects on pulmonary gas exchange when compared to PEEP 15 cmH2O alone. In experimental lung injury, improvements in gas exchange are most distinct during mechanical ventilation with PEEP 15 cmH2O without significantly impairing hemodynamics. Partial liquid ventilation and inhaled NO did not cause an additive increase of PaO2.

Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

Energy Technology Data Exchange (ETDEWEB)

Mantzaras, I.; Schneider, A.

2006-03-15

The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

Partially filled intermediate band of Cr-doped GaN films

International Nuclear Information System (INIS)

Sonoda, S.

2012-01-01

We investigated the band structure of sputtered Cr-doped GaN (GaCrN) films using optical absorption, photoelectron yield spectroscopy, and charge transport measurements. It was found that an additional energy band is formed in the intrinsic band gap of GaN upon Cr doping, and that charge carriers in the material move in the inserted band. Prototype solar cells showed enhanced short circuit current and open circuit voltage in the n-GaN/GaCrN/p-GaN structure compared to the GaCrN/p-GaN structure, which validates the proposed concept of an intermediate-band solar cell.

Characteristic of nitrous oxide production in partial denitrification process with high nitrite accumulation.

Science.gov (United States)

Du, Rui; Peng, Yongzhen; Cao, Shenbin; Wang, Shuying; Niu, Meng

2016-03-01

Nitrous oxide (N2O) production during the partial denitrification process with nitrate (NO3(-)-N) to nitrite (NO2(-)-N) transformation ratio of 80% was investigated in this study. Results showed that N2O was seldom observed before complete depletion of NO3(-)-N, but it was closely related to the reduction of NO2(-)-N rather than NO3(-)-N. High COD/NO3(-)-N was in favor of N2O production in partial denitrification with high NO2(-)-N accumulation. It was seriously enhanced at constant acidic pH due to the free nitrous acid (FNA) inhibition. However, the N2O production was much lower at initial pH of 5.5 and 6.5 due to the pH increase during denitrification process. Significantly, the pH turning point could be chosen as a controlled parameter to denote the end of NO3(-)-N reduction, which could not only achieve high NO2(-)-N accumulation but also decrease the N2O production significantly for practical application. Copyright © 2015 Elsevier Ltd. All rights reserved.

Visualizing a Catalyst at Work during the Ignition of the Catalytic Partial Oxidation of Methane

DEFF Research Database (Denmark)

Kimmerle, Bertram; Grunwaldt, Jan-Dierk; Baiker, Alfons

2009-01-01

We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which...... in combination with temperature profiling by IR-thermography and catalytic activity measurements by online mass spectrometry gives insight into the first stages of the ignition of the reaction toward hydrogen and carbon monoxide....

Thermogravimetric control of intermediate compounds in uranium metallurgy

International Nuclear Information System (INIS)

Gasco Sanchez, L.; Fernandez Cellini, R.

1959-01-01

The thermal decomposition of some intermediate compounds in the metallurgy of the uranium as uranium peroxide, ammonium uranate, uranium and ammonium penta-fluoride, uranium tetrafluoride and uranous oxide has been study by means of the Chevenard's thermo balance. Some data on pyrolysis of synthetic mixtures of intermediate compounds which may occasionally appear during the industrial process, are given. Thermogravimetric methods of control are suggested, usable in interesting products in the uranium metallurgy. (Author) 20 refs

Thin film oxygen partial pressure sensor

Science.gov (United States)

Wortman, J. J.; Harrison, J. W.; Honbarrier, H. L.; Yen, J.

1972-01-01

The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.

Carrier confinement in Ge/Si quantum dots grown with an intermediate ultrathin oxide layer

Science.gov (United States)

Kuryliuk, V.; Korotchenkov, O.; Cantarero, A.

2012-02-01

We present computational results for strain effects on charge carrier confinement in GexSi1-x quantum dots (QDs) grown on an oxidized Si surface. The strain and free carrier probability density distributions are obtained using the continuum elasticity theory and the effective-mass approximation implemented by a finite-element modeling scheme. Using realistic parameters and conditions for hemisphere and pyramid QDs, it is pointed out that an uncapped hemisphere dot deposited on the Si surface with an intermediate ultrathin oxide layer offers advantageous electron-hole separation distances with respect to a square-based pyramid grown directly on Si. The enhanced separation is associated with a larger electron localization depth in the Si substrate for uncapped hemisphere dots. Thus, for dot diameters smaller than 15-20 nm and surface density of the dots (nQD) ranging from about 1010 to 1012 cm-2, the localization depth may be enhanced from about 8 nm for a pyramid to 38 nm for a hemisphere dot. We find that the effect in a hemisphere dot is very sensitive to the dot density and size, whereas the localization depth is not significantly affected by the variation of the Ge fraction x in GexSi1-x and the aspect ratio of the dot. We also calculate the effect of the fixed oxide charge (Qox) with densities ranging from 10-9 to 10-7 C/cm2 for 10-Ωcm p-type Si wafers on the carrier confinement. Although the confinement potential can be strongly perturbed by the charge at nQD less than ≈4×1011 cm-2, it is not very sensitive to the value of Qox at higher nQD. Since, to our knowledge, there are no data on carrier confinement for Ge QDs deposited on oxidized Si surfaces, these results might be applicable to functional devices utilizing separated electrons and holes such as photovoltaic devices, spin transistors, and quantum computing components. The use of hemisphere QDs placed on oxidized Si rather than pyramid dots grown on bare Si may help to confine charge carriers deeper

Nitrous Oxide Production in a Granule-based Partial Nitritation Reactor: A Model-based Evaluation.

Science.gov (United States)

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2017-04-03

Sustainable wastewater treatment has been attracting increasing attentions over the past decades. However, the production of nitrous oxide (N 2 O), a potent GHG, from the energy-efficient granule-based autotrophic nitrogen removal is largely unknown. This study applied a previously established N 2 O model, which incorporated two N 2 O production pathways by ammonia-oxidizing bacteria (AOB) (AOB denitrification and the hydroxylamine (NH 2 OH) oxidation). The two-pathway model was used to describe N 2 O production from a granule-based partial nitritation (PN) reactor and provide insights into the N 2 O distribution inside granules. The model was evaluated by comparing simulation results with N 2 O monitoring profiles as well as isotopic measurement data from the PN reactor. The model demonstrated its good predictive ability against N 2 O dynamics and provided useful information about the shift of N 2 O production pathways inside granules for the first time. The simulation results indicated that the increase of oxygen concentration and granule size would significantly enhance N 2 O production. The results further revealed a linear relationship between N 2 O production and ammonia oxidation rate (AOR) (R 2  = 0.99) under the conditions of varying oxygen levels and granule diameters, suggesting that bulk oxygen and granule size may exert an indirect effect on N 2 O production by causing a change in AOR.

Advancing Sequential Managed Aquifer Recharge Technology (SMART Using Different Intermediate Oxidation Processes

Directory of Open Access Journals (Sweden)

Karin Hellauer

2017-03-01

Full Text Available Managed aquifer recharge (MAR systems are an efficient barrier for many contaminants. The biotransformation of trace organic chemicals (TOrCs strongly depends on the redox conditions as well as on the dissolved organic carbon availability. Oxic and oligotrophic conditions are favored for enhanced TOrCs removal which is obtained by combining two filtration systems with an intermediate aeration step. In this study, four parallel laboratory-scale soil column experiments using different intermittent aeration techniques were selected to further optimize TOrCs transformation during MAR: no aeration, aeration with air, pure oxygen and ozone. Rapid oxygen consumption, nitrate reduction and dissolution of manganese confirmed anoxic conditions within the first filtration step, mimicking traditional bank filtration. Aeration with air led to suboxic conditions, whereas oxidation by pure oxygen and ozone led to fully oxic conditions throughout the second system. The sequential system resulted in an equal or better transformation of most TOrCs compared to the single step bank filtration system. Despite the fast oxygen consumption, acesulfame, iopromide, iomeprol and valsartan were degraded within the first infiltration step. The compounds benzotriazole, diclofenac, 4-Formylaminoantipyrine, gabapentin, metoprolol, valsartan acid and venlafaxine revealed a significantly enhanced removal in the systems with intermittent oxidation compared to the conventional treatment without aeration. Further improvement of benzotriazole and gabapentin removal by using pure oxygen confirmed potential oxygen limitation in the second column after aeration with air. Ozonation resulted in an enhanced removal of persistent compounds (i.e., carbamazepine, candesartan, olmesartan and further increased the attenuation of gabapentin, methylbenzotriazole, benzotriazole, and venlafaxine. Diatrizoic acid revealed little degradation in an ozone–MAR hybrid system.

INTERMEDIATE STAGES OF REACTIONS FORMING CARBIDES OF TITANIUM, ZIRCONIUM, VANADIUM, NIOBIUM, AND TANTALIUM

Science.gov (United States)

intermediate and final products, and also during the calculation of approximate heat values of their formation, the passage of the reaction is confirmed...for obtaining TiC, and ZrC through the stage of intermediate oxides Ti2O3, Ti3O5, TiO and Zr2O3, ZrO, respectively and also for the reaction of...forming carbides of V (from V2O3 + 5C), of Nb and Ta (from Nb2O5 + 7C and Ta205 + 7C) through the stage of intermediate oxides VO, V4O and TaO2, Ta4O. The

New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Allan J. Jacobson

2006-09-30

Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode-electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. The initial choices for study were perovskite oxides based on substituted LaFeO{sub 3} (P1 compositions), where significant data in single cell tests exist at PNNL for example, for La{sub 0.8}Sr{sub 0.2}FeO{sub 3} cathodes on both YSZ and CSO/YSZ. The materials selection was then extended to La{sub 2}NiO{sub 4} compositions (K1 compositions), and then in a longer range task we evaluated the possibility of completely unexplored group of materials that are also perovskite related, the ABM{sub 2}O{sub 5+{delta}}. A key component of the research strategy was to evaluate for each cathode material composition, the key performance parameters, including ionic and electronic conductivity, surface exchange rates, stability with respect to the specific electrolyte choice, and thermal expansion coefficients. In the initial phase, we did this in parallel with

Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

International Nuclear Information System (INIS)

Siefken, L.J.

1999-01-01

Models were designed to resolve deficiencies in the SCDAP/RELAP5/MOD3.2 calculations of the configuration and integrity of hot, partially oxidized cladding. These models are expected to improve the calculations of several important aspects of fuel rod behavior. First, an improved mapping was established from a compilation of PIE results from severe fuel damage tests of the configuration of melted metallic cladding that is retained by an oxide layer. The improved mapping accounts for the relocation of melted cladding in the circumferential direction. Then, rules based on PIE results were established for calculating the effect of cladding that has relocated from above on the oxidation and integrity of the lower intact cladding upon which it solidifies. Next, three different methods were identified for calculating the extent of dissolution of the oxidic part of the cladding due to its contact with the metallic part. The extent of dissolution effects the stress and thus the integrity of the oxidic part of the cladding. Then, an empirical equation was presented for calculating the stress in the oxidic part of the cladding and evaluating its integrity based on this calculated stress. This empirical equation replaces the current criterion for loss of integrity which is based on temperature and extent of oxidation. Finally, a new rule based on theoretical and experimental results was established for identifying the regions of a fuel rod with oxidation of both the inside and outside surfaces of the cladding. The implementation of these models is expected to eliminate the tendency of the SCDAP/RELAP5 code to overpredict the extent of oxidation of the upper part of fuel rods and to underpredict the extent of oxidation of the lower part of fuel rods and the part with a high concentration of relocated material. This report is a revision and reissue of the report entitled, Improvements in Modeling of Cladding Oxidation and Meltdown

Fuel processor integrated H{sub 2}S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

Energy Technology Data Exchange (ETDEWEB)

Gardner, T.H.; Berry, D.A.; Lyons, K.D.; Beer, S.K.; Freed, A.D. [U.S. Department of Energy, Morgantown, WV (USA). National Energy Technology Laboratory

2002-12-01

H{sub 2}S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O{sub 2}-blown coal-derived synthesis gas. The H{sub 2}S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H{sub 2}S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H{sub 2}S and 0.3 order in O{sub 2}. 18 refs., 14 figs., 3 tabs.

Nitrous oxide production in intermittently aerated Partial Nitritation-Anammox reactor: oxic N₂O production dominates and relates with ammonia removal rate

DEFF Research Database (Denmark)

Blum, Jan-Michael; Jensen, Marlene Mark; Smets, Barth F.

2018-01-01

Emissions of the greenhouse gas nitrous oxide from the Partial Nitritation-Anammox process are of concern and can determine the carbon footprint of the process. In order to reduce nitrous oxide emissions intermittent aeration regimes have been shown to be a promising mode of operation, possibly due...

Ceramic Composite Intermediate Temperature Stress-Rupture Properties Improved Significantly

Science.gov (United States)

Morscher, Gregory N.; Hurst, Janet B.

2002-01-01

Silicon carbide (SiC) composites are considered to be potential materials for future aircraft engine parts such as combustor liners. It is envisioned that on the hot side (inner surface) of the combustor liner, composites will have to withstand temperatures in excess of 1200 C for thousands of hours in oxidizing environments. This is a severe condition; however, an equally severe, if not more detrimental, condition exists on the cold side (outer surface) of the combustor liner. Here, the temperatures are expected to be on the order of 800 to 1000 C under high tensile stress because of thermal gradients and attachment of the combustor liner to the engine frame (the hot side will be under compressive stress, a less severe stress-state for ceramics). Since these composites are not oxides, they oxidize. The worst form of oxidation for strength reduction occurs at these intermediate temperatures, where the boron nitride (BN) interphase oxidizes first, which causes the formation of a glass layer that strongly bonds the fibers to the matrix. When the fibers strongly bond to the matrix or to one another, the composite loses toughness and strength and becomes brittle. To increase the intermediate temperature stress-rupture properties, researchers must modify the BN interphase. With the support of the Ultra-Efficient Engine Technology (UEET) Program, significant improvements were made as state-of-the-art SiC/SiC composites were developed during the Enabling Propulsion Materials (EPM) program. Three approaches were found to improve the intermediate-temperature stress-rupture properties: fiber-spreading, high-temperature silicon- (Si) doped boron nitride (BN), and outside-debonding BN.

High temperature mechanisms and kinetics of SiC oxidation under low partial pressures of oxygen: application to the fuel cladding of gas fast reactors

International Nuclear Information System (INIS)

Hun, N.

2011-01-01

Gas Fast Reactor (GFR) is one of the different Generation IV concepts under investigation for energy production. SiC/SiC composites are candidates of primary interest for a GFR fuel cladding use, thanks to good corrosion resistance among other properties. The mechanisms and kinetics of SiC oxidation under operating conditions have to be identified and quantified as the corrosion can decrease the mechanical properties of the composite. An experimental device has been developed to study the oxidation of silicon carbide under high temperature and low oxygen partial pressure. The results pointed out that not only parabolic oxidation, but also interfacial reactions and volatilization occur under such conditions. After determining the kinetics of each mechanism, as functions of oxygen partial pressure and temperature, the data are used for the modeling of the composites oxidation. The model will be used to predict the lifetime of the composite in operating conditions. (author) [fr

Ammonia oxidation at high pressure and intermediate temperatures

DEFF Research Database (Denmark)

Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

2016-01-01

were interpreted in terms of a detailed chemical kinetic model. The rate constant for the reaction of the important intermediate H2NO with O2 was determined from ab initio calculations to be 2.3 × 102 T2.994 exp (−9510 K/T) cm3 mol−1 s−1. The agreement between experimental results and model work...

Effect of thermally grown oxide (TGO) microstructure on the durability of TBCs with PtNiAl diffusion bond coats

Energy Technology Data Exchange (ETDEWEB)

Spitsberg, Irene [Materials and Process Engineering Department, GE Aircraft Engines, Evendale, OH (United States)]. E-mail: irene.spitsberg@kennametal.com; More, Karren [Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States)

2006-02-15

The role of pre-oxidation surface treatments on the oxide microstructure and the failure mechanism of multi-layer thermal barrier systems based on Pt-modified NiAl bond coats and electron beam deposited thermal barrier coatings (TBCs) have been studied. The primary pre-oxidation experimental variable was the partial pressure of oxygen in the pre-oxidizing atmosphere at constant temperature and bond coat composition. The durability of TBCs deposited on surfaces following different pre-oxidation treatments were measured and compared using furnace cycling tests. The oxide layers corresponding to different levels of TBC performance were characterized microstructurally, chemically, and compositionally using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques. TBC performance was enhanced by the formation of a surface oxide having a coarse-grained columnar structure during the pre-oxidation process. Increased TBC durability was consistent with a slower oxide growth rate during exposure of the TBC to high-temperature, cyclic conditions, as was observed for this particular pre-oxidation condition. An oxide microstructure having fewer through-thickness transport pathways (grain boundaries) should also result in slower lateral oxide growth rates, consistent with a slowed rate of ratcheting as was observed in the pre-oxidized samples that had the best TBC performance. The desired surface oxide grain structure was achieved by pre-oxidizing the bond coat prior to TBC deposition at an intermediate partial pressure of oxygen.

Corrosion of steel in carbonated media: The oxidation processes of chukanovite (Fe2(OH)2CO3)

International Nuclear Information System (INIS)

Azoulay, I.; Rémazeilles, C.; Refait, Ph.

2014-01-01

Highlights: • Oxidation of chukanovite does not lead to carbonated green rust. • Both lepidocrocite and goethite can result from the oxidation of chukanovite. • Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate. • Chukanovite crystal structure withstands a partial oxidation of Fe(II) to Fe(III). - Abstract: The oxidation of aqueous suspensions of chukanovite (Fe 2 (OH) 2 CO 3 ) obtained by mixing NaOH, FeCl 2 and Na 2 CO 3 solutions was studied. The reaction was monitored by recording the pH and the redox potential of a platinum electrode immersed in the suspension. The precipitate was analyzed at various oxidation stages by infrared spectroscopy. The end products were also characterized by X-ray diffraction. The oxidation by air of the suspensions leads to lepidocrocite and goethite without formation of an intermediate green rust compound. Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate with a crystal structure closely related to that of chukanovite

Characterization of biodegradation intermediates of nonionic surfactants by MALDI-MS. 2. Oxidative biodegradation profiles of uniform octylphenol polyethoxylate in 18O-labeled water.

Science.gov (United States)

Sato, Hiroaki; Shibata, Atsushi; Wang, Yang; Yoshikawa, Hiromichi; Tamura, Hiroto

2003-01-01

This paper reports the characterization of the biodegradation intermediates of octylphenol octaethoxylate (OP(8)EO) by means of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The biodegradation test study was carried out in a pure culture (Pseudomonas putida S-5) under aerobic conditions using OP(8)EO as the sole carbon source and (18)O-labeled water as an incubation medium. In the MALDI-MS spectra of biodegraded samples, a series of OP(n)EO molecules with n = 2-8 EO units and their corresponding carboxylic acid products (OP(n)EC) were observed. The use of purified OP(8)EO enabled one to distinguish the shortened OPEO molecules as biodegradation intermediates. Furthermore, the formation of OP(8)EC (the oxidized product of OP(8)EO) supported the notion that terminal oxidation is a step in the biodegradation process. When biodegradation study was carried out in (18)O-labeled water, incorporation of (18)O atoms into the carboxyl group was observed for OPEC, while no incorporation was observed for the shortened OPEO products. These results could provide some rationale to the biodegradation mechanism of alkylphenol polyethoxylates.

MHD oxidant intermediate temperature ceramic heater study

Science.gov (United States)

Carlson, A. W.; Chait, I. L.; Saari, D. P.; Marksberry, C. L.

1981-09-01

The use of three types of directly fired ceramic heaters for preheating oxygen enriched air to an intermediate temperature of 1144K was investigated. The three types of ceramic heaters are: (1) a fixed bed, periodic flow ceramic brick regenerative heater; (2) a ceramic pebble regenerative heater. The heater design, performance and operating characteristics under conditions in which the particulate matter is not solidified are evaluated. A comparison and overall evaluation of the three types of ceramic heaters and temperature range determination at which the particulate matter in the MHD exhaust gas is estimated to be a dry powder are presented.

Mixed fuel strategy for carbon deposition mitigation in solid oxide fuel cells at intermediate temperatures.

Science.gov (United States)

Su, Chao; Chen, Yubo; Wang, Wei; Ran, Ran; Shao, Zongping; Diniz da Costa, João C; Liu, Shaomin

2014-06-17

In this study, we propose and experimentally verified that methane and formic acid mixed fuel can be employed to sustain solid oxide fuel cells (SOFCs) to deliver high power outputs at intermediate temperatures and simultaneously reduce the coke formation over the anode catalyst. In this SOFC system, methane itself was one part of the fuel, but it also played as the carrier gas to deliver the formic acid to reach the anode chamber. On the other hand, the products from the thermal decomposition of formic acid helped to reduce the carbon deposition from methane cracking. In order to clarify the reaction pathways for carbon formation and elimination occurring in the anode chamber during the SOFC operation, O2-TPO and SEM analysis were carried out together with the theoretical calculation. Electrochemical tests demonstrated that stable and high power output at an intermediate temperature range was well-maintained with a peak power density of 1061 mW cm(-2) at 750 °C. With the synergic functions provided by the mixed fuel, the SOFC was running for 3 days without any sign of cell performance decay. In sharp contrast, fuelled by pure methane and tested at similar conditions, the SOFC immediately failed after running for only 30 min due to significant carbon deposition. This work opens a new way for SOFC to conquer the annoying problem of carbon deposition just by properly selecting the fuel components to realize their synergic effects.

Temperature oscillations in methanol partial oxidation reactor for the production of hydrogen

Energy Technology Data Exchange (ETDEWEB)

Kim, Jinsu; Byeon, Jeonguk; Seo, Il Gyu; Lee, Hyun Chan; Kim, Dong Hyun; Lee, Jietae [Kyungpook National University, Daegu (Korea, Republic of)

2013-04-15

Methanol partial oxidation (POX) is a well-known reforming reaction for the production of hydrogen from methanol. Since POX is relatively fast and highly exothermic, this reforming method will be efficient for the fast start-up and load-following operation. However, POX generates hot spots around catalyst and even oscillations in the reactor temperature. These should be relieved for longer operations of the reactor without catalyst degradations. For this, temperature oscillations in a POX reactor are investigated experimentally. Various patterns of temperature oscillations according to feed flow rates of reactants and reactor temperatures are obtained. The bifurcation phenomena from regular oscillations to chaotic oscillations are found as the methanol flow rate increases. These experimental results can be used for theoretical analyses of oscillations and for designing safe reforming reactors.

Temperature oscillations in methanol partial oxidation reactor for the production of hydrogen

International Nuclear Information System (INIS)

Kim, Jinsu; Byeon, Jeonguk; Seo, Il Gyu; Lee, Hyun Chan; Kim, Dong Hyun; Lee, Jietae

2013-01-01

Methanol partial oxidation (POX) is a well-known reforming reaction for the production of hydrogen from methanol. Since POX is relatively fast and highly exothermic, this reforming method will be efficient for the fast start-up and load-following operation. However, POX generates hot spots around catalyst and even oscillations in the reactor temperature. These should be relieved for longer operations of the reactor without catalyst degradations. For this, temperature oscillations in a POX reactor are investigated experimentally. Various patterns of temperature oscillations according to feed flow rates of reactants and reactor temperatures are obtained. The bifurcation phenomena from regular oscillations to chaotic oscillations are found as the methanol flow rate increases. These experimental results can be used for theoretical analyses of oscillations and for designing safe reforming reactors

An allene oxide and 12-oxophytodienoic acid are key intermediates in jasmonic acid biosynthesis by Fusarium oxysporum.

Science.gov (United States)

Oliw, Ernst H; Hamberg, Mats

2017-08-01

Fungi can produce jasmonic acid (JA) and its isoleucine conjugate in large quantities, but little is known about the biosynthesis. Plants form JA from 18:3 n -3 by 13 S -lipoxygenase (LOX), allene oxide synthase, and allene oxide cyclase. Shaking cultures of Fusarium oxysporum f. sp. tulipae released over 200 mg of jasmonates per liter. Nitrogen powder of the mycelia expressed 10 R -dioxygenase-epoxy alcohol synthase activities, which was confirmed by comparison with the recombinant enzyme. The 13 S -LOX of F. oxysporum could not be detected in the cell-free preparations. Incubation of mycelia in phosphate buffer with [17,17,18,18,18- 2 H 5 ]18:3 n -3 led to biosynthesis of a [ 2 H 5 ]12-oxo-13-hydroxy-9 Z ,15 Z -octadecadienoic acid (α-ketol), [ 2 H 5 ]12-oxo-10,15 Z -phytodienoic acid (12-OPDA), and [ 2 H 5 ]13-keto- and [ 2 H 5 ]13 S -hydroxyoctadecatrienoic acids. The α-ketol consisted of 90% of the 13 R stereoisomer, suggesting its formation by nonenzymatic hydrolysis of an allene oxide with 13 S configuration. Labeled and unlabeled 12-OPDA were observed following incubation with 0.1 mM [ 2 H 5 ]18:3 n -3 in a ratio from 0.4:1 up to 47:1 by mycelia of liquid cultures of different ages, whereas 10 times higher concentration of [ 2 H 5 ]13 S -hydroperoxyoctadecatrienoic acid was required to detect biosynthesis of [ 2 H 5 ]12-OPDA. The allene oxide is likely formed by a cytochrome P450 or catalase-related hydroperoxidase. We conclude that F. oxysporum , like plants, forms jasmonates with an allene oxide and 12-OPDA as intermediates. Copyright © 2017 by the American Society for Biochemistry and Molecular Biology, Inc.

Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

International Nuclear Information System (INIS)

Fossing, H.

1992-01-01

Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

Advanced STEM/EDX investigation on an oxide scale thermally grown on a high-chromium iron–nickel alloy under very low oxygen partial pressure

International Nuclear Information System (INIS)

Latu-Romain, L.; Madi, Y.; Mathieu, S.; Robaut, F.; Petit, J.-P.; Wouters, Y.

2015-01-01

Highlights: • A scale grown on a high-chromium iron–nickel alloy under low oxygen partial pressure was studied. • STEM-EDX maps at high resolution on a transversal thin lamella have been conducted. • The real complexity of the oxide layer has been highlighted. • These results explain the elevated number of semiconducting contributions. - Abstract: A thermal oxide scale has been grown on a high-chromium iron-nickel alloy under very low oxygen partial pressure (1050 °C, 10"−"1"0 Pa). In this paper, a special attention has been paid to morphological and chemical characterizations of the scale by scanning transmission electron microscopy and energy dispersive X-ray analysis at high resolution on a cross-section thin lamella beforehand prepared by using a combined focused ion beam/scanning electron microscope instrument. The complexity of the oxide layer is highlighted, and the correlation between the present results and the ones of a photoelectrochemical study is discussed.

Electrical, thermal and electrochemical properties of SmBa_1_−_xSr_xCo_2O_5_+_δ cathode materials for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Subardi, Adi; Chen, Ching-Cheng; Cheng, Meng-Hsien; Chang, Wen-Ku; Fu, Yen-Pei

2016-01-01

The effects of Sr doping on the Ba-site of SmBaCo_2O_5_+_δ in term of structure characteristics, thermal expansion coefficients (TECs), electrical properties and electrochemical performance have been investigated as cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The TECs of SBSC-based cathodes are calculated from 19.8 − 20.5 × 10"−"6 K"−"1 in the temperature range of 100–800 °C, and the TEC values decrease with increasing Sr content. The oxygen content and the average oxidation state of cobalt increase with increasing Sr content determined by the X-ray photoelectron spectroscopy (XPS) and Thermogravimetry analysis (TGA) results. At a given temperature, the electrical conductivity values are in the order as follows: SBSC55 > SBSC73 > SBSC91. This behavior might be due to the increase in electronic hole. The electrical conductivities of SBSC55 at 600 °C are distributed in the range of 660 S/cm of p(O_2) = 0.01 atm to 1168 S/cm of p(O_2) = 0.21 atm, indicating that the cathode can endure reducing atmosphere. SBSC55 with high electrical conductivity in p(O_2) = 0.01 atm is ascribed to SBSC55 with stable double-perovskite structure at such low oxygen partial pressure. The SBSC55 cathode showed the highest power density of 304 mW/cm"2 at operating temperature of 700 °C. Based on the electrochemical properties, SBSC55 is a potential cathode for IT-SOFCs.

Thermal catalytic oxidation of octachloronaphthalene over anatase TiO2 nanomaterial and its hypothesized mechanism

Science.gov (United States)

Su, Guijin; Li, Qianqian; Lu, Huijie; Zhang, Lixia; Huang, Linyan; Yan, Li; Zheng, Minghui

2015-12-01

As an environmentally-green technology, thermal catalytic oxidation of octachloronaphthalene (CN-75) over anatase TiO2 nanomaterials was investigated at 300 °C. A wide range of oxidation intermediates, which were investigated using various techniques, could be of three types: naphthalene-ring, single-benzene-ring, and completely ring-opened products. Reactive oxygen species on anatase TiO2 surface, such as O2-• and O2-, contributed to oxidative degradation. Based on these findings, a novel oxidation degradation mechanism was proposed. The reaction at (101) surface of anatase TiO2 was used as a model. The naphthalene-ring oxidative products with chloronaphthols and hydroxyl-pentachloronaphthalene-dione, could be formed via attacking the carbon of naphthalene ring at one or more positions by nucleophilic O2-. Lateral cleavage of the naphthalene ring at different C1-C10 and C4-C9, C1-C2 and C4-C9, C1-C2 or and C3-C4 bond positions by electrophilic O2-• could occur. This will lead to the formation of tetrachlorophenol, tetrachloro-benzoic acid, tetrachloro-phthalaldehyde, and tetrachloro-acrolein-benzoic acid, partially with further transformation into tetrachlorobenzene-dihydrodiol and tetrachloro-salicylic acid. Unexpectedly, the symmetric half section of CN-75 could be completely remained with generating the intricate oxidative intermediates characteristically containing tetrachlorobenzene structure. Complete cleavage of naphthalene ring could produce the ring-opened products, such as formic and acetic acids.

SUPERCRITICAL WATER PARTIAL OXIDATION PHASE I - PILOT-SCALE TESTING / FEASIBILITY STUDIES FINAL REPORT

Energy Technology Data Exchange (ETDEWEB)

SPRITZER,M; HONG,G

2005-01-01

Under Cooperative Agreement No. DE-FC36-00GO10529 for the Department of Energy, General Atomics (GA) is developing Supercritical Water Partial Oxidation (SWPO) as a means of producing hydrogen from low-grade biomass and other waste feeds. The Phase I Pilot-scale Testing/Feasibility Studies have been successfully completed and the results of that effort are described in this report. The Key potential advantages of the SWPO process is the use of partial oxidation in-situ to rapidly heat the gasification medium, resulting in less char formation and improved hydrogen yield. Another major advantage is that the high-pressure, high-density aqueous environment is ideal for reaching and gasifying organics of all types. The high water content of the medium encourages formation of hydrogen and hydrogen-rich products and is especially compatible with high water content feeds such as biomass materials. The high water content of the medium is also effective for gasification of hydrogen-poor materials such as coal. A versatile pilot plant for exploring gasification in supercritical water has been established at GA's facilities in San Diego. The Phase I testing of the SWPO process with wood and ethanol mixtures demonstrated gasification efficiencies of about 90%, comparable to those found in prior laboratory-scale SCW gasification work carreid out at the University of Hawaii at Manoa (UHM) as well as other biomass gasification experience with conventional gasifiers. As in the prior work at UHM, a significant amount of the hydrogen found in the gas phase products is derived from the water/steam matrix. The studies at UHM utilized an indirectly heated gasifier with an acitvated carbon catalyst. In contrast, the GA studies utilized a directly heated gasifier without catalyst, plus a surrogate waste fuel. Attainment of comparable gasification efficiencies without catalysis is an important advancement for the GA process, and opens the way for efficient hydrogen production from low

The partial pressure of oxygen affects biomarkers of oxidative stress in cultured rainbow trout (Oncorhynchus mykiss) hepatocytes.

Science.gov (United States)

Finne, E F; Olsvik, P A; Berntssen, M H G; Hylland, K; Tollefsen, K E

2008-09-01

Oxidative stress, the imbalance between production of reactive oxygen species and the cellular detoxification of these reactive compounds, is believed to be involved in the pathology of various diseases. Several biomarkers for oxidative stress have been proposed to serve as tools in toxicological and ecotoxicological research. Not only may exposure to various pro-oxidants create conditions of cellular oxidative stress, but hyperoxic conditions may also increase the production of reactive oxygen species. The objective of the current study was to determine the extent to which differences in oxygen partial pressure would affect biomarkers of oxidative stress in a primary culture of hepatocytes from rainbow trout (Oncorhynchus mykiss). Membrane integrity, metabolic activity, levels of total and oxidized glutathione (tGSH/GSSG) was determined, as well as mRNA expression levels of the antioxidant enzymes superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GSSG-R), gamma-glutamyl-cystein synthetase (GCS) and thioredoxin (TRX). The results show that different biomarkers of oxidative stress are affected when the cell culture is exposed to atmospheric oxygen, and that changes such as increased GSSG content and induction of GSSG-R and GSH-Px can be reduced by culturing the cells under lower oxygen tension. Oxygen tension may thus influence results of in vitro based cell research and is particularly important when assessing parameters in the antioxidant defence system. Further research is needed to establish the magnitude of this effect in different cellular systems.

Oxidative stress in the hydrocoral Millepora alcicornis exposed to CO2-driven seawater acidification

Science.gov (United States)

Luz, Débora Camacho; Zebral, Yuri Dornelles; Klein, Roberta Daniele; Marques, Joseane Aparecida; Marangoni, Laura Fernandes de Barros; Pereira, Cristiano Macedo; Duarte, Gustavo Adolpho Santos; Pires, Débora de Oliveira; Castro, Clovis Barreira e.; Calderon, Emiliano Nicolas; Bianchini, Adalto

2018-06-01

Global impacts are affecting negatively coral reefs' health worldwide. Ocean acidification associated with the increasing CO2 partial pressure in the atmosphere can potentially induce oxidative stress with consequent cellular damage in corals and hydrocorals. In the present study, parameters related to oxidative status were evaluated in the hydrocoral Millepora alcicornis exposed to three different levels of seawater acidification using a mesocosm system. CO2-driven acidification of seawater was performed until reaching 0.3, 0.6 and 0.9 pH units below the current pH of seawater pumped from the coral reef adjacent to the mesocosm. Therefore, treatments corresponded to control (pH 8.1), mild (pH 7.8), intermediate (pH 7.5) and severe (pH 7.2) seawater acidification. After 0, 16 and 30 d of exposure, hydrocorals were collected and the following parameters were analyzed in the holobiont: antioxidant capacity against peroxyl radicals (ACAP), total glutathione (GSHt) concentration, reduced (GSH) and oxidized (GSSG) glutathione ratio (GSH/GSSG), lipid peroxidation (LPO) and protein carbonyl group (PC) levels. ACAP was increased in hydrocorals after 16 d of exposure to intermediate levels of seawater acidification. GSHt and GSH/GSSG did not change over the experimental period. LPO was increased at any level of seawater acidification, while PC content was increased in hydrocorals exposed to intermediate and severe seawater acidification for 30 d. These findings indicate that the antioxidant defense system of M. alcicornis is capable of coping with acidic conditions for a short period of time (16 d). Additionally, they clearly show that a long-term (30 d) exposure to seawater acidification induces oxidative stress with consequent oxidative damage to lipids and proteins, which could compromise hydrocoral health.

Effect of mass-transport limitations on the performance of a packed bed membrane reactor for partial oxidations. Intraparticle mass transport

NARCIS (Netherlands)

Sint Annaland, van M.; Kurten, U.; Kuipers, J.A.M.

2007-01-01

For partial oxidation systems, where the reaction order in oxygen of the formation rate of the target product is smaller than the reaction order in oxygen of the consecutive reaction rate toward the waste product, a packed bed membrane reactor can be applied to distributively dose oxygen along the

Effect of Mass-Transport Limitations on the Performance of a Packed Bed Membrane Reactor for Partial Oxidations. Intraparticle Mass Transport

NARCIS (Netherlands)

van Sint Annaland, M.; Kurten, U.; Kuipers, J.A.M.

2007-01-01

For partial oxidation systems, where the reaction order in oxygen of the formation rate of the target product is smaller than the reaction order in oxygen of the consecutive reaction rate toward the waste product, a packed bed membrane reactor can be applied to distributively dose oxygen along the

Stepwise expansion of the bacteriophage ϕ6 procapsid: possible packaging intermediates.

Science.gov (United States)

Nemecek, Daniel; Cheng, Naiqian; Qiao, Jian; Mindich, Leonard; Steven, Alasdair C; Heymann, J Bernard

2011-11-25

The initial assembly product of bacteriophage ϕ6, the procapsid, undergoes major structural transformation during the sequential packaging of its three segments of single-stranded RNA. The procapsid, a compact icosahedrally symmetric particle with deeply recessed vertices, expands to the spherical mature capsid, increasing the volume available to accommodate the genome by 2.5-fold. It has been proposed that expansion and packaging are linked, with each stage in expansion presenting a binding site for a particular RNA segment. To investigate procapsid transformability, we induced expansion by acidification, heating, and elevated salt concentration. Cryo-electron microscopy reconstructions after all three treatments yielded the same partially expanded particle. Analysis by cryo-electron tomography showed that all vertices of a given capsid were either in a compact or an expanded state, indicating a highly cooperative transition. To benchmark the mature capsid, we analyzed filled (in vivo packaged) capsids. When these particles were induced to release their RNA, they reverted to the same intermediate state as expanded procapsids (intermediate 1) or to a second, further expanded state (intermediate 2). This partial reversibility of expansion suggests that the mature spherical capsid conformation is obtained only when sufficient outward pressure is exerted by packaged RNA. The observation of two intermediates is consistent with the proposed three-step packaging process. The model is further supported by the observation that a mutant capable of packaging the second RNA segment without previously packaging the first segment has enhanced susceptibility for switching spontaneously from the procapsid to the first intermediate state. Published by Elsevier Ltd.

Sputtered indium oxide films

International Nuclear Information System (INIS)

Gillery, F.H.

1986-01-01

A method is described for depositing on a substrate multiple layer films comprising at least one primary layer of a metal oxide and at least one primary layer of a metal other than the metal of the oxide layer. The improvement described here comprises improving the adhesion between the metal oxide and metal layers by depositing between the layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers. An article of manufacture is described comprising a nonmetallic substrate, and deposited thereon in any order: a. at least one coating layer of metal; b. at least one coating layer of an oxide of a metal other than the metal of the metal layer; and c. deposited between the metal and metal oxide layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers

A first-principles investigation of the effect of Pt cluster size on CO and NO oxidation intermediates and energetics

International Nuclear Information System (INIS)

Xu, Ye; Getman, Rachel B; Shelton, William Allison Jr.; Schneider, William F

2008-01-01

As catalysis research strives toward designing structurally and functionally well-defined catalytic centers containing as few active metal atoms as possible, the importance of understanding the reactivity of small metal clusters, and in particular of systematic comparisons of reaction types and cluster sizes, has grown concomitantly. Here we report density functional theory calculations (GGA-PW91) that probe the relationship between particle size, intermediate structures, and energetics of CO and NO oxidation by molecular and atomic oxygen on Ptx clusters (x = 1-5 and 10). The preferred structures, charge distributions, vibrational spectra, and energetics are systematically examined for oxygen (O2, 2O, and O), CO, CO2, NO, and NO2, for CO/NO co-adsorbed with O2, 2O, and O, and for CO2/NO2 co-adsorbed with O. The binding energies of oxygen, CO, NO, and the oxidation products CO2 and NO2 are all markedly enhanced on Ptx compared to Pt(111), and they trend toward the Pt(111) levels as cluster size increases. Because of the strong interaction of both the reactants and products with the Ptx clusters, deep energy sinks develop on the potential energy surfaces of the respective oxidation processes, indicating worse reaction energetics than on Pt(111). Thus the smallest Pt clusters are less effective for catalyzing CO and NO oxidation in their original state than bulk Pt. Our results further suggests that oxidation by molecular O2 is thermodynamically more facile than oxidation by atomic O on Ptx. Conditions and applications in which the Ptx clusters may be effective catalysts are discussed

Results of fission product release from intermediate-scale MCCI [molten core-concrete interaction] tests

International Nuclear Information System (INIS)

Spencer, B.W.; Thompson, D.H.; Fink, J.K.; Gunther, W.H.; Sehgal, B.R.

1988-01-01

A program of reactor-material molten core-concrete interaction (MCCI) tests and related analyses are under way at Argonne National Laboratory under sponsorship of the Electric Power Research Institute (EPRI). The particular objective of these tests is to provide data pertaining to the release of nonvolatile fission products such as La, Ba, and Sr, plus other aerosol materials, from the coupled thermal-hydraulic and chemical processes of the MCCI. The first stages of the program involving small and intermediate-scale tests have been completed. Three small-scale tests (/approximately/5 kg corium) and nine intermediate-scale tests (/approximately/30 kg corium) were performed between September 1985 and September 1987. Real reactor materials were used in these tests. Sustained internal heat generation at nominally 1 kW per kg of melt was provided by direct electrical heating of the corium mixture. MCCI tests were performed with both fully and partially oxidized corium mixtures that contained a variety of nonradioactive materials such as La 2 O 3 , BaO, and SrO to represent fission products. Both limestone/common sand and basaltic concrete basemats were used. The system was instrumented for characterization of the thermal hydraulic, chemical, gas release, and aerosol release processes

Partial Word Knowledge: Frontier Words in the L2 Mental Lexicon

Science.gov (United States)

Zareva, Alla

2012-01-01

The study set out to examine the partial word knowledge of native speakers, L2 advanced, and intermediate learners of English with regard to four word features from Richards' (1976) taxonomy of aspects describing what knowing a word entails. To capture partial familiarity, the participants completed in writing a test containing low and mid…

27Al MAS NMR spectroscopic identification of reaction intermediates in the carbothermal reduction and nitridation of alumina

International Nuclear Information System (INIS)

Jung, Woo-Sik; Chae, Seen-Ae

2010-01-01

The reaction intermediates in the carbothermal reduction and nitridation (CRN) reaction of γ-Al 2 O 3 were identified by 27 Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. This identification ruled out the possibility of a reaction mechanism involving the gaseous reaction intermediates. In the CRN reaction of γ-Al 2 O 3 , AlO 4 units were converted to AlN stepwise via AlN x O 4-x (x = 1, 2, 3) intermediates, while AlO 6 units were more slowly converted to AlN than AlO 4 units and the NMR peaks of partially nitridated AlO 6 units were not detected. The NMR peak intensities of partially nitridated AlO 4 units became weaker with increasing reaction temperature.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

Science.gov (United States)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Adiabatic Fixed-Bed Gasification of Colombian Coffee Husk Using Air-Steam Blends for Partial Oxidation

Directory of Open Access Journals (Sweden)

Javier Bonilla

2017-01-01

Full Text Available The increasing energy consumption, mostly supplied by fossil fuels, has motivated the research and development of alternative fuel technologies to decrease the humanity’s dependence on fossil fuels, which leads to pollution of natural sources. Small-scale biomass gasification, using air-steam blends for partial oxidation, is a good alternative since biomass is a neutral carbon feedstock for sustainable energy generation. This research presents results obtained from an experimental study on coffee husk (CH gasification, using air-steam blends for partial oxidation in a 10 kW fixed-bed gasifier. Parametric studies on equivalence ratio (ER (1.53 < ER < 6.11 and steam-fuel (SF ratio (0.23 < SF < 0.89 were carried out. The results show that increasing both SF and ER results in a syngas rich in CH4 and H2 but poor in CO. Also, decreased SF and ER decrease the peak temperature (Tpeak at the gasifier combustion zone. The syngas high heating value (HHV ranged from 3112 kJ/SATPm3 to 5085 kJ/SATPm3 and its maximum value was obtained at SF = 0.87 and ER = 4.09. The dry basis molar concentrations of the species, produced under those operating conditions (1.53 < ER < 6.11 and 0.23 < SF < 0.89, were between 1.12 and 4.1% for CH4, between 7.77 and 13.49% for CO, and between 7.54 and 19.07% for H2. Other species were in trace amount.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

2012-01-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao

2012-12-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Self-propagating solar light reduction of graphite oxide in water

Energy Technology Data Exchange (ETDEWEB)

Todorova, N.; Giannakopoulou, T.; Boukos, N.; Vermisoglou, E. [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece); Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece)

2017-01-01

Highlights: • Graphite oxide was partially reduced by solar light irradiation in water media. • No addition of catalysts nor reductive agent were used for the reduction. • Specific capacitance increased stepwise with increase of irradiation time. • Self-propagating reduction of graphene oxide by solar light is suggested. - Abstract: Graphite Oxide (GtO) is commonly used as an intermediate material for preparation of graphene in the form of reduced graphene oxide (rGO). Being a semiconductor with tunable band gap rGO is often coupled with various photocatalysts to enhance their visible light activity. The behavior of such rGO-based composites could be affected after prolonged exposure to solar light. In the present work, the alteration of the GtO properties under solar light irradiation is investigated. Water dispersions of GtO manufactured by oxidation of natural graphite via Hummers method were irradiated into solar light simulator for different periods of time without addition of catalysts or reductive agent. The FT-IR analysis of the treated dispersions revealed gradual reduction of the GtO with the increase of the irradiation time. The XRD, FT-IR and XPS analyses of the obtained solid materials confirmed the transition of GtO to rGO under solar light irradiation. The reduction of the GtO was also manifested by the CV measurements that revealed stepwise increase of the specific capacitance connected with the restoration of the sp{sup 2} domains. Photothermal self-propagating reduction of graphene oxide in aqueous media under solar light irradiation is suggested as a possible mechanism. The self-photoreduction of GtO utilizing solar light provides a green, sustainable route towards preparation of reduced graphene oxide. However, the instability of the GtO and partially reduced GO under irradiation should be considered when choosing the field of its application.

Fast Partial Evaluation of Pattern Matching in Strings

DEFF Research Database (Denmark)

Ager, Mads Sig; Danvy, Olivier; Rohde, Henning Korsholm

2003-01-01

We show how to obtain all of Knuth, Morris, and Pratt's linear-time string matcher by partial evaluation of a quadratic-time string matcher with respect to a pattern string. Although it has been known for 15 years how to obtain this linear matcher by partial evaluation of a quadratic one, how...... to obtain it in linear time has remained an open problem.Obtaining a linear matcher by partial evaluation of a quadratic one is achieved by performing its backtracking at specialization time and memoizing its results. We show (1) how to rewrite the source matcher such that its static intermediate...... computations can be shared at specialization time and (2) how to extend the memoization capabilities of a partial evaluator to static functions. Such an extended partial evaluator, if its memoization is implemented efficiently, specializes the rewritten source matcher in linear time....

Structural changes of noble metal catalysts during ignition and extinction of the partial oxidation of methane studied by advanced QEXAFS techniques

DEFF Research Database (Denmark)

Grunwaldt, Jan-Dierk; Beier, M.; Kimmerle, B.

2009-01-01

The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystals...... to discuss the potential and limitation of this technique in catalysis and related areas. With respect to the noble metal catalysed partial oxidation of methane, several interesting observations were made: structural changes during ignition were-independent of the chosen reaction conditions......-significantly faster than during the extinction of the reaction. The dynamic behavior of the catalysts was dependent on the flow conditions and the respective noble metal component(s). Higher reaction gas flow led to a faster ignition process. While the ignition over Pt-Rh/Al2O3 occurred at lower temperature than over...

Systematic evaluation of Co-free LnBaFe2O5+δ (Ln = Lanthanides or Y) oxides towards the application as cathodes for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Chen Dengjie; Wang Fucun; Shi Huangang; Ran Ran; Shao Zongping

2012-01-01

Co-free oxides with a nominal composition of LnBaFe 2 O 5+δ , where Ln = La, Pr, Nd, Sm, Gd, and Y, were synthesized and phase structure, oxygen content, electronic conductivity, oxygen desorption, thermal expansion, microstructure and electrochemical performance were systematically investigated. Among the series of materials tested, LaBaFe 2 O 5+δ oxide showed the largest electronic conductivity and YBaFe 2 O 5+δ oxide had the smallest thermal expansion coefficient (TEC) of 14.6 × 10 −6 K −1 within a temperature range of 200–900 °C. All LnBaFe 2 O 5+δ oxides typically possess the TEC values smaller than 20 × 10 −6 K −1 . The oxygen content, electronic conductivity and TEC values are highly dependent on the cation size of the Ln 3+ dopant. The lowest electrode polarization resistance in air under open circuit voltage condition was obtained for SmBaFe 2 O 5+δ electrode and was approximately 0.043, 0.084, 0.196, 0.506 and 1.348 Ω cm 2 at 800, 750, 700, 650 and 600 °C, respectively. The SmBaFe 2 O 5+δ oxide also demonstrated the best performance after a cathodic polarization. A cell with a SmBaFe 2 O 5+δ cathode delivered peak power densities of 1026, 748, 462, 276 and 148 mW cm −2 at 800, 750, 700, 650 and 600 °C, respectively. The results suggest that certain LnBaFe 2 O 5+δ oxides have sufficient electrochemical performance to be promising candidates for cathodes in intermediate-temperature solid oxide fuel cells.

Carrier behavior in special multilayer device composed of different transition metal oxide-based intermediate connectors

International Nuclear Information System (INIS)

Deng, Yan-Hong; Chen, Xiang-Yu; Ou, Qing-Dong; Wang, Qian-Kun; Jiang, Xiao-Cheng; Zhang, Dan-Dan; Li, Yan-Qing

2014-01-01

The impact of illumination on the connection part of the tandem organic light-emitting diodes was studied by using a special organic multilayer sample consisted of two organic active layers coupled with different transition metal oxide (TMO)-based intermediate connectors (ICs). Through measuring the current density-voltage characteristic, interfacial electronic structures, and capacitance-voltage characteristic, we observe an unsymmetrical phenomenon in current density-voltage and capacitance-voltage curves of Mg:Alq 3 /MoO 3 and MoO 3 composed devices, which was induced by the charge spouting zone near the ICs region and the recombination state in the MoO 3 layer. Moreover, Mg:Alq 3 /MoO 3 composed device displays a photovoltaic effect and the V oc shifts to forward bias under illumination. Our results demonstrate that the TMO-based IC structure coupled with photovoltaic effect can be a good approach for the study of photodetector, light sensor, and so on.

High-energy X-ray diffraction studies of short- and intermediate-range structure in oxide glasses

International Nuclear Information System (INIS)

Suzuya, Kentaro

2002-01-01

The feature of high-energy X-ray diffraction method is explained. The oxide glasses studies by using BL04B2, high-energy X-ray diffraction beam line of SPring-8, and the random system materials by high-energy monochromatic X-ray diffraction are introduced. An advantage of third generation synchrotron radiation is summarized. On SPring-8, the high-energy X-ray diffraction experiments of random system are carried out by BL04B2 and BL14B1 beam line. BL04B2 can select Si (111)(E=37.8 keV, λ=0.033 nm) and Si(220)(E=61.7 keV, λ=0.020 nm) as Si monochromator. The intermediate-range structure of (MgO) x (P 2 O 5 ) 1-x glass ,MgP 2 O 6 glass, B 2 O 3 glass, SiO 2 and GeO 2 are explained in detail. The future and application of high-energy X-ray diffraction are stated. (S.Y.)

Partially and fully de-alloyed glassy ribbons based on Au: Application in methanol electro-oxidation studies

Energy Technology Data Exchange (ETDEWEB)

Paschalidou, Eirini Maria, E-mail: epaschal@unito.it [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Scaglione, Federico [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Gebert, Annett; Oswald, Steffen [Leibniz Institut für Festkörper- und Werkstoffforschung IFW, Helmholtzstraße 20, 01069, Dresden (Germany); Rizzi, Paola; Battezzati, Livio [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy)

2016-05-15

In this work, electrochemical de-alloying of an amorphous alloy, Au{sub 40}Cu{sub 28}Ag{sub 7}Pd{sub 5}Si{sub 20}, cast in ribbon form by melt spinning, has been performed, obtaining self standing nanoporous materials suitable for use as electrodes for electrocatalytic applications. The de-alloying encompasses removal of less noble elements and the crystallization of Au, resulting in interconnected ligaments whose size and morphology are described as a function of time. Depending on de-alloying time, the crystals may contain residual amounts of Cu, Ag and Pd, as shown by Auger Electron Spectroscopy (AES), Energy Dispersive Spectroscopy (EDS) and Cyclic Voltammetry (CV) in a basic solution. Current density peaks in the 0.16–0.28 V range (vs Ag/AgCl) indicate that the porous ribbons are active for the electro-oxidation of methanol. The partially de-alloyed samples, which still partially contain the amorphous phase because of the shorter etching times, have finer ligaments and display peaks at lower potential. However, the current density decreases rapidly during repeated potential scans. This is attributed to the obstruction of Au sites, mainly by the Cu oxides formed during the scans. The fully de-alloyed ribbons display current peaks at about 0.20 V and remain active for hundreds of scans at more than 60% of the initial current density. They can be fully re-activated to achieve the same performance levels after a brief immersion in nitric acid. The good activity is due to trapped Ag and Pd atoms in combination with ligament morphology. - Graphical abstract: Fine ligaments and pores made by de-alloying a glassy ribbon of a Au-based alloy, homogeneously produced across the thickness (25 μm) for studying methanol's electro-oxidation behavior. - Highlights: • Size and composition of nanoporous layers tailored in de-alloying Au-based glassy ribbons. • From amorphous precursor fine crystals occur in ligaments with residual Pd and Ag. • Fully de

Response to Reactive Nitrogen Intermediates in Mycobacterium tuberculosis: Induction of the 16-Kilodalton α-Crystallin Homolog by Exposure to Nitric Oxide Donors

OpenAIRE

Garbe, T. R.; Hibler, N. S.; Deretic, V.

1999-01-01

In contrast to the apparent paucity of Mycobacterium tuberculosis response to reactive oxygen intermediates, this organism has evolved a specific response to nitric oxide challenge. Exposure of M. tuberculosis to NO donors induces the synthesis of a set of polypeptides that have been collectively termed Nox. In this work, the most prominent Nox polypeptide, Nox16, was identified by immunoblotting and by N-terminal sequencing as the α-crystallin-related, 16-kDa small heat shock protein, sHsp16...

Thin film devices used as oxygen partial pressure sensors

Science.gov (United States)

Canady, K. S.; Wortman, J. J.

1970-01-01

Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

Science.gov (United States)

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

Science.gov (United States)

Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

2015-11-28

Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is

Partial oxidation of methane to methanol over catalyst ZSM-5 from coal fly ash and rice husk ash

Directory of Open Access Journals (Sweden)

Mirda Yanti Fusia

2017-01-01

Full Text Available Methane is one of the greenhouse gases that can be converted into liquid fuels such as methanol to retain most of the energy of methane and produce a cleaner environment. The conversion of methane to methanol using ZMS-5 represents a breakthrough in the utilization of methane. However, material sources for zeolite synthesis as catalyst usually are pro-analysis grade materials, which are expensive. Therefore, in this research, coal fly ash and rice husk ash were used as raw materials for mesoporous ZSM-5 zeolite synthesis. First, coal fly ash and rice husk were subjected to pre-treatment to extract silicate (SiO44− and aluminate (AlO45− and impurities separation. The ZSM-5 zeolite was synthesized through hydrothermal treatment using two types of templates. After ZSM-5 was synthesized, it was modified with Cobalt through impregnation method. The catalytic activity of both ZSM-5 and Co/ZSM-5 zeolites as heterogeneous catalysts in partial oxidation of methane were preliminary tested and compared with that commercial one. The result showed that the zeolite catalyst ZSM-5 from fly ash coal and rice husk ash has the potential to be used as catalysts in the partial oxidation of methane to methanol.

Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

DEFF Research Database (Denmark)

Jensen, Frank Bo

2008-01-01

The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

La0.6Sr0.4Co0.2Fe0.8O3-δ nanofiber cathode for intermediate-temperature solid oxide fuel cells by water-based sol-gel electrospinning: Synthesis and electrochemical behaviour

DEFF Research Database (Denmark)

Enrico, Anna; Zhang, Wenjing (Angela); Traulsen, Marie Lund

2018-01-01

Water-based sol-gel electrospinning is employed to manufacture perovskite oxide La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) nanofiber cathodes for intermediate-temperature solid oxide fuel cells. LSCF fibrous scaffolds are synthesized through electrospinning of a sol-gel solution employing water as the only...

Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite; Estudo de filme de grafeno/oxido de grafeno obtido por reducao quimica parcial do oxido de grafite

Energy Technology Data Exchange (ETDEWEB)

Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H., E-mail: juliagascho@hotmail.com [Universidade do Estado de Santa Catarina (UDESC), Joinville, SC (Brazil). Programa de Pos-Graduacao em Ciencia e Engenharia de Materiais

2014-07-01

This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

Methane partial oxidation over a LaCr0.85Ru0.15O3 catalyst : Characterization, activity tests and kinetic modeling

NARCIS (Netherlands)

Melchiori, T.; Di Felice, L.; Mota, N.; Navarro, R.M.; Fierro, J.L.G.; Sint Annaland, van M.; Gallucci, F.

2014-01-01

A new LaCr0.85Ru0.15O3 perovskite-type catalyst for CH4 partial oxidation with a high activity and selectivity for syngas with good thermal stability and resistance against coking has been developed. In this paper, the catalyst preparation method, catalyst characterization, results of catalytic

Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2, 3- dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex

Directory of Open Access Journals (Sweden)

Rajneesh Dutt Kaushik

2015-03-01

Full Text Available The formation of ternary intermediate unstable complex during the oxidation of aromatic amines by periodate ion catalysed by MnII has been proposed in case of some anilines. This paper is the first report on stopped-flow kinetic study and evaluation of stability constant of ternary complex forming in the MnII - catalysed periodate oxidation of 2, 3-dimethylaniline (D in acetone-water medium. Stop-flow spectrophotometric method was used to study the ternary complex formation and to determine its stability constant. The stop-flow trace shows the reaction to occur in two steps. The first step, which is presumably the formation of ternary complex, is relatively fast while the second stage is relatively quite slow. The stability constant evaluated for D - MnII - IO4- ternary complex by determining  equilibrium absorbance is (2.2 ± 1.0 × 105. Kinetics of ternary complex formation was defined by the rate law(A  under pseudo first order conditions. ln{[C2]eq / ( [C2]eq -[C2]} = kobs . t (A where, kobs is the pseudo first order rate constant, [C2] is concentration of ternary complex at given time t, and [C2]eq is the equilibrium concentration of ternary complex. © 2015 BCREC UNDIP. All rights reservedReceived: 3rd October 2014; Revised: 4th December 2014; Accepted: 15th December 2014How to Cite: Kaushik, R.D., Agarwal, R., Tyagi, P., Singh, O., Singh, J. (2015. Stopped Flow Kinetics of MnII Catalysed Periodate Oxidation of 2,3-dimethylaniline - Evaluation of Stability Constant of the Ternary Intermediate Complex. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 78-87. (doi:10.9767/bcrec.10.1.7621.78-87Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7621.78-87

Exergy Analysis of an Intermediate Temperature Solid Oxide Fuel Cell-Gas Turbine Hybrid System Fed with Ethanol

Directory of Open Access Journals (Sweden)

Fotini Tzorbatzoglou

2012-10-01

Full Text Available In the present work, an ethanol fed Solid Oxide Fuel Cell-Gas Turbine (SOFC-GT system has been parametrically analyzed in terms of exergy and compared with a single SOFC system. The solid oxide fuel cell was fed with hydrogen produced from ethanol steam reforming. The hydrogen utilization factor values were kept between 0.7 and 1. The SOFC’s Current-Volt performance was considered in the range of 0.1–3 A/cm2 at 0.9–0.3 V, respectively, and at the intermediate operating temperatures of 550 and 600 °C, respectively. The curves used represent experimental results obtained from the available bibliography. Results indicated that for low current density values the single SOFC system prevails over the SOFC-GT hybrid system in terms of exergy efficiency, while at higher current density values the latter is more efficient. It was found that as the value of the utilization factor increases the SOFC system becomes more efficient than the SOFC-GT system over a wider range of current density values. It was also revealed that at high current density values the increase of SOFC operation temperature leads in both cases to higher system efficiency values.

Photocatalytic oxidation of polycyclic aromatic hydrocarbons: Intermediates identification and toxicity testing

International Nuclear Information System (INIS)

Woo, O.T.; Chung, W.K.; Wong, K.H.; Chow, Alex T.; Wong, P.K.

2009-01-01

Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic pollutants and their low water solubility limits their degradation in aqueous solution. The presence of water-miscible solvent such as acetone can increase the water solubility of PAHs, however acetone will also affect the degradation of PAH. In this study the effects of acetone on the photocatalytic degradation efficiency and pathways of 5 selected PAHs, namely naphthalene (2 rings), acenaphthylene (3 rings), phenanthrene (3 rings), anthracene (3 rings) and benzo[a]anthracene (4 rings) were investigated. The Microtox toxicity test was used to determine whether the PCO system can completely detoxify the parental PAHs and its intermediates. The addition of 16% acetone can greatly alter the degradation pathway of naphthalene and anthracene. Based on intermediates identified from degradation of the 5 PAHs, the location of parental PAHs attacked by reactive free radicals can be correlated with the localization energies of different positions of the compound. For toxicity analysis, irradiation by UV light was found to induce acute toxicity by generating intermediates/degradation products from PAHs and possibly acetone. Lastly, all PAHs (10 mg l -1 ) can be completely detoxified by titanium dioxide (100 mg l -1 ) within 24 h under UVA irradiation (3.9 mW cm -2 ).

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

Science.gov (United States)

Serra, José M.; Buchkremer, Hans-Peter

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

Science.gov (United States)

2009-05-01

methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

Oxygen binding to partially nitrosylated hemoglobin.

Science.gov (United States)

Fago, Angela; Crumbliss, Alvin L; Hendrich, Michael P; Pearce, Linda L; Peterson, Jim; Henkens, Robert; Bonaventura, Celia

2013-09-01

Reactions of nitric oxide (NO) with hemoglobin (Hb) are important elements in protection against nitrosative damage. NO in the vasculature is depleted by the oxidative reaction with oxy Hb or by binding to deoxy Hb to generate partially nitrosylated Hb (Hb-NO). Many aspects of the formation and persistence of Hb-NO are yet to be clarified. In this study, we used a combination of EPR and visible absorption spectroscopy to investigate the interactions of partially nitrosylated Hb with O2. Partially nitrosylated Hb samples had predominantly hexacoordinate NO-heme geometry and resisted oxidation when exposed to O2 in the absence of anionic allosteric effectors. Faster oxidation occurred in the presence of 2,3-diphosphoglycerate (DPG) or inositol hexaphosphate (IHP), where the NO-heme derivatives had higher levels of pentacoordinate heme geometry. The anion-dependence of the NO-heme geometry also affected O2 binding equilibria. O2-binding curves of partially nitrosylated Hb in the absence of anions were left-shifted at low saturations, indicating destabilization of the low O2 affinity T-state of the Hb by increasing percentages of NO-heme, much as occurs with increasing levels of CO-heme. Samples containing IHP showed small decreases in O2 affinity, indicating shifts toward the low-affinity T-state and formation of inert α-NO/β-met tetramers. Most remarkably, O2-equilibria in the presence of the physiological effector DPG were essentially unchanged by up to 30% NO-heme in the samples. As will be discussed, under physiological conditions the interactions of Hb with NO provide protection against nitrosative damage without impairing O2 transport by Hb's unoccupied heme sites. This article is part of a Special Issue entitled: Oxygen Binding and Sensing Proteins. Copyright © 2013 Elsevier B.V. All rights reserved.

Hybrid Nitrous Oxide Production from a Partial Nitrifying Bioreactor: Hydroxylamine Interactions with Nitrite.

Science.gov (United States)

Terada, Akihiko; Sugawara, Sho; Hojo, Keisuke; Takeuchi, Yuki; Riya, Shohei; Harper, Willie F; Yamamoto, Tomoko; Kuroiwa, Megumi; Isobe, Kazuo; Katsuyama, Chie; Suwa, Yuichi; Koba, Keisuke; Hosomi, Masaaki

2017-03-07

The goal of this study was to elucidate the mechanisms of nitrous oxide (N 2 O) production from a bioreactor for partial nitrification (PN). Ammonia-oxidizing bacteria (AOB) enriched from a sequencing batch reactor (SBR) were subjected to N 2 O production pathway tests. The N 2 O pathway test was initiated by supplying an inorganic medium to ensure an initial NH 4 + -N concentration of 160 mg-N/L, followed by 15 NO 2 - (20 mg-N/L) and dual 15 NH 2 OH (each 17 mg-N/L) spikings to quantify isotopologs of gaseous N 2 O ( 44 N 2 O, 45 N 2 O, and 46 N 2 O). N 2 O production was boosted by 15 NH 2 OH spiking, causing exponential increases in mRNA transcription levels of AOB functional genes encoding hydroxylamine oxidoreductase (haoA), nitrite reductase (nirK), and nitric oxide reductase (norB) genes. Predominant production of 45 N 2 O among N 2 O isotopologs (46% of total produced N 2 O) indicated that coupling of 15 NH 2 OH with 14 NO 2 - produced N 2 O via N-nitrosation hybrid reaction as a predominant pathway. Abiotic hybrid N 2 O production was also observed in the absence of the AOB-enriched biomass, indicating multiple pathways for N 2 O production in a PN bioreactor. The additional N 2 O pathway test, where 15 NH 4 + was spiked into 400 mg-N/L of NO 2 - concentration, confirmed that the hybrid N 2 O production was a dominant pathway, accounting for approximately 51% of the total N 2 O production.

Prediction of activation energies for aromatic oxidation by cytochrome P450

DEFF Research Database (Denmark)

Rydberg, Patrik; Ryde, Ulf; Olsen, Lars

2008-01-01

We have estimated the activation energy for aromatic oxidation by compound I in cytochrome P450 for a diverse set of 17 substrates using state-of-the-art density functional theory (B3LYP) with large basis sets. The activation energies vary from 60 to 87 kJ/mol. We then test if these results can...... be reproduced by computationally less demanding methods. The best methods (a B3LYP calculation of the activation energy of a methoxy-radical model or a partial least-squares model of the semiempirical AM1 bond dissociation energies and spin densities of the tetrahedral intermediate for both a hydroxyl...

Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

Directory of Open Access Journals (Sweden)

M. Boy

2013-04-01

Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

Hydrogen Production by Catalytic Partial Oxidation of Coke Oven Gas in BaCo0.7Fe0.3-xZrxO3-δ Ceramic Membrane Reactors

Directory of Open Access Journals (Sweden)

Yao Weilin

2016-01-01

Full Text Available The BaCo0.7Fe0.3-xZrxO3-δ (BCFZ, x = 0.04–0.12 mixed ionic–electronic conducting (MIEC membranes were synthesized with a sol–gel method and evaluated as potential membrane reactor materials for the partial oxidation of coke oven gas (COG. The effect of zirconium content on the phase structure, microstructure and performance of the BCFZ membrane under He or COG atmosphere were systemically investigated. The BaCo0.7Fe0.24Zr0.06O3-δ membrane exhibited the best oxygen permeability and good operation stability, which could be a potential candidate of the membrane materials for hydrogen production through the partial oxidation of COG.

Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

DEFF Research Database (Denmark)

Hannemann, S.; Grunwaldt, Jan-Dierk; Kimmerle, B.

2009-01-01

The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on-...

Mixed conducting materials for partial oxidation of hydrocarbons

Directory of Open Access Journals (Sweden)

Frade, J. R.

2004-06-01

Full Text Available Thermodynamic calculations with additional conditions for the conservation of carbon and hydrogen were used to predict the gas composition obtained by partial oxidation of methane as a function of oxygen partial pressure and temperature; this was used to assess the stability and oxygen permeability requirements of mixed conducting membrane materials proposed for this purpose. A re-examination of known mixed conductors shows that most materials with highest permeability still fail to fulfil the requirements of stability under reducing conditions. Other materials possess sufficient stability but their oxygen permeability is insufficient. Different approaches were thus used to attempt to overcome those limitations, including changes in composition in the A and B site positions of ABO3 perovskites, and tests of materials with different structure types. Promising results were obtained mainly for some materials with perovskite or related K2NiF4-type structures. Limited stability of the most promising materials shows that one should rely mainly on kinetic limitations in the permeate side to protect the mixed conductor from severe reducing conditions.

Se han usado cálculos termodinámicos con condiciones adicionales para la conservación del carbono e hidrógeno para predecir la composición del gas obtenido mediante la oxidación parcial del metano en función de la presión parcial de oxígeno y de la temperatura; esto se ha usado para asegurar los requerimientos de estabilidad y permeabilidad al oxígeno de los materiales conductores mixtos empleados como membrana para este propósito. Un nuevo exámen de los conductores mixtos conocidos muestra que la mayoría de los materiales con la mayor permeabilidad todavía fallan en el cumplimiento de los requerimientos de estabilidad bajo condiciones reductoras. Otros materiales poseen suficiente estabilidad, pero su permeabilidad al oxígeno es insuficiente. Por ello se han empleado diferentes

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

Science.gov (United States)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

The Relationship Between Structural and Catalytic Activity of α and γ-Bismuth-Molybdate Catalysts for Partial Oxidation of Propylene to Acrolein

Science.gov (United States)

Fansuri, H.; Pham, G. H.; Wibawanta, S.; Zhang, D. K.; French, David

Bismuth-molybdate catalysts are known to be effective for catalytic partial oxidation of propylene to acrolein. Their properties and the kinetics and reaction mechanisms for acrolein production have been extensively studied, especially in their basic forms, such as α, β, and γ-bismuth-molybdate. Although the reaction mechanisms have been reported widely in the literature, a general agreement has not been reached, especially from a catalyst-structure point of view. The present contribution reports an effort to understand the structural changes of α and γ-bismuth-molybdate catalysts at varying temperatures as examined using high temperature XRD and to relate the catalyst performance (activity and selectivity) for propylene partial oxidation to acrolein. The XRD analysis was performed at temperature between 250 and 450°C in ambient atmosphere and the Rietveld refinement method was used to extract unit cell parameters. The results showed a distinct similarity between the shapes of the thermal expansion of the catalysts and their activity and selectivity curves, indicating a significant role that the catalyst interatomic structure plays in the overall reaction mechanism.

Electrochemical performance of Nd1.8Ce0.2CuO4+δ:Ce0.9Gd0.1O2 composite cathode for intermediate temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Khandale, A.P.; Bhoga, S.S.

2012-01-01

Intermediate temperature solid oxide fuel cells (IT-SOFCs) are viewed as a promising power generation systems with high efficiency and low pollution. Recently, mixed ionic-electronic conductors (MIECs), with K 2 NiF 4 - type structure, attracted much attention as cathode for IT-SOFC

Simulation study of a PEM fuel cell system fed by hydrogen produced by partial oxidation

Energy Technology Data Exchange (ETDEWEB)

Ozdogan, S [Marmara University, Faculty of Engineering, Istanbul (Turkey); Ersoz, A; Olgun, H [TUBITAK Marmara Research Center, Energy Systems and Environmental Research Institute, Kocaeli (Turkey)

2003-09-01

Within the frame of sustainable development, efficient and clean, if possible zero emission energy production technologies are of utmost importance in various sectors such as utilities, industry, households and transportation. Low-temperature fuel cell systems are suitable for powering transportation systems such as automobiles and trucks in an efficient and low-emitting manner. Proton exchange membrane (PEM) fuel cell systems constitute the most promising low temperature fuel cell option being developed globally. PEM fuel cells generate electric power from air and hydrogen or from a hydrogen rich gas via electrochemical reactions. Water and waste heat are the only by-products of PEM fuel cells. There is great interest in converting current hydrocarbon based common transportation fuels such as gasoline and diesel into hydrogen rich gases acceptable by PEM fuel cells. Hydrogen rich gases can be produced from conventional transportation fuels via various reforming technologies. Steam reforming, partial oxidation and auto-thermal reforming are the three major reforming technologies. In this paper, we discuss the results of a simulation study for a PEM fuel cell with partial oxidation. The Aspen HYSYS 3.1 code has been used for simulation purposes. Two liquid hydrocarbon fuels have been selected to investigate the effect of average molecular weights of hydrocarbons, on the fuel processing efficiency. The overall system efficiency depends on the fuel preparation and fuel cell efficiencies as well as on the heat integration within the system. It is desired to investigate the overall system efficiencies for net electrical power production at 100 kW considering bigger scale transport applications. Results indicate that fuel properties, fuel preparation system operating parameters and PEM fuel cell polarization curve characteristics all affect the overall system efficiency. (authors)

Reversible solid oxide fuel cells (R-SOFCs) with chemically stable proton-conducting oxides

KAUST Repository

Bi, Lei; Boulfrad, Samir; Traversa, Enrico

2015-01-01

Proton-conducting oxides offer a promising way of lowering the working temperature of solid oxide cells to the intermediate temperate range (500 to 700. °C) due to their better ionic conductivity. In addition, the application of proton

Physical transformations of iron oxide and silver nanoparticles from an intermediate scale field transport study

Science.gov (United States)

Emerson, Hilary P.; Hart, Ashley E.; Baldwin, Jonathon A.; Waterhouse, Tyler C.; Kitchens, Christopher L.; Mefford, O. Thompson; Powell, Brian A.

2014-02-01

In recent years, there has been increasing concern regarding the fate and transport of engineered nanoparticles (NPs) in environmental systems and the potential impacts on human and environmental health due to the exponential increase in commercial and industrial use worldwide. To date, there have been relatively few field-scale studies or laboratory-based studies on environmentally relevant soils examining the chemical/physical behavior of the NPs following release into natural systems. The objective of this research is to demonstrate the behavior and transformations of iron oxide and silver NPs with different capping ligands within the unsaturated zone. Here, we show that NP transport within the vadose zone is minimal primarily due to heteroaggregation with soil surface coatings with results that >99 % of the NPs remained within 5 cm of the original source after 1 year in intermediate-scale field lysimeters. These results suggest that transport may be overestimated when compared to previous laboratory-scale studies on pristine soils and pure minerals and that future work must incorporate more environmentally relevant parameters.

Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

DEFF Research Database (Denmark)

Huang, Yunjie; Li, Q.F.; Pan, Chao

2012-01-01

A series of metal phosphates were synthesized and screened as potential proton conductor electrolytes for fuel cells and electrolysers operational at intermediate temperatures. Among the selected, niobium and bismuth phosphates exhibited a proton conductivity of 10-2 and 10-7 S cm-1, respectively......, under the anhydrous atmosphere at 250 °C, showing close correlation with the presence of hydroxyl groups in the phosphate phases. At the water partial pressure of above 0.6 atm, both phosphates possessed a proton conductivity to a level of above 3 x 10-2 S cm-1. Reasonable stability of the proton...... conductivity was observed under either a constant low water partial pressure or under a humidity cycling test within a period of more than 80 hours....

The MHD intermediate shock interaction with an intermediate wave: Are intermediate shocks physical?

International Nuclear Information System (INIS)

Wu, C.C.

1988-01-01

Contrary to the usual belief that MHD intermediate shocks are extraneous, the authors have recently shown by numerical solutions of dissipative MHD equations that intermediate shocks are admissible and can be formed through nonlinear steepening from a continuous wave. In this paper, he clarifies the differences between the conventional view and the results by studying the interaction of an MHD intermediate shock with an intermediate wave. The study reaffirms his results. In addition, the study shows that there exists a larger class of shocklike solutions in the time-dependent dissiaptive MHD equations than are given by the MHD Rankine-Hugoniot relations. it also suggests a mechanism for forming rotational discontinuities through the interaction of an intermediate shock with an intermediate wave. The results are of importance not only to the MHD shock theory but also to studies such as magnetic field reconnection models

Partial oxidation of n- and i-pentane over promoted vanadium-phosphorus oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Zazhigalov, V.A.; Mikhajluk, B.D.; Komashko, G.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

1998-12-31

It is known, that the cost of raw materials for catalytic oxidation processes is about 60% of the product price. Cheap initial compounds to produce variety of products and to replace olefins and aromatic hydrocarbons are paraffins. That is why catalytic systems which could be possibly rather efficient in selective oxidation of paraffin hydrocarbons are under very close investigation now. One of such processes in n-pentane oxidation. The obtained results on n-pentane oxidation over VPO catalysts were quite encouraging in respect of possible reach high selectivity and yield of phthalic anhydride. However, in our work it was shown that the main product of n-pentane oxidation in the presence of VPO catalytic system as well as VPMeO was maleic anhydride. Some later our results were confirmed in, where to grow the selectivity towards phthalic anhydride the Co-additive was introduced. On the basis of the proposal made before on the mechanism of paraffins conversion over the vanadyl pyrophosphate surface with their activation at the first and fourth carbon atoms, we assumed possible methylmaleic (citraconic) anhydride forming at n- and i-pentane oxidation. This assumption has been recently supported by both our and other researchers` experimental results. In it was also hypothized possible mechanistic features for phthalic anhydride forming from n-pentane. The present work deals with the results of n- and i-pentane oxidation over VPO catalysts promoted with Bi, Cs, Te, Zr. (orig.)

Enzymatic Upgrading of Heavy Crudes via Partial Oxidation or Conversion of PAHs

Energy Technology Data Exchange (ETDEWEB)

Borole, A P; Davison, B H; Kuritz, T

2002-07-01

The objective of this program was to investigate new enzyme-based technologies for upgrading of heavy oils. Enzymes were selected for screening from those capable of conversion of polyaromatic hydrocarbons (PAHs) reported in the literature. Oxidative reactions of PAHs using hydrogen peroxide as an oxidant with conversion to partially oxidized products were used. The enzymes (lignin peroxidase, cytochrome c) were tested in various organic solvents and found to loose activity in pure organic solvents. A thermodynamic analysis revealed lack of effective interaction between the substrate and enzyme as the cause for low activity. The protein cytochrome c was modified to work in organic media by chemical hydrophobic group attachment. Two different modifications were made: attachment of polyethylene glycol (PEG) and alkyl groups. Alkyl groups, being small could be attached at interior locations within the core of the enzyme and possibly near the active site. Increase in the threshold solvent concentration where maximum enzyme activity occurred indicated potential of this strategy for effective enzyme-substrate interaction. Further improvements in enzyme activity called for other diverse methods due to the unavailability of sufficient chemical modification sites. Genetic techniques were therefore explored for further improvements. These experiments focused on cloning of a gene for the fungal enzyme lignin peroxidase (lip) into yeast Pichia pastoris, which would allow easy manipulation of the gene. However, differences in the fungal and yeast cellular machinery impeded significant expression of the fungal enzyme. Several strategies were explored to allow higher-level expression of the enzyme, which was required for enzyme improvement. The strategies used in this investigation are described in the report. Industrial in-kind support was available throughout the project period. review of the research results was carried out on a regular basis (bimonthly reports and annual

Adiabatic Gasification and Pyrolysis of Coffee Husk Using Air-Steam for Partial Oxidation

Directory of Open Access Journals (Sweden)

Catalina Rodriguez

2011-01-01

Full Text Available Colombian coffee industry produces about 0.6 million tons of husk (CH per year which could serve as feedstock for thermal gasification to produce gaseous and liquid fuels. The current paper deals with: (i CH adiabatic gasification modeling using air-steam blends for partial oxidation and (ii experimental thermogravimetric analysis to determine the CH activation energy (E. The Chemical Equilibrium with Applications Program (CEA, developed by NASA, was used to estimate the effect of equivalence ratio (ER and steam to fuel ratio (S : F on equilibrium temperature and gas composition of ~150 species. Also, an atom balance model was developed for comparison purposes. The results showed that increased ER and (S : F ratios produce mixtures that are rich in H2 and CO2 but poor in CO. The value for the activation energy was estimated to be 221 kJ/kmol.

Experimental investigation and thermodynamic simulation of the uranium oxide-zirconium oxide-iron oxide system in air

Czech Academy of Sciences Publication Activity Database

Petrov, Y. B.; Udalov, Y. P.; Šubrt, Jan; Bakardjieva, Snejana; Sázavský, P.; Kiselová, M.; Selucký, P.; Bezdička, Petr; Joumeau, C.; Piluso, P.

2011-01-01

Roč. 37, č. 2 (2011), s. 212-229 ISSN 1087-6596 Institutional research plan: CEZ:AV0Z40320502 Keywords : uranium oxide * zirconium oxide * iron oxide * fusibility curve * oxygen partial pressure * crystallization * phase composition Subject RIV: CA - Inorganic Chemistry Impact factor: 0.492, year: 2011

Fast Partial Evaluation of Pattern Matching in Strings

DEFF Research Database (Denmark)

Ager, Mads Sig; Danvy, Olivier; Rohde, Henning Korsholm

2006-01-01

We show how to obtain all of Knuth, Morris, and Pratt's linear-time string matcher by specializing a quadratic-time string matcher with respect to a pattern string. Although it has been known for 15 years how to obtain this linear matcher by partial evaluation of a quadratic one, how to obtain...... it in linear time has remained an open problem. Obtaining a linear matcher by partial evaluation of a quadratic one is achieved by performing its backtracking at specialization time and memoizing its results. We show (1) how to rewrite the source matcher such that its static intermediate computations can...... be shared at specialization time and (2) how to extend the memoization capabilities of a partial evaluator to static functions. Such an extended partial evaluator, if its memoization is implemented efficiently, specializes the rewritten source matcher in linear time. Finally, we show that the method also...

Fast Partial Evaluation of Pattern Matching in Strings

DEFF Research Database (Denmark)

Ager, Mads Sig; Danvy, Olivier; Rohde, Henning Korsholm

2003-01-01

We show how to obtain all of Knuth, Morris, and Pratt's linear-time string matcher by specializing a quadratic-time string matcher with respect to a pattern string. Although it has been known for 15 years how to obtain this linear matcher by partial evaluation of a quadratic one, how to obtain...... it in linear time has remained an open problem. Obtaining a linear matcher by partial evaluation of a quadratic one is achieved by performing its backtracking at specialization time and memoizing its results. We show (1) how to rewrite the source matcher such that its static intermediate computations can...... be shared at specialization time and (2) how to extend the memoization capabilities of a partial evaluator to static functions. Such an extended partial evaluator, if its memoization is implemented efficiently, specializes the rewritten source matcher in linear time. Finally, we show that the method also...

Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

Directory of Open Access Journals (Sweden)

Saravana Prakash Thirumuruganandham

2010-01-01

Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

Science.gov (United States)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

Partial to complete wetting transitions in immiscible ternary blends with PLA: the influence of interfacial confinement.

Science.gov (United States)

Zolali, Ali M; Favis, Basil D

2017-04-12

In this study it is shown that the three different intermediate phases in melt blended ternary PLA/PHBV/PBS, PLA/PBAT/PE and PLA/PE/PBAT systems all demonstrate partial wetting, but have very different wetting behaviors as a function of composition and annealing. The interfacial tension of the various components, their spreading coefficients and the contact angles of the confined partially wet droplets at the interface are examined in detail. A wetting transition from partially wet droplets to a complete layer at the interface is observed for both PHBV and PBAT by increasing the concentration and also by annealing. In contrast, in PLA/PE/PBAT, the partially wet droplets of PE at the interface of PLA/PBAT coalesce and grow in size, but remain partially wet even at a high PE concentration of 20% and after 30 min of quiescent annealing. The dewetting speed of the intermediate phase is found to be the principal factor controlling these wetting transitions. This work shows the significant potential for controlled wetting and structuring in ternary polymer systems.

Bias-induced migration of ionized donors in amorphous oxide semiconductor thin-film transistors with full bottom-gate and partial top-gate structures

Directory of Open Access Journals (Sweden)

Mallory Mativenga

2012-09-01

Full Text Available Bias-induced charge migration in amorphous oxide semiconductor thin-film transistors (TFTs confirmed by overshoots of mobility after bias stressing dual gated TFTs is presented. The overshoots in mobility are reversible and only occur in TFTs with a full bottom-gate (covers the whole channel and partial top-gate (covers only a portion of the channel, indicating a bias-induced uneven distribution of ionized donors: Ionized donors migrate towards the region of the channel that is located underneath the partial top-gate and the decrease in the density of ionized donors in the uncovered portion results in the reversible increase in mobility.

The reaction mechanism of the partial oxidation of methane to synthesis gas: a transient kinetic study over rhodium and a comparison with platinum

NARCIS (Netherlands)

Mallens, E.P.J.; Hoebink, J.H.B.J.; Marin, G.B.M.M.

1997-01-01

The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice

Nanostructured LnBaCo2O6− (Ln = Sm, Gd with layered structure for intermediate temperature solid oxide fuel cell cathodes

Directory of Open Access Journals (Sweden)

Augusto E. Mejía Gómez

2017-04-01

Full Text Available In this work, we present the combination of two characteristics that are beneficial for solid oxide fuel cell (SOFC cathodic performance in one material. We developed and evaluated for the first time nanostructured layered perovskites of formulae LnBaCo2O6-d with Ln = Sm and Gd (SBCO and GBCO, respectively as SOFC cathodes, finding promising electrochemical properties in the intermediate temperature range. We obtained those nanostructures by using porous templates to confine the chemical reagents in regions of 200-800 nm. The performance of nanostructured SBCO and GBCO cathodes was analyzed by electrochemical impedance spectroscopy technique under different operating conditions using Gd2O3-doped CeO2 as electrolyte. We found that SBCO cathodes displayed lower area-specific resistance than GBCO ones, because bulk diffusion of oxide ions is enhanced in the former. We also found that cathodes synthesized using smaller template pores exhibited better performance.

Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

Science.gov (United States)

Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

2018-04-01

Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

Partial thermodynamic functions of hydrogen in complex hydrated vanadium(5) and tungsten(6) oxides

International Nuclear Information System (INIS)

Volkov, V.L.; Zakharova, G.S.

2003-01-01

The partial thermodynamic characteristics of hydrogen in the complex hydrated vanadium(5) and tungsten(6) oxides, obtained through the sol-gel method, of the general formula H 2 V 12-y W y O 31+δ ·nH 2 O (0 ≤ x ≤ 0.33) are determined through the emf method. The changes in these values (ΔG-bar(H 2 ), ΔH-bar(H 2 ) and ΔS-bar(H 2 )) in dependence on the compound composition are discussed. It is established that ΔG-bar(H 2 ) phases, amorphous to X-rays are determined by the ΔS-bar(H 2 ) value and crystalline ones by ΔH-bar(H 2 ). The scheme of the phase relationships of the H 2 O-H-WO 3 -V 2 O 5 system, whereto the given phases are related are presented [ru

First Principles Studies of Perovskites for Intermediate Temperature Solid Oxide Fuel Cell Cathodes

KAUST Repository

Salawu, Omotayo Akande

2017-05-15

Fundamental advances in cathode materials are key to lowering the operating temperature of solid oxide fuel cells (SOFCs). Detailed understanding of the structural, electronic and defect formation characteristics are essential for rational design of cathode materials. In this thesis we employ first principles methods to study La(Mn/Co)O3 and LnBaCo2O5+δ (Ln = Pr, Gd; δ = 0.5, 1) as cathode for SOFCs. Specifically, factors affecting the O vacancy formation and migration are investigated. We demonstrate that for LaMnO3 the anisotropy effects often neglected at high operating temperatures become relevant when the temperature is lowered. We show that this fact has consequences for the material properties and can be further enhanced by strain and Sr doping. Tensile strain promotes both the O vacancy formation and migration in pristine and Sr doped LaMnO3, while Sr doping enhances the O vacancy formation but not the migration. The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in LaCoO3 are studied. All three dopants are found to facilitate O vacancy formation. Substitution of La3+ with Ba2+/Mg2+ yields the lowest O vacancy formation energy for low/intermediate spin Co, implying that not only the structure, but also the spin state of Co is a key parameter. Only for low spin Co the ionic radius is correlated with the O migration barrier. Enhanced migration for intermediate spin Co is ascribed to the availability of additional space at the transition state. For LnBaCo2O5+δ we compare the O vacancy formation in GdBaCo2O5.5 (Pmmm symmetry) and GdBaCo2O6 (P4/mmm symmetry), and the influence of Sr doping. The O vacancy formation energy is demonstrated to be smaller in the already O deficient compound. This relation is maintained under Sr doping. It turns out that Sr doping can be utilized to significantly enhance the O vacancy formation in both compounds. The observed trends are

Effect of Internal Factors and External Factors on Learning Achievement Intermediate Financial Accounting Course I

OpenAIRE

Huda, Syamsul; Diana, Nana

2017-01-01

The purpose of this study was to determine the effect of internal and external factors of students on the achievement of intermediate financial accounting courses 1 partially and simultaneously. This type of research is quantitative, while the data used in this study is primary data in the form of questionnaires and secondary data in the form of midterm semester exam on intermediate financial accounting 1 semester odd academic year 2016/2017. Hypothesis testing using multiple regression analy...

A new partial SOI-LDMOSFET with a modified buried oxide layer for improving self-heating and breakdown voltage

International Nuclear Information System (INIS)

Jamali Mahabadi, S E; Orouji, Ali A; Keshavarzi, P; Moghadam, Hamid Amini

2011-01-01

In this paper, for the first time, we propose a partial silicon-on-insulator (P-SOI) lateral double-diffused metal-oxide-semiconductor-field-effect-transistor (LDMOSFET) with a modified buried layer in order to improve breakdown voltage (BV) and self-heating effects (SHEs). The main idea of this work is to control the electric field by shaping the buried layer. With two steps introduced in the buried layer, the electric field distribution is modified. Also a P-type window introduced makes the substrate share the vertical voltage drop, leading to a high vertical BV. Moreover, four interface electric field peaks are introduced by the buried P-layer, the Si window and two steps, which modulate the electric field in the SOI layer and the substrate. Hence, a more uniform electric field is obtained; consequently, a high BV is achieved. Furthermore, the Si window creates a conduction path between the active layer and substrate and alleviates the SHE. Two-dimensional simulations show that the BV of double step partial silicon on insulator is nearly 69% higher and alleviates SHEs 17% in comparison with its single step partial SOI counterpart and nearly 265% higher and alleviate SHEs 18% in comparison with its conventional SOI counterpart

Hydrogen or synthesis gas production via the partial oxidation of methane over supported nickel-cobalt catalysts

Energy Technology Data Exchange (ETDEWEB)

Koh, Alaric C.W. [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Chen, Luwei; Lin, Jianyi [Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Kee Leong, Weng [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Johnson, Brian F.G.; Khimyak, Tetyana [University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW (United Kingdom)

2007-05-15

Activity, selectivity, and coking-resistance of a series of Ni{sub x}Co{sub y} (where x,y are the respective metal loadings of 0, 1, 2 or 3 wt.%; x+y=3) bimetallic catalysts supported on CaAl{sub 2}O{sub 4}/Al{sub 2}O{sub 3} have been studied for hydrogen/synthesis gas production via the catalytic partial oxidation (CPO) of methane. Catalysts were characterized by temperature programmed reduction (TPR), transmission electron microscopy (TEM) and X-ray fluorescence multi-element analysis (XRF). Their activity for the partial oxidation of methane to hydrogen and carbon monoxide (at 1 bar, gas hourly space velocity (GHSV) of 144,000cm{sup 3}g{sup -1}h{sup -1} and CH{sub 4}/O{sub 2} molar ratio of 2) was investigated, and coke deposited on the spent catalysts was studied by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The activity was found to decrease in the order of Ni{sub 2}Co>Ni{sub 3}>NiCo{sub 2}>>Co{sub 3}, while CO and H{sub 2} selectivities were found to be in the order ofNi{sub 2}Co>Ni{sub 3}{approx}NiCo{sub 2}>Co{sub 3}. Ni{sub 2}Co is also shown to be more resistant to coking as compared to Ni{sub 3}, which is a current catalyst of choice. Results show that not only does Ni{sub 2}Co have the highest activity and selectivity among all the catalysts tested, it is also relatively resistant to coking. This finding would be helpful for catalyst design to achieve high coking resistivity catalysts for hydrogen production from CPO of methane. (author)

Diesel soot oxidation under controlled conditions

OpenAIRE

Song, Haiwen

2003-01-01

This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University, 11/12/2003. In order to improve understanding of diesel soot oxidation, an experimental rig was designed and set up, in which the soot oxidation conditions, such as temperature, oxygen partial pressure, and CO2 partial pressure, could be varied independently of each other. The oxidizing gas flow in the oxidizer was under laminar condition. This test rig comprised a naturally-aspirated single ...

Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates

International Nuclear Information System (INIS)

Lee, Yuan-Pern

2015-01-01

The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH 2 OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O 2 , with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates. Their structures and spectral parameters have been characterized; their significant zwitterionic nature is hence confirmed. CH 2 OO, along with other products, has also been detected directly with microwave spectroscopy in gaseous ozonolysis reactions of ethene. The detailed kinetics of the source reaction, CH 2 I + O 2 , which is critical to laboratory studies of CH 2 OO, are now understood satisfactorily. The kinetic investigations using direct detection identified some important atmospheric reactions, including reactions with NO 2 , SO 2 , water dimer, carboxylic acids, and carbonyl compounds. Efforts toward the characterization of larger Criegee intermediates and the investigation of related reactions are in progress. Some reactions of CH 3 CHOO are found to depend on conformation. This perspective examines progress toward the direct spectral characterization of Criegee intermediates and investigations of the associated reaction kinetics, and indicates some unresolved problems and prospective challenges for this exciting field of research

Nanotubes of rare earth cobalt oxides for cathodes of intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Sacanell, Joaquin [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina); Leyva, A. Gabriela [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Escuela de Ciencia y Tecnologia, UNSAM. Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Bellino, Martin G.; Lamas, Diego G. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina)

2010-04-02

In this work we studied the electrochemical properties of cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) prepared with nanotubes of La{sub 0.6}Sr{sub 0.4}CoO{sub 3} (LSCO). Their nanostructures consist of agglomerated nanoparticles in tubular structures of sub-micrometric diameter. The resulting cathodes are highly porous both at the micro- and the nanoscale. This fact increases significantly the access to active sites for the oxygen reduction. We investigated the influence of the diameter of the precursor nanotubes on the polarization resistance of the LSCO cathodes on CeO{sub 2}-10 mol.% Sm{sub 2}O{sub 3} (SDC) electrolytes under air atmosphere, evaluated in symmetrical [LSCO/SDC/LSCO] cells. Our results indicate an optimized performance when the diameter of precursor nanotubes is sufficiently small to become dense nanorods after cathode sintering. We present a phenomenological model that successfully explains the behavior observed and considers that a small starting diameter acts as a barrier that prevents grains growth. This is directly related with the lack of contact points between nanotubes in the precursor, which are the only path for the growth of ceramic grains. We also observed that a conventional sintering process (of 1 h at 1000 C with heating and cooling rates of 10 C min{sup -1}) has to be preferred against a fast firing one (1 or 2 min at 1100 C with heating and cooling rates of 100 C min{sup -1}) in order to reach a higher performance. However, a good adhesion of the cathode can be achieved with both methods. Our results suggest that oxygen vacancy diffusion is enhanced while decreasing LSCO particle size. This indicates that the high performance of our nanostructured cathodes is not only related with the increase of the number of active sites for oxygen reduction but also to the fact that the nanotubes are formed by nanoparticles. (author)

Cobalt-free cathode material SrFe{sub 0.9}Nb{sub 0.1}O{sub 3-{delta}} for intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Zhou, Qingjun [State Key Laboratory of Superhard Materials and College of Physics, Jilin University, Changchun 130012 (China); College of Science, Civil Aviation University of China, Tianjin 300300 (China); Zhang, Leilei; He, Tianmin [State Key Laboratory of Superhard Materials and College of Physics, Jilin University, Changchun 130012 (China)

2010-02-15

A cobalt-free cubic perovskite oxide, SrFe{sub 0.9}Nb{sub 0.1}O{sub 3-{delta}} (SFN) was investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD results showed that SFN cathode was chemically compatible with the electrolyte Sm{sub 0.2}Ce{sub 0.8}O{sub 1.9} (SDC) for temperatures up to 1050 C. The electrical conductivity of SFN sample reached 34-70 S cm{sup -1} in the commonly operated temperatures of IT-SOFCs (600-800 C). The area specific resistance was 0.138 {omega} cm{sup 2} for SFN cathode on SDC electrolyte at 750 C. A maximum power density of 407 mW cm{sup -2} was obtained at 800 C for single-cell with 300 {mu}m thick SDC electrolyte and SFN cathode. (author)

Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

KAUST Repository

Monge Palacios, Manuel

2018-01-29

We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

Science.gov (United States)

Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

2018-03-01

Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

Composite cathode La0.15Bi0.85O1.5-Ag for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Gao Zhan; Mao Zongqiang; Huang Jianbing; Gao Ruifeng; Wang Cheng; Liu Zhixiang

2008-01-01

Composites consisting of silver and lanthanum stabilized bismuth oxide (La 0.15 Bi 0.85 O 1.5 ) were investigated as cathodes for intermediate-temperature solid oxide fuel cells with doped ceria as electrolyte. No stable phases were formed via reaction between La 0.15 Bi 0.85 O 1.5 and Ag. The microstructure of the interfaces between composite cathodes and Ce 0.8 Sm 0.2 O 1.5 electrolytes was studied by scanning electron microscopy after sintering at various temperatures. Impedance spectroscopy measurements revealed that the performance of cathode fired at 700 deg. C was the best. When the optimum fraction of Ag was 50 vol.%, polarization resistance values for the LSB-Ag50 cathode were as low as 0.14 Ω cm 2 at 700 deg. C and 0.18 Ω cm 2 at 650 deg. C. The steady-state polarization investigations on LSB and LSB-Ag50 cathodes were performed using typical three-electrode test cells in air. The results showed that the LSB-Ag50 composite cathode exhibited a lower overpotential and higher exchange current density than LSB, which indicated the electrochemical performance of LSB-Ag50 for the oxygen reduction reaction was superior to the LSB

Enhanced Sensitivity of Anti-Symmetrically Structured Surface Plasmon Resonance Sensors with Zinc Oxide Intermediate Layers

Directory of Open Access Journals (Sweden)

Nan-Fu Chiu

2013-12-01

Full Text Available We report a novel design wherein high-refractive-index zinc oxide (ZnO intermediary layers are used in anti-symmetrically structured surface plasmon resonance (SPR devices to enhance signal quality and improve the full width at half maximum (FWHM of the SPR reflectivity curve. The surface plasmon (SP modes of the ZnO intermediary layer were excited by irradiating both sides of the Au film, thus inducing a high electric field at the Au/ZnO interface. We demonstrated that an improvement in the ZnO (002 crystal orientation led to a decrease in the FWHM of the SPR reflectivity curves. We optimized the design of ZnO thin films using different parameters and performed analytical comparisons of the ZnO with conventional chromium (Cr and indium tin oxide (ITO intermediary layers. The present study is based on application of the Fresnel equation, which provides an explanation and verification for the observed narrow SPR reflectivity curve and optical transmittance spectra exhibited by (ZnO/Au, (Cr/Au, and (ITO/Au devices. On exposure to ethanol, the anti-symmetrically structured showed a huge electric field at the Au/ZnO interface and a 2-fold decrease in the FWHM value and a 1.3-fold larger shift in angle interrogation and a 4.5-fold high-sensitivity shift in intensity interrogation. The anti-symmetrically structured of ZnO intermediate layers exhibited a wider linearity range and much higher sensitivity. It also exhibited a good linear relationship between the incident angle and ethanol concentration in the tested range. Thus, we demonstrated a novel and simple method for fabricating high-sensitivity, high-resolution SPR biosensors that provide high accuracy and precision over relevant ranges of analyte measurement.

Echinococcus multilocularis and Its Intermediate Host: A Model of Parasite-Host Interplay

Directory of Open Access Journals (Sweden)

Dominique Angèle Vuitton

2010-01-01

Full Text Available Host-parasite interactions in the E. multilocularis-intermediate host model depend on a subtle balance between cellular immunity, which is responsible for host's resistance towards the metacestode, the larval stage of the parasite, and tolerance induction and maintenance. The pathological features of alveolar echinococcosis. the disease caused by E. multilocularis, are related both to parasitic growth and to host's immune response, leading to fibrosis and necrosis, The disease spectrum is clearly dependent on the genetic background of the host as well as on acquired disturbances of Th1-related immunity. The laminated layer of the metacestode, and especially its carbohydrate components, plays a major role in tolerance induction. Th2-type and anti-inflammatory cytokines, IL-10 and TGF-β, as well as nitric oxide, are involved in the maintenance of tolerance and partial inhibition of cytotoxic mechanisms. Results of studies in the experimental mouse model and in patients suggest that immune modulation with cytokines, such as interferon-α, or with specific antigens could be used in the future to treat patients with alveolar echinococcosis and/or to prevent this very severe parasitic disease.

Effect of systemic nitric oxide synthase inhibition on optic disc oxygen partial pressure in normoxia and in hypercapnia.

Science.gov (United States)

Petropoulos, Ioannis K; Pournaras, Jean-Antoine C; Stangos, Alexandros N; Pournaras, Constantin J

2009-01-01

To investigate the effect of systemic nitric oxide synthase (NOS) inhibition on optic disc oxygen partial pressure (PO(2)) in normoxia and hypercapnia. Intervascular optic disc PO(2) was measured in 12 anesthetized minipigs by using oxygen-sensitive microelectrodes placed 0.1), despite a 21% increase of mean arterial pressure. Optic disc PO(2) increase under hypercapnia was blunted after L-NAME injection (DeltaPO(2) = 0.6 +/- 1.1 mm Hg; 3%; P > 0.1), and this effect was reversible by L-arginine. Moreover, L-NAME reduced the response to carbogen by 29% (DeltaPO(2) = 9.1 +/- 4.4 mm Hg; 49%; P = 0.01 versus before L-NAME). The response to hyperoxia was not affected. Whereas systemic NOS inhibition did not affect optic disc PO(2) in normoxia, a blunting effect was noted on the CO(2)-induced optic disc PO(2) increase. Nitric oxide appears to mediate the hypercapnic optic disc PO(2) increase.

Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

Directory of Open Access Journals (Sweden)

J. Lee-Taylor

2012-08-01

Full Text Available The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere. Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA formation for various preexisting organic aerosol concentration (COA. As expected, simulation results show that (i SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii SOA yield decreases with decreasing COA, (iii SOA production rates increase with increasing COA and (iv the number of oxidation steps (i.e. generations needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA, suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA with large yields. The limitations of the model are discussed.

Conductance of partially disordered graphene: crossover from temperature-dependent to field-dependent variable-range hopping

International Nuclear Information System (INIS)

Cheah, C Y; Jaurigue, L C; Kaiser, A B; Gómez-Navarro, C

2013-01-01

We report an analysis of low-temperature measurements of the conductance of partially disordered reduced graphene oxide, finding that the data follow a simple crossover scenario. At room temperature, the conductance is dominated by two-dimensional (2D) electric field-assisted, thermally driven (Pollak–Riess) variable-range hopping (VRH) through highly disordered regions. However, at lower temperatures T, we find a smooth crossover to follow the exp(−E 0 /E) 1/3 field-driven (Shklovskii) 2D VRH conductance behaviour when the electric field E exceeds a specific crossover value E C (T) 2D =(E a E 0 1/3 /3) 3/4 determined by the scale factors E 0 and E a for the high-field and intermediate-field regimes respectively. Our crossover scenario also accounts well for experimental data reported by other authors for three-dimensional disordered carbon networks, suggesting wide applicability. (paper)

Detection of thermally grown oxides in thermal barrier coatings by nondestructive evaluation

Science.gov (United States)

Fahr, A.; Rogé, B.; Thornton, J.

2006-03-01

The thermal-barrier coatings (TBC) sprayed on hot-section components of aircraft turbine engines commonly consist of a partially stabilized zirconia top-coat and an intermediate bond-coat applied on the metallic substrate. The bond-coat is made of an aluminide alloy that at high engine temperatures forms thermally grown oxides (TGO). Although formation of a thin layer of aluminum oxide at the interface between the ceramic top-coat and the bond-coat has the beneficial effect of protecting the metallic substrate from hot gases, oxide formation at splat boundaries or pores within the bond-coat is a source of weakness. In this study, plasma-sprayed TBC specimens are manufactured from two types of bond-coat powders and exposed to elevated temperatures to form oxides at the ceramic-bond-coat boundary and within the bond-coat. The specimens are then tested using nondestructive evaluation (NDE) and destructive metallography and compared with the as-manufactured samples. The objective is to determine if NDE can identify the oxidation within the bond-coat and give indication of its severity. While ultrasonic testing can provide some indication of the degree of bond-coat oxidation, the eddy current (EC) technique clearly identifies severe oxide formation within the bond-coat. Imaging of the EC signals as the function of probe location provides information on the spatial variations in the degree of oxidation, and thereby identifies which components or areas are prone to premature damage.

Catalyst development and systems analysis of methanol partial oxidation for the fuel processor - fuel cell integration

Energy Technology Data Exchange (ETDEWEB)

Newson, E; Mizsey, P; Hottinger, P; Truong, T B; Roth, F von; Schucan, Th H [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

Methanol partial oxidation (pox) to produce hydrogen for mobile fuel cell applications has proved initially more successful than hydrocarbon pox. Recent results of catalyst screening and kinetic studies with methanol show that hydrogen production rates have reached 7000 litres/hour/(litre reactor volume) for the dry pox route and 12,000 litres/hour/(litre reactor volume) for wet pox. These rates are equivalent to 21 and 35 kW{sub th}/(litre reactor volume) respectively. The reaction engineering problems remain to be solved for dry pox due to the significant exotherm of the reaction (hot spots of 100-200{sup o}C), but wet pox is essentially isothermal in operation. Analyses of the integrated fuel processor - fuel cell systems show that two routes are available to satisfy the sensitivity of the fuel cell catalysts to carbon monoxide, i.e. a preferential oxidation reactor or a membrane separator. Targets for individual system components are evaluated for the base and best case systems for both routes to reach the combined 40% efficiency required for the integrated fuel processor - fuel cell system. (author) 2 figs., 1 tab., 3 refs.

Oxidation of inorganic compounds of sulphur by various sulphur bacteria

Energy Technology Data Exchange (ETDEWEB)

Parker, C D; Prisk, J

1953-01-01

Cultures of thiobacillus thiooxidans, Th. thioparus, Th. novellus, Thiobacillus b strains t and kand Th. concretivorus, Thiobacillus x and the m strains, organisms isolated from concrete were examined to elucidate the mode of oxidation and to establish the identity of the organisms recently isolated from corroded concrete. Thiosulphate was oxidized by all these bacteria. Th. thiooxidans, Th. concretivorus and Thiobacillus x first converted it to tetrathionate and sulphate and then oxidized the tetrathionate to sulphate and free sulphuric acid. Thiobaciullus x differed from the other two in that, owing to a lesser acid tolerance, some tetrathionate was found in the final products of oxidation. Th. Thioparus converted thiosulphate to sulphate and sulphur, followed by partial oxidation of the sulphur to sulphuric acid. Th. novellus produced sulphate and sulphuric acid. Thiobacillus b, the t and k strains and the m strains formed sulphate and tetrathionate with temporary increase in pH value; only Thiobacillus x oxidized tetrationate, yielding sulphate and sulphuric acid. Elementary sulphur was oxidized by Th. thiooxidans, th. Concretivorus, thiobacillus x and Th. thioparus; the rates of oxidation decreased in that order, and the only product was sulphuric acid. Hydrogen sulphide was oxidized only at low concentrations and only by th. Concretivorus and Thiobacillus x; sulphuric acid was the end-product, and elementary sulphur may have been an intermediate. Thiobacillus x differed from Th. thiooxidans in pH range for growth and from Th. thioparus in its method of oxidation of thiosulphate, tetrathionate and H/sub 2/S. The m strains were similar to thiobacillus b and the t and k strains of trautwein.

Wet-air oxidation cleans up black wastewater

Energy Technology Data Exchange (ETDEWEB)

1993-09-01

Sterling Organics produces the analgesic paracetamol (acetaminophen) at its Dudley, England, plant. The wastewater from the batch process contains intermediates such as para-aminophenol (PAP) and byproducts such as thiosulfates, sulfites and sulfides. To stay ahead of increasingly strict environmental legislation, Sterling Organics installed a wet-air oxidation system at the Dudley facility in August 1992. The system is made by Zimpro Environmental Inc. (Rothschild, Wis.). Zimpro's wet-air oxidation system finds a way around the limitations of purely chemical or physical processes. In the process, compressed air at elevated temperature and pressure oxidizes the process intermediates and byproducts and removes the color from the wastewater.

Effect of Mass-Transport Limitations on the Performance of a Packed Bed Membrane Reactor for Partial Oxidations. Transport from the Membrane to the Packed Bed

NARCIS (Netherlands)

van Sint Annaland, M.; Kurten, U.; Kuipers, J.A.M.

2007-01-01

With a packed bed membrane reactor, the product yield can be significantly enhanced for partial oxidation systems, via distributive addition of oxygen to the reaction mixture along the axial coordinate of the reactor, provided that the reaction order in oxygen of the formation rate of the target

Effect of mass-transport limitations on the performance of a packed bed membrane reactor for partial oxidations. Transport from the membrane to the packed bed

NARCIS (Netherlands)

Sint Annaland, van M.; Kurten, U.; Kuipers, J.A.M.

2007-01-01

With a packed bed membrane reactor, the product yield can be significantly enhanced for partial oxidation systems, via distributive addition of oxygen to the reaction mixture along the axial coordinate of the reactor, provided that the reaction order in oxygen of the formation rate of the target

Oxidative Metabolites of Curcumin Poison Human Type II Topoisomerases†

Science.gov (United States)

Ketron, Adam C.; Gordon, Odaine N.; Schneider, Claus; Osheroff, Neil

2013-01-01

The polyphenol curcumin is the principal flavor and color component of the spice turmeric. Beyond its culinary uses, curcumin is believed to positively impact human health and displays antioxidant, anti-inflammatory, antibacterial, and chemopreventive properties. It also is in clinical trials as an anticancer agent. In aqueous solution at physiological pH, curcumin undergoes spontaneous autoxidation that is enhanced by oxidizing agents. The reaction proceeds through a series of quinone methide and other reactive intermediates to form a final dioxygenated bicyclopentadione product. Several naturally occurring polyphenols that can form quinones have been shown to act as topoisomerase II poisons (i.e., increase levels of topoisomerase II-mediated DNA cleavage). Because several of these compounds have chemopreventive properties, we determined the effects of curcumin, its oxidative metabolites, and structurally related degradation products (vanillin, ferulic acid, and feruloylmethane), on the DNA cleavage activities of human topoisomerase IIα and IIβ. Intermediates in the curcumin oxidation pathway increased DNA scission mediated by both enzymes ~4-5–fold. In contrast, curcumin and the bicyclopentadione, as well as vanillin, ferulic acid, and feruloylmethane, had no effect on DNA cleavage. As found for other quinone-based compounds, curcumin oxidation intermediates acted as redox-dependent (as opposed to interfacial) topoisomerase II poisons. Finally, under conditions that promote oxidation, the dietary spice turmeric enhanced topoisomerase II-mediated DNA cleavage. Thus, even within the more complex spice formulation, oxidized curcumin intermediates appear to function as topoisomerase II poisons. PMID:23253398

Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

Energy Technology Data Exchange (ETDEWEB)

Duncan, A

2001-12-31

Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

CO2 separation by calcium looping from full and partial fuel oxidation processes

International Nuclear Information System (INIS)

Sivalingam, Senthoorselvan

2013-01-01

This thesis work deals with the research and development of calcium looping process for CO 2 separation from full and partial fuel oxidation based power generation systems. CO 2 is the main greenhouse gas and undoubtedly a major contributor to the global warming. It is estimated that more than one third of the total anthropogenic CO 2 emissions come from fossil fuel based heat and power generation. Moreover, fossil fuels are unlikely to be phased out rapidly, since developing alternative energy sources not only take time but also require huge investments and infrastructure. An alternative way to reduce emissions in a medium term is to capture the CO 2 from fossil fueled power plants and store it away from the atmosphere. This process system combining a bunch of technologies is called carbon capture and storage (CCS). CO 2 capture is an important and costly part of CCS and an array of technologies is considered for this. Calcium looping (CaL) is one of such and seems to offer effective and efficient CO 2 separation from fuel oxidation processes. CaL process involves separation of CO 2 at high temperatures (600-700 C) by calcium sorbents (CaO). CO 2 reacts with CaO in a carbonation process and produces CaCO 3 . In a subsequent thermal regeneration (>850 C) called calcination, the CO 2 is released from CaCO 3 . By alternating carbonations and calcinations over multiple cycles, CO 2 is separated from a gas stream. Moreover, the CaL is realised in industrial scale with dual fluidised bed reactors for CO 2 capture (the carbonator) and sorbent regeneration (the calciner). As a process in the development, research is still required in many aspects from thermodynamic modeling to experimental studies. Research works have been carried out in process simulations, sorbent reactivity and optimisation studies in a controlled reactor environment and process parametric studies in a semi-pilot scale CaL test facility. ASPEN Plus power plant simulations integrating the CaL based CO 2

Mathematical Modelling of Intraretinal Oxygen Partial Pressure

African Journals Online (AJOL)

Erah

oxygen availability) is required for retinal oxidative metabolism. .... retina was described using Hill's equation and Fick's law. ... ganglion cell / nerve fiber layer and the superficial ..... parameter values producing the best. Figure 2: Partial ...

Phase behavior and reactive transport of partial melt in heterogeneous mantle model

Science.gov (United States)

Jordan, J.; Hesse, M. A.

2013-12-01

The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation

OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

The syngas production by partial oxidation using a homogeneous charge compression ignition engine

International Nuclear Information System (INIS)

Yang, Yoon Cheol; Lim, Mun Sup; Chun, Young Nam

2009-01-01

It is essential to develop the environment-friendly alternative energies urgently considering the limited fossil fuel and the global warming caused by environmental destruction. In this research, the new technology was studied to produce syngas from methane or simulated biogas with a HCCI reforming engine. The purpose is to provide the basics for the research on biogas treatment mainly comprising of methane and carbon dioxide, the cause of global warming. This experiment was conducted on the changes in syngas concentration according to the variations of oxygen/methane ratio, total flow rate, intake heating temperature, CO 2 in mixture and oxygen enrichment with partial oxidation. Through the parametric screening studies, optimum conditions and their results in this study was taken as follows; The maximum content of syngas was; 27.4% at 0.3 of oxygen/methane ratio, 32.38% at 117.3 L/min of total flow rate, and 35.83% at 355 C of intake heating temperature. 41.06% of syngas was produced at 50.33% of oxygen enrichment ratio. (author)

mediated oxidation of vic-dioxime to furoxan

Indian Academy of Sciences (India)

membered heterocycles and exhibit nitric oxide (NO) ... copper complexes (via chelation through nitrogen atoms of ... ammonium nitrate, this oxidation process was observed to take ... failed to produce the blue intermediate species at low ...

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

Science.gov (United States)

Moctezuma, Edgar; Leyva, Elisa; Aguilar, Claudia A; Luna, Raúl A; Montalvo, Carlos

2012-12-01

The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

KAUST Repository

Park, Jung-Hyun

2016-01-22

Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

KAUST Repository

Park, Jung-Hyun; Shin, Chae-Ho

2016-01-01

Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

High pressure oxidation of C2H4/NO mixtures

DEFF Research Database (Denmark)

Giménez-López, J.; Alzueta, M.U.; Rasmussen, C.T.

2011-01-01

An experimental and kinetic modeling study of the interaction between C2H4 and NO has been performed under flow reactor conditions in the intermediate temperature range (600–900K), high pressure (60bar), and for stoichiometries ranging from reducing to oxidizing conditions. The main reaction...... pathways of the C2H4/O2/NOx conversion, the capacity of C2H4 to remove NO, and the influence of the presence of NOx on the C2H4 oxidation are analyzed. Compared to the C2H4/O2 system, the presence of NOx shifts the onset of reaction 75–150K to lower temperatures. The mechanism of sensitization involves...... the reaction HOCH2CH2OO+NO→CH2OH+CH2O+NO2, which pushes a complex system of partial equilibria towards products. This is a confirmation of the findings of Doughty et al. [3] for a similar system at atmospheric pressure. Under reducing conditions and temperatures above 700K, a significant fraction of the NOx...

Graph-representation of oxidative folding pathways

Directory of Open Access Journals (Sweden)

Kaján László

2005-01-01

Full Text Available Abstract Background The process of oxidative folding combines the formation of native disulfide bond with conformational folding resulting in the native three-dimensional fold. Oxidative folding pathways can be described in terms of disulfide intermediate species (DIS which can also be isolated and characterized. Each DIS corresponds to a family of folding states (conformations that the given DIS can adopt in three dimensions. Results The oxidative folding space can be represented as a network of DIS states interconnected by disulfide interchange reactions that can either create/abolish or rearrange disulfide bridges. We propose a simple 3D representation wherein the states having the same number of disulfide bridges are placed on separate planes. In this representation, the shuffling transitions are within the planes, and the redox edges connect adjacent planes. In a number of experimentally studied cases (bovine pancreatic trypsin inhibitor, insulin-like growth factor and epidermal growth factor, the observed intermediates appear as part of contiguous oxidative folding pathways. Conclusions Such networks can be used to visualize folding pathways in terms of the experimentally observed intermediates. A simple visualization template written for the Tulip package http://www.tulip-software.org/ can be obtained from V.A.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

Science.gov (United States)

Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

2007-06-18

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

Energy Technology Data Exchange (ETDEWEB)

Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

2007-06-18

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P{sub O{sub 2}} were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P{sub O{sub 2}}, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD{sub RB}) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

International Nuclear Information System (INIS)

Suarez-Ojeda, Maria Eugenia; Kim, Jungkwon; Carrera, Julian; Metcalfe, Ian S.; Font, Josep

2007-01-01

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P O 2 ) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P O 2 were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P O 2 , which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD RB ) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture

Microwave assisted sintering of gadolinium doped barium cerate electrolyte for intermediate temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Kumar, Arumugam Senthil, E-mail: senthu.ramp@gmail.com [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Balaji, Ramamoorthy [Department of Physics, PSG College of Technology, Coimbatore, 641 004, Tamilnadu (India); Jayakumar, Srinivasalu [Department of Physics, PSG Institute of Technology and Applied Research, Coimbatore, 641 062, Tamilnadu (India); Pradeep, Chandran [Department of Physics, Indian Institute of Technology, Madras, 600 036, Tamilnadu (India)

2016-10-01

In Solid Oxide Fuel Cell (SOFC), electrolyte plays a vital role to increase the energy conversion efficiency. The main hurdle of such electrolyte in fuel cell is its higher operating temperature (1000 °C) which results in design limitation and higher fabrication cost. In order to reduce the operating temperature of SOFC, a suitable electrolyte has been prepared through co-precipitation method followed by microwave sintering of solid ceramic. The calcination temperature for the as-prepared powder was identified using Differential Scanning Calorimetry. The crystal structure of the sample was found to exhibit its orthorhombic perovskite structure. The particle size was determined using High-Resolution Transmission Electron Microscope with uniform in shape and size, match with XRD results and confirmed from structural analysis. Thus, the sample prepared via co-precipitation method and the solid ceramic sintered through microwave can be a promising electrolyte for fuel cells operated at intermediate temperature. - Highlights: • To synthesis the composite electrolyte by chemical method and sinter using microwave. • To reduce the operating temperature of electrolyte for high ionic conductivity in SOFC's. • To study the phase purity and to develop nanocomposite at reduced temperature.

Absolute total and partial dissociative cross sections of pyrimidine at electron and proton intermediate impact velocities

Energy Technology Data Exchange (ETDEWEB)

Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Sigaud, Lucas; Montenegro, Eduardo C. [Instituto de Física, Universidade Federal do Rio de Janeiro, PO 68528, 21941-972 Rio de Janeiro, RJ (Brazil); Tavares, Andre C. [Departamento de Física, Pontificia Universidade Católica do Rio de Janeiro, PO 38071, Rua Marquês de São Vicente 225, 22453-900 Rio de Janeiro, RJ (Brazil)

2014-02-14

Absolute total non-dissociative and partial dissociative cross sections of pyrimidine were measured for electron impact energies ranging from 70 to 400 eV and for proton impact energies from 125 up to 2500 keV. MOs ionization induced by coulomb interaction were studied by measuring both ionization and partial dissociative cross sections through time of flight mass spectrometry and by obtaining the branching ratios for fragment formation via a model calculation based on the Born approximation. The partial yields and the absolute cross sections measured as a function of the energy combined with the model calculation proved to be a useful tool to determine the vacancy population of the valence MOs from which several sets of fragment ions are produced. It was also a key point to distinguish the dissociation regimes induced by both particles. A comparison with previous experimental results is also presented.

Anomalous X-ray scattering studies of short-, intermediate- and extended-range order in glasses

International Nuclear Information System (INIS)

Price, D.L.; Saboungi, M.L.; Armand, P.; Cox, D.E.

1998-01-01

The authors present the formalism of anomalous x-ray scattering as applied to partial structure analysis of disordered materials, and give an example of how the technique has been applied, together with that of neutron diffraction, to investigate short-, intermediate- and extended-range order in vitreous germania and rubidium germanate

Chaperones, but not oxidized proteins, are ubiquitinated after oxidative stress

DEFF Research Database (Denmark)

Kästle, Marc; Reeg, Sandra; Rogowska-Wrzesinska, Adelina

2012-01-01

of these proteins by MALDI tandem mass spectrometry (MALDI MS/MS). As a result we obtained 24 different proteins which can be categorized into the following groups: chaperones, energy metabolism, cytoskeleton/intermediate filaments, and protein translation/ribosome biogenesis. The special set of identified......, ubiquitinated proteins confirm the thesis that ubiquitination upon oxidative stress is no random process to degrade the mass of oxidized proteins, but concerns a special group of functional proteins....

Iron Oxides of Mars: Evidence for Contemporary Weathering

Science.gov (United States)

Huguenin, R. L.

1985-01-01

Reflectance spectra of Mars were analyzed using a multiple high order derivative spectroscopy technique. Among the results of the analysis was the presence of suites of bands in each of the spectra that can be attributed to Fe(3e) phases. Several of the spectra contained bands that are very close to the band positions in the laboratory spectra of goethite, an hexagonal hydrated ferric oxide. Spectra of other areas showed absorption bands that were within 3% of the positions for hematite, and hexagonal close packed unhydrated Fe203. Remaining areas showed bands that are intermediate in position to the goethite and hematite bands, suggesting that there may be mixtures of goethite and hematite, and/or intermediate (partially dehydrated goethite) phases present in those areas. Both bright areas and dark areas showed suites of goethite bands and hematite bands, and there does not therefore appear to be a correlation with albedo. The areas that showed the goethite bands are, however, within zones of ongoing or historically frequent dust cloud activity, and the areas with the hematite bands were outside of the zones of frequent dust cloud activity. This suggests the possiblility that the more hydrated phase may occur within a mobile dust component.

Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

Science.gov (United States)

Assiongbon, K. A.; Roy, D.

2005-12-01

Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

Dual Expander Cycle Rocket Engine with an Intermediate, Closed-cycle Heat Exchanger

Science.gov (United States)

Greene, William D. (Inventor)

2008-01-01

A dual expander cycle (DEC) rocket engine with an intermediate closed-cycle heat exchanger is provided. A conventional DEC rocket engine has a closed-cycle heat exchanger thermally coupled thereto. The heat exchanger utilizes heat extracted from the engine's fuel circuit to drive the engine's oxidizer turbomachinery.

A density functional theory study of partial oxidation of propylene on Cu2O(0 0 1) and CuO(0 0 1) surfaces

Science.gov (United States)

Düzenli, Derya; Atmaca, Deniz Onay; Gezer, Miray Gülbiter; Onal, Isik

2015-11-01

This work theoretically investigates propylene epoxidation reaction on Cu2O(0 0 1) and CuO(0 0 1) surfaces using periodical DFT method to determine the active copper species within the reaction mechanism. The transition states and energy profiles are calculated for the formation of surface intermediates such as oxametallopropylene (OMP) over Cu2O(0 0 1) and oxygen bridging (OB) over CuO(0 0 1) and allylic H-stripping reaction (AHS) over both surfaces as well as for formation of products. Propylene oxide (PO) and acetone are obtained through OMP and OB surface intermediates and acrolein generation is observed through allylic H-stripping reaction (AHS). The calculations revealed that the corresponding surface intermediates for epoxidation reaction need to overcome an activation barrier of 13 kcal/mol over CuO surface whereas they occur without an energy barrier over Cu2O surface indicating the higher activity of Cu+ species. Acrolein is also found to be a thermodynamically more favorable product for both surfaces especially over CuO surface due to the presence of more surface oxygen atoms on which the basicity has been evaluated by the adsorption of sulfur dioxide. This indicates that the lattice oxygen inherent in both surface types does not participate in PO production.

Excellent performance of Pt-C/TiO2 for methanol oxidation: Contribution of mesopores and partially coated carbon

Science.gov (United States)

Wu, Xinbing; Zhuang, Wei; Lu, Linghong; Li, Licheng; Zhu, Jiahua; Mu, Liwen; Li, Wei; Zhu, Yudan; Lu, Xiaohua

2017-12-01

Partial deposition of carbon onto mesoporous TiO2 (C/TiO2) were prepared as supporting substrate for Pt catalyst development. Carbon deposition is achieved by in-situ carbonization of furfuryl alcohol. The hybrid catalysts were characterized by XRD, Raman, SEM and TEM and exhibited outstanding catalytic activity and stability in methanol oxidation reaction. The heterogeneous carbon coated on mesoporous TiO2 fibers provided excellent electrical conductivity and strong interfacial interaction between TiO2 support and Pt metal nanoparticles. Methanol oxidation reaction results showed that the activity of Pt-C/TiO2 is 3.0 and 1.5 times higher than that of Pt-TiO2 and Pt-C, respectively. In addition, the Pt-C/TiO2 exhibited a 6.7 times enhanced stability compared with Pt-C after 2000 cycles. The synergistic effect of C/TiO2 is responsible for the enhanced activity of Pt-C/TiO2, and its excellent durability could be ascribed to the strong interfacial interaction between Pt nanoparticles and C/TiO2 support.

Cost-effectiveness of anti-oxidant vitamins plus zinc treatment to prevent the progression of intermediate age-related macular degeneration. A Singapore perspective.

Science.gov (United States)

Saxena, Nakul; George, Pradeep Paul; Heng, Bee Hoon; Lim, Tock Han; Yong, Shao Onn

2015-06-01

To determine if providing high dose anti-oxidant vitamins and zinc treatment age-related eye disease study (AREDS formulation) to patients with intermediate age-related macular degeneration (AMD) aged 40-79 years from Singapore is cost-effective in preventing progression to wet AMD. A hypothetical cohort of category 3 and 4 AMD patients from Singapore was followed for 5 calendar years to determine the number of patients who would progress to wet AMD given the following treatment scenarios: (a) AREDS formulation or placebo followed by ranibizumab (as needed) for wet AMD. (b) AREDS formulation or placebo followed by bevacizumab (monthly) for wet AMD. (c) AREDS formulation or placebo followed by aflibercept (VIEW I and II trial treatment regimen). Costs were estimated for the above scenarios from the providers' perspective, and cost-effectiveness was measured by cost per disability-adjusted life year (DALY) averted with a disability weight of 0.22 for wet AMD. The costs were discounted at an annual rate of 3%. Over 5400 patients could be prevented from progressing to wet AMD cumulatively if AREDS formulation were prescribed. AREDS formulation followed by ranibizumab was cost-effective compared to placebo-ranibizumab or placebo-aflibercept combinations (cost per DALY averted: SGD$23,662.3 and SGD$21,138.8, respectively). However, bevacizumab (monthly injections) alone was more cost-effective compared to AREDS formulation followed by bevacizumab. Prophylactic treatment with AREDS formulation for intermediate AMD patients followed by ranibizumab or for patients who progressed to wet AMD was found to be cost-effective. These findings have implications for intermediate AMD screening, treatment and healthcare planning in Singapore.

Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

DEFF Research Database (Denmark)

Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

2015-01-01

was varied from very oxidizing to strongly reducing conditions. The results supplement high-pressure data from RCM (900–1100 K) and shock tubes (900–2200 K). At the reducing conditions ( U = 12), oxidation started at 748–775 K while it was shifted to 798–823 K for stoichiometric and oxidizing conditions ( U...

Comparison of using different bridge prosthetic designs for partial defect restoration through mathematical modeling.

Science.gov (United States)

Styranivska, Oksana; Kliuchkovska, Nataliia; Mykyyevych, Nataliya

2017-01-01

To analyze the stress-strain states of bone and abutment teeth during the use of different prosthetic designs of fixed partial dentures with the use of relevant mathematical modeling principles. The use of Comsol Multiphysics 3.5 (Comsol AB, Sweden) software during the mathematical modeling of stress-strain states provided numerical data for analytical interpretation in three different clinical scenarios with fixed dentures and different abutment teeth and demountable prosthetic denture with the saddle-shaped intermediate part. Microsoft Excel Software (Microsoft Office 2017) helped to evaluate absolute mistakes of stress and strain parameters of each abutment tooth during three modeled scenarios and normal condition and to summarize data into the forms of tables. In comparison with the fixed prosthetic denture supported by the canine, first premolar, and third molar, stresses at the same abutment teeth with the use of demountable denture with the saddle-shaped intermediate part decreased: at the mesial abutment tooth by 2.8 times, at distal crown by 6.1 times, and at the intermediate part by 11.1 times, respectively, the deformation level decreased by 3.1, 1.9, and 1.4 times at each area. The methods of mathematical modeling proved that complications during the use of fixed partial dentures based on the overload effect of the abutment teeth and caused by the deformation process inside the intermediate section of prosthetic construction.

Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

Directory of Open Access Journals (Sweden)

Samuel Hernández Anzaldo

2016-06-01

Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

Ecological advantages of partial migration as a conditional strategy.

Science.gov (United States)

Vélez-Espino, Luis A; McLaughlin, Robert L; Robillard, Melissa

2013-05-01

Partial migration is a widespread phenomenon characterized by migrant and resident forms from the same population. In phenotypically plastic taxa with indeterminate growth, resident and migrant ecophenotypes can differ in size and life history traits in ways expected to maximize fitness in the different habitats they exploit. Studies of partial migration in different taxa have advocated either density-dependence or environmental stochasticity as explanations for partial migration. We used a demographic approach for a virtual Brook Trout population to demonstrate the ecological consequences of partial migration under interacting density dependence and environmental stochasticity. The maintenance of partial migration as a conditional strategy in species/populations where resident and migrant forms exhibit life history asymmetries provides ecological advantages. We show that density-dependent migration is expected to increase population fitness under constant environmental conditions or low environmental variation, but decreases population fitness under high environmental variation. These conditions favor intermediate levels of migration as an advantageous tactic. However, there are threshold rates of return migration below which partial migration is no longer a viable tactic. Our modeling approach also allowed the exploration of the distribution of the population by life stage and habitat in response to the strength of density dependence, costs of migration, and return rates, and demonstrated the importance of the conservation of ecophenotypes in partially migratory populations. Copyright © 2013 Elsevier Inc. All rights reserved.

Selective oxidation

International Nuclear Information System (INIS)

Cortes Henao, Luis F.; Castro F, Carlos A.

2000-01-01

It is presented a revision and discussion about the characteristics and factors that relate activity and selectivity in the catalytic and not catalytic partial oxidation of methane and the effect of variables as the temperature, pressure and others in the methane conversion to methanol. It thinks about the zeolites use modified for the catalytic oxidation of natural gas

Gender variation, partial male sterility and labile sex expression in gynodioecious Plantago coronopus

NARCIS (Netherlands)

Koelewijn, HP; VanDamme, JMM

Gynodioecy is a breeding system consisting of male steriles (MS, females) and hermaphrodites (H). There is however within such sq stems a third, often neglected, class of partially male sterile plants (PMS), i.e. plants with an intermediate sex expression. In natural populations of Plantago

Gender variation, partial male sterility and labile sex expression in gynodioecious Plantago coronopus

NARCIS (Netherlands)

Koelewijn, H.P.; Van Damme, J.M.M.

1996-01-01

Gynodioecy is a breeding system consisting of male steriles (MS, females) and hermaphrodites (H). There is however within such sq stems a third, often neglected, class of partially male sterile plants (PMS), i.e. plants with an intermediate sex expression. In natural populations of Plantago

Reaction phenomena of catalytic partial oxidation of methane under the impact of carbon dioxide addition and heat recirculation

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Lin, Shih-Cheng

2015-01-01

The reaction phenomena of CPOM (catalytic partial oxidation of methane) in a Swiss-roll reactor are studied numerically where a rhodium-based catalyst bed is embedded at the center of the reactor. CO 2 is added into the feed gas and excess enthalpy recovery is performed to evaluate their influences on CPOM performance. In the study, the mole ratio of O 2 to CH 4 (O 2 /CH 4 ratio) is fixed at 0.5 and the mole ratio of CO 2 to O 2 (CO 2 /O 2 ratio) is in the range of 0–2. The results reveal that CO 2 addition into the influent has a slight effect on methane combustion, but significantly enhances dry reforming and suppresses steam reforming. The reaction extents of steam reforming and dry reforming in CPOM without heat recovery and CO 2 addition are in a comparable state. Once CO 2 is added into the feed gas, the dry reforming is enhanced, thereby dominating CH 4 consumption. Compared to the reactor without excess enthalpy recovery, heat recirculation drastically increases the maximum reaction temperature and CH 4 conversion in the catalyst bed; it also intensifies the H 2 selectivity, H 2 yield, CO 2 conversion, and syngas production rate. The predictions indicate that the heat recirculation is able to improve the syngas formation up to 45%. - Highlights: • Catalytic partial oxidation of methane with CO 2 addition and heat recovery is studied. • CO 2 addition has a slight effect on methane combustion. • CO 2 addition significantly enhances dry reforming and suppresses steam reforming. • Dry reforming dominates CH 4 consumption when CO 2 addition is large. • Heat recirculation can improve the syngas formation up to 45%

Partial Oxidation of n-Butane over a Sol-Gel Prepared Vanadium Phosphorous Oxide

Directory of Open Access Journals (Sweden)

Juan M. Salazar

2013-01-01

Full Text Available Vanadium phosphorous oxide (VPO is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO4∙0.5H2O (the precursor followed by in situ activation to produce (VO2P2O7 (the active phase. This paper discusses an alternative synthesis method based on sol-gel techniques. Vanadium (V triisopropoxide oxide was reacted with ortho-phosphoric acid in an aprotic solvent. The products were dried at high pressure in an autoclave with a controlled excess of solvent. This procedure produced a gel of VOPO4 with interlayer entrapped molecules. The surface area of the obtained materials was between 50 and 120 m2/g. Alcohol produced by the alkoxide hydrolysis reduced the vanadium during the drying step, thus VOPO4 was converted to the precursor. This procedure yielded non-agglomerated platelets, which were dehydrated and evaluated in a butane-air mixture. Catalysts were significantly more selective than the traditionally prepared materials with similar intrinsic activity. It is suggested that the small crystallite size obtained increased their selectivity towards maleic anhydride.

Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

International Nuclear Information System (INIS)

Inagaki, Toru; Nishiwaki, Futoshi; Kanou, Jirou; Yamasaki, Satoru; Hosoi, Kei; Miyazawa, Takashi; Yamada, Masaharu; Komada, Norikazu

2006-01-01

The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 o C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O 3-δ , Ni-(CeO 2 ) 1-x (SmO 1.5 ) x cermet anode, and Sm(Sr)CoO 3-δ cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 o C was obtained using high temperature off-gas from SOFC

Demonstration of high efficiency intermediate-temperature solid oxide fuel cell based on lanthanum gallate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Toru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan)]. E-mail: inagaki@rdd.kepco.co.jp; Nishiwaki, Futoshi [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Kanou, Jirou [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Yamasaki, Satoru [Kansai Electric Power Co. Inc., Energy Use R and D Center, 11-20 Nakoji 3-chome, Amagasaki, Hyogo 661-0974 (Japan); Hosoi, Kei [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Miyazawa, Takashi [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Yamada, Masaharu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan); Komada, Norikazu [Mitsubishi Materials Corporation, Central Research Institute, 1002-14 Mukohyama, Naka-machi, Naka-gun, Ibaraki 311-0102 (Japan)

2006-02-09

The Kansai Electric Power Co., Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been jointly developing intermediate-temperature solid oxide fuel cells (SOFCs). The operation temperatures between 600 and 800 {sup o}C were set as the target, which enable SOFC to use less expensive metallic separators for cell-stacking and to carry out internal reforming of hydrocarbon fuels. The electrolyte-supported planar-type cells were fabricated using highly conductive lanthanum gallate-based electrolyte, La(Sr)Ga(Mg,Co)O{sub 3-{delta}}, Ni-(CeO{sub 2}){sub 1-x}(SmO{sub 1.5}) {sub x} cermet anode, and Sm(Sr)CoO{sub 3-{delta}} cathode. The 1 kW-class power generation modules were fabricated using a seal-less stack of the cells and metallic separators. The 1 kW-class prototype power generation system with the module was developed with the high performance cell, which showed the thermally self-sustainability. The system included an SOFC module, a dc-ac inverter, a desulfurizer, and a heat recovery unit. It provided stable ac power output of 1 kW with the electrical efficiency of 45% LHV based on ac output by using city gas as a fuel, which was considered to be excellent for such a small power generation system. And the hot water of 90 {sup o}C was obtained using high temperature off-gas from SOFC.

Theoretical modelling of intermediate band solar cell materials based on metal-doped chalcopyrite compounds

International Nuclear Information System (INIS)

Palacios, P.; Sanchez, K.; Conesa, J.C.; Fernandez, J.J.; Wahnon, P.

2007-01-01

Electronic structure calculations are carried out for CuGaS 2 partially substituted with Ti, V, Cr or Mn to ascertain if some of these systems could provide an intermediate band material able to give a high efficiency photovoltaic cell. Trends in electronic level positions are analyzed and more accurate advanced theory levels (exact exchange or Hubbard-type methods) are used in some cases. The Ti-substituted system seems more likely to yield an intermediate band material with the desired properties, and furthermore seems realizable from the thermodynamic point of view, while those with Cr and Mn might give half-metal structures with applications in spintronics

Theoretical modelling of intermediate band solar cell materials based on metal-doped chalcopyrite compounds

Energy Technology Data Exchange (ETDEWEB)

Palacios, P [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain); Sanchez, K [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain); Conesa, J C [Instituto de Catalisis y Petroleoquimica, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid (Spain); Fernandez, J J [Dpt. de Fisica Fundamental, Universidad Nacional de Educacion a Distancia, 28080, Madrid (Spain); Wahnon, P [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain)

2007-05-31

Electronic structure calculations are carried out for CuGaS{sub 2} partially substituted with Ti, V, Cr or Mn to ascertain if some of these systems could provide an intermediate band material able to give a high efficiency photovoltaic cell. Trends in electronic level positions are analyzed and more accurate advanced theory levels (exact exchange or Hubbard-type methods) are used in some cases. The Ti-substituted system seems more likely to yield an intermediate band material with the desired properties, and furthermore seems realizable from the thermodynamic point of view, while those with Cr and Mn might give half-metal structures with applications in spintronics.

Heat and mass transfer analysis intermediate temperature solid oxide fuel cells (IT-SOFC)

International Nuclear Information System (INIS)

Timurkutluk, B.; Mat, M. M.; Kaplan, Y.

2007-01-01

Solid oxide fuel cells (SOFCs) have been considered as next generation energy conversion system due to their high efficiency, clean and quite operation with fuel flexibility. To date, yittria stabilized zirconia (YSZ) electrolytes have been mainly used for SOFC applications at high temperatures around 1000 degree C because of their high ionic conductivity, chemical stability and good mechanical properties. However, such a high temperature is undesirable for fuel cell operations in the viewpoint of stability. Moreover, high operation temperature necessitates high cost interconnect and seal materials. Thus, the reduction in the operation temperature of SOFCs is one of the key issues in the aspects of the cost reduction and the long term operation without degradation as well as commercialization of the SOFC systems. With the reducing temperature, not only low cost stainless steels and glass materials can be used as interconnect and sealing materials respectively but the manufacturing technology will also extend. Therefore, the design of complex geometrical SOFC component will also be possible. One way to reduce the operation temperature of SOFC is use of an alternative electrolyte material to YSZ showing acceptable properties at intermediate temperatures (600-800 degree C). As being one of IT-SOFC electrolyte materials, gadolinium doped ceria (GDC) has been taken great deals. In this study, a mathematical model for mass and heat transfer for a single cell GDC electrolyte SOFC system was developed and numerical solutions were evaluated. In order to verify the mathematical model, set of experiments were performed by taking species from four different samples randomly and five various temperature measurements. The numerical results reasonably agree with experimental data

Microbial resource management for the mitigation of nitrous oxide emissions from the Partial Nitritation- Anammox process

DEFF Research Database (Denmark)

Blum, Jan-Michael

Urban wastewater treatment plants are designed to remove pathogens and pollutants from wastewater in order to provide sanitation and to protect receiving water bodies from eutrophication. Reactive nitrogen, mainly in the form of ammonium, is one of the components in wastewater that is converted...... to dinitrogen gas during treatment. The Partial Nitritation-Anammox process (PNA) uses the capacity of autotrophic aerobic and anaerobic ammonia oxidizing bacteria (AOB and AnAOB) to perform this task. The process is mainly applied to treat ammonium-rich wastewater streams with low concentrations of organic...... with the specific ammonia removal rate, while during non-aerated phases net N2O production rates were positively correlated with the nitrite concentration (NO2-). Operation of PNA at reduced specific ammonia removal rates is, therefore, a feasible strategy to mitigate N2O emissions. However, when high ammonium...

Changes of turbidity during the phenol oxidation by photo-Fenton treatment.

Science.gov (United States)

Villota, Natalia; Camarero, Luis M; Lomas, Jose M; Perez, Jonatan

2014-11-01

Turbidity presented by phenol solutions oxidized with Fenton reagent shows the tendency of a first order intermediate kinetics. Thus, turbidity can be considered a representative parameter of the presence of intermediate oxidation species, which are generated along the decomposition of toxic and reluctant contaminants, such as phenol. Moreover, that parameter presents a linear dependence with the catalyst dosage, but is also determined by the initial contaminant load. When analyzing the oxidation mechanism of phenol, it is found that the maximum turbidity occurs when the treatment is carried out at oxidant to phenol molar ratios R = 4.0. These oxidation conditions correspond to the presence of a reaction mixture mainly composed of dihydroxylated rings, precursors of the muconic acid formation. The oxidation via "para" comprises the formation reactions of charge transfer complexes (quinhydrone), between the para-dihydroxylated intermediates (hydroquinone) and the para-substituted quinones (p-benzoquinone), which are quite unstable and reactive species, quickly decomposed into hydroxyhydroquinones. Working with oxidant ratios up to R = 6.0, the maximum observed value of turbidity in the oxidized solutions is kept almost constant. It is found that, in these conditions, the pyrogallol formation is maximal, what is generated through the degradation of ortho-species (catechol and ortho-benzoquinone) and meta-substituted (resorcinol). Operating with ratios over R = 6.0, these intermediates are decomposed into biodegradable acids, generating lower turbidity in the solution. Then, the residual turbidity is a function of the molar ratio of the ferrous ions vs. moles of oxidant utilized in the essays, that lets to estimate the stoichiometric dosage of catalyst as 20 mg/L at pH = 3.0, whereas operating in stoichiometric conditions, R = 14.0, the residual turbidity of water results almost null.

On the chemistry of ethanol on basic oxides: revising mechanisms and intermediates in the Lebedev and Guerbet reactions.

Science.gov (United States)

Chieregato, Alessandro; Velasquez Ochoa, Juliana; Bandinelli, Claudia; Fornasari, Giuseppe; Cavani, Fabrizio; Mella, Massimo

2015-01-01

A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1-butanol (Guerbet reaction) and 1,3-butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter-relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1-butanol or butadiene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antimony doped barium strontium ferrite perovskites as novel cathodes for intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Ling, Yihan, E-mail: lyhyy@mail.ustc.edu.cn [School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou, 221116 (China); Lu, Xiaoyong [China Anhui Key Laboratory of Low Temperature Co-fired Materials, Department of Chemistry, Huainan Normal University, Huainan, Anhui, 232001 (China); Niu, Jinan; Chen, Hui [School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou, 221116 (China); Ding, Yanzhi [China Anhui Key Laboratory of Low Temperature Co-fired Materials, Department of Chemistry, Huainan Normal University, Huainan, Anhui, 232001 (China); Ou, Xuemei [School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou, 221116 (China); Zhao, Ling [Department of Material Science and Chemistry, China University of Geosciences, Wuhan, 430074 (China)

2016-05-05

Antimony was doped to barium strontium ferrite to produce ferrite-based perovskites with a composition of Ba{sub 0.5}Sr{sub 0.5}Fe{sub 1−x}Sb{sub x}O{sub 3−δ} (x = 0.0, 0.05, 0.1) as novel cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The perovskite properties including oxygen nonstoichiometry (δ), mean valence of B-site, tolerance factors, thermal expansion coefficient (TEC) and electrical conductivity (σ) are explored as a function of antimony content. By defect chemistry analysis, the TECs decrease since the variable oxygen vacancy concentration is decreased by Sb doping, and σ decreases with x due to the reduced charge concentration of Fe{sup 4+} content. Consequently, the electrochemical performance was substantially improved and the interfacial polarization resistance was reduced from 0.213 to 0.120 Ωcm{sup 2} at 700 °C with Sb doping. The perovskite with x = 1.0 is suggested as the most promising composition as SOFC cathode material. - Highlights: • Antimony is doped to barium strontium ferrite to produce novel cathodes. • δ, TECs and σ are evaluated as a function of antimony content. • The electrochemical performance is substantially improved with antimony doping.

Inactivation of thiol-dependent enzymes by hypothiocyanous acid: role of sulfenyl thiocyanate and sulfenic acid intermediates

Science.gov (United States)

Barrett, Tessa J.; Pattison, David I.; Leonard, Stephen E.; Carroll, Kate S.; Davies, Michael J.; Hawkins, Clare L.

2012-01-01

Myeloperoxidase (MPO) forms reactive oxidants including hypochlorous and hypothiocyanous acids (HOCl and HOSCN) under inflammatory conditions. HOCl causes extensive tissue damage and plays a role in the progression of many inflammatory-based diseases. Although HOSCN is a major MPO oxidant, particularly in smokers, who have elevated plasma thiocyanate, the role of this oxidant in disease is poorly characterized. HOSCN induces cellular damage by targeting thiols. However, the specific targets and mechanisms involved in this process are not well defined. We show that exposure of macrophages to HOSCN results in the inactivation of intracellular enzymes, including creatine kinase (CK) and glyceraldehyde-3-phosphate dehydrogenase (GAPDH). In each case, the active-site thiol residue is particularly sensitive to oxidation, with evidence for reversible inactivation and the formation of sulfenyl thiocyanate and sulfenic acid intermediates, on treatment with HOSCN (less than fivefold molar excess). Experiments with DAz-2, a cell-permeable chemical trap for sulfenic acids, demonstrate that these intermediates are formed on many cellular proteins, including GAPDH and CK, in macrophages exposed to HOSCN. This is the first direct evidence for the formation of protein sulfenic acids in HOSCN-treated cells and highlights the potential of this oxidant to perturb redox signaling processes. PMID:22248862

Opening of small and intermediate calcium-activated potassium channels induces relaxation mainly mediated by nitric-oxide release in large arteries and endothelium-derived hyperpolarizing factor in small arteries from rat

DEFF Research Database (Denmark)

Stankevicius, Edgaras; Dalsgaard, Thomas; Kroigaard, Christel

2011-01-01

This study was designed to investigate whether calcium-activated potassium channels of small (SK(Ca) or K(Ca)2) and intermediate (IK(Ca) or K(Ca)3.1) conductance activated by 6,7-dichloro-1H-indole-2,3-dione 3-oxime (NS309) are involved in both nitric oxide (NO) and endothelium-derived hyperpolar......This study was designed to investigate whether calcium-activated potassium channels of small (SK(Ca) or K(Ca)2) and intermediate (IK(Ca) or K(Ca)3.1) conductance activated by 6,7-dichloro-1H-indole-2,3-dione 3-oxime (NS309) are involved in both nitric oxide (NO) and endothelium...... in human umbilical vein endothelial cells (HUVECs), and calcium concentrations were investigated in both HUVECs and mesenteric arterial endothelial cells. In both superior (∼1093 μm) and small mesenteric (∼300 μm) arteries, NS309 evoked endothelium- and concentration-dependent relaxations. In superior....... In small mesenteric arteries, NS309 relaxations were reduced slightly by ADMA, whereas apamin plus an IK(Ca) channel blocker almost abolished relaxation. Iberiotoxin did not change NS309 relaxation. HUVECs expressed mRNA for SK(Ca) and IK(Ca) channels, and NS309 induced increases in calcium, outward...

Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation.

Science.gov (United States)

Planes, G A; Rodríguez, J L; Miras, M C; García, G; Pastor, E; Barbero, C A

2010-09-21

Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO(2) are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO(2) during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO(2) by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed.

Green chemistry perspectives of methane conversion via oxidative methylation of aromatics over zeolite catalysts

Energy Technology Data Exchange (ETDEWEB)

Adebajo, M.O. [University of Queensland, St Lucia, Qld. (Australia)

2007-06-15

This paper provides a general overview of the recent work that we and other researchers have done on the utilisation of methane for catalytic methylation of aromatic compounds and for direct coal liquefaction for the production of liquid hydrocarbons. In particular, the paper presents a detailed description of more recent substantial experimental evidence that we have provided for the requirement of oxygen as a stoichiometry reactant for benzene methylation with methane over moderately acidic zeolite catalysts. The reaction, which has been termed 'oxidative methylation', was thus postulated to involve a two-step mechanism involving intermediate methanol formation by methane partial oxidation, followed by benzene methylation with methanol in the second step. However, strongly acidic zeolites can cause cracking of benzene to yield methylated products in the absence of oxygen. The participation of methane and oxygen, and the effective use of zeolite catalysts in this methylation reaction definitely have some positive green chemistry implications. Thus, the results of these previous studies are also discussed in this review in light of the principles and tools of green chemistry. Various metrics were used to evaluate the greenness, cost-effectiveness, and material and energy efficiency of the oxidative methylation reaction.

Intermediate treatments

Science.gov (United States)

John R. Jones; Wayne D. Shepperd

1985-01-01

Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

Combined crystallographic and spectroscopic analysis of Trematomus bernacchii hemoglobin highlights analogies and differences in the peculiar oxidation pathway of Antarctic fish hemoglobins.

Science.gov (United States)

Merlino, Antonello; Vitagliano, Luigi; Howes, Barry D; Verde, Cinzia; di Prisco, Guido; Smulevich, Giulietta; Sica, Filomena; Vergara, Alessandro

2009-12-01

Recent studies have demonstrated that hemoglobins isolated from Antarctic fish undergo peculiar oxidation processes. Here we show, by combining crystallographic and spectroscopic data, that the oxidation pathway of Trematomus bernacchii hemoglobin (HbTb) is distinct from that observed for the major component of Trematomus newnesi (Hb1Tn), despite the high sequence identity of the two proteins and structural similarity of their ferrous and fully oxidized states. Resonance Raman analysis of HbTb autoxidation upon air-exposure reveals the absence of the oxidized pentacoordinated state that was observed for Hb1Tn. The HbTb oxidation pathway is characterized by two ferric species: an aquo hexacoordinated high spin state and a bis-histidyl hexacoordinated low spin form, which appear in the early stages of the oxidation process. The high resolution structure of an intermediate along the oxidation pathway has been determined at 1.4 A resolution. The analysis of the electron density of the heme pocket shows, for both the alpha and the beta iron, the coexistence of multiple binding states. In this partially oxidized form, HbTb exhibits significant deviations from the canonical R state both at the local and global level. The analysis of these modifications highlights the structural correlation between key functional regions of the protein.

Synthesis of ZSM-5 zeolite from coal fly ash and rice husk: characterization and application for partial oxidation of methane to methanol

Science.gov (United States)

Krisnandi, Y. K.; Yanti, F. M.; Murti, S. D. S.

2017-04-01

Indonesian fly ash (SiO2/Al2O3 mole ratio = 3.59) was used together with rice husk (SiO2 92%) as raw material for mesoporous ZSM-5 zeolite synthesis. Prior being used, coal fly ash and rice husk were subjected to pre-treatment in order to extract silicate (SiO4 4-) and aluminate (AlO4 5-) and to remove the impurities. Then the ZSM-5 zeolite were synthesized through hydrothermal treatment using two types of templates (TPAOH and PDDA). The as-synthesized ZSM-5 was characterized using FTIR, XRD, SEM-EDX, and BET. The result of FTIR showed peaks at 1250-950 cm-1 (v asymetric T-O), 820-650 cm-1 (v symetric T-O), and at 650-500 cm-1 confirming the presence of the five number ring of the pentasil structure. The result of XRD showed the appearance of certain peaks in the position 2 theta between 7-9° and 22-25° indicative of ZSM-5 structure, but also showed the pattern of low intensity magnetite and hematite. The SEM image showed the rough surface of hexagonal crystals from ZSM-5 structure, indicative of mesoporosity in the structure. EDX result showed Si/Al ratio of 20, while surface area analysis gave SA of 43.16. The ZSM-5 zeolites then was modified with cobalt oxide through impregnation method. The catalytic activity as heterogeneous catalysts in partial oxidation of methane was tested. The result showed that hence the catalytic activity of ZSM-5 and Co/ZSM-5 from fly ash and rice husk were still inferior compared to the pro-analysis sourced-counterpart, they were potential to be used as catalyst in the partial oxidation of methane to methanol.

Molecular cytogenetic characterization and stem rust resistance of five wheat-thinopyrum ponticum partial amphiploids

Science.gov (United States)

Partial amphiploids created by crossing common wheat (Triticum aestivum L.) and Thinopyrum ponticum (Podp.), Barkworth & D. R. Dewey may be resistant to major wheat diseases and are an important intermediate material in wheat breeding. In this study, we examined chromosome composition of five Xiaoy...

Exploring the negative temperature coefficient behavior of acetaldehyde based on detailed intermediate measurements in a jet-stirred reactor

KAUST Repository

Tao, Tao; Sun, Wenyu; Hansen, Nils; Jasper, Ahren W.; Moshammer, Kai; Chen, Bingjie; Wang, Zhandong; Huang, Can; Dagaut, Philippe; Yang, Bin

2018-01-01

Acetaldehyde is an observed emission species and a key intermediate produced during the combustion and low-temperature oxidation of fossil and bio-derived fuels. Investigations into the low-temperature oxidation chemistry of acetaldehyde are essential to develop a better core mechanism and to better understand auto-ignition and cool flame phenomena. Here, the oxidation of acetaldehyde was studied at low-temperatures (528–946 K) in a jet-stirred reactor (JSR) with the corrected residence time of 2.7 s at 700 Torr. This work describes a detailed set of experimental results that capture the negative temperature coefficient (NTC) behavior in the low-temperature oxidation of acetaldehyde. The mole fractions of 28 species were measured as functions of the temperature by employing a vacuum ultra-violet photoionization molecular-beam mass spectrometer. To explain the observed NTC behavior, an updated mechanism was proposed, which well reproduces the concentration profiles of many observed peroxide intermediates. The kinetic analysis based on the updated mechanism reveals that the NTC behavior of acetaldehyde oxidation is caused by the competition between the O-addition to and the decomposition of the CHCO radical.

Exploring the negative temperature coefficient behavior of acetaldehyde based on detailed intermediate measurements in a jet-stirred reactor

KAUST Repository

Tao, Tao

2018-03-20

Acetaldehyde is an observed emission species and a key intermediate produced during the combustion and low-temperature oxidation of fossil and bio-derived fuels. Investigations into the low-temperature oxidation chemistry of acetaldehyde are essential to develop a better core mechanism and to better understand auto-ignition and cool flame phenomena. Here, the oxidation of acetaldehyde was studied at low-temperatures (528–946 K) in a jet-stirred reactor (JSR) with the corrected residence time of 2.7 s at 700 Torr. This work describes a detailed set of experimental results that capture the negative temperature coefficient (NTC) behavior in the low-temperature oxidation of acetaldehyde. The mole fractions of 28 species were measured as functions of the temperature by employing a vacuum ultra-violet photoionization molecular-beam mass spectrometer. To explain the observed NTC behavior, an updated mechanism was proposed, which well reproduces the concentration profiles of many observed peroxide intermediates. The kinetic analysis based on the updated mechanism reveals that the NTC behavior of acetaldehyde oxidation is caused by the competition between the O-addition to and the decomposition of the CHCO radical.

Do Partial Home Smoking Bans Signal Progress toward a Smoke-Free Home?

Science.gov (United States)

Kegler, Michelle C.; Haardörfer, Regine; Bundy, Lucja T.; Escoffery, Cam; Berg, Carla J.; Fernandez, Maria; Williams, Rebecca; Hovell, Mel

2016-01-01

Understanding who establishes partial home smoking bans, what these bans cover, and whether they are an intermediate step in going smoke-free would help to inform smoke-free home interventions. Participants were recruited from United Way of Greater Atlanta's 2-1-1 contact center. Data were collected at baseline, 3 and 6 months via telephone…

Water oxidation by photosystem II: H(2)O-D(2)O exchange and the influence of pH support formation of an intermediate by removal of a proton before dioxygen creation.

Science.gov (United States)

Gerencsér, László; Dau, Holger

2010-11-30

Understanding the chemistry of photosynthetic water oxidation requires deeper insight into the interrelation between electron transfer (ET) and proton relocations. In photosystem II membrane particles, the redox transitions of the water-oxidizing Mn complex were initiated by nanosecond laser flashes and monitored by absorption spectroscopy at 360 nm (A(360)). In the oxygen evolution transition (S(3) + hν → S(0) + O(2)), an exponential decrease in A(360) (τ(O(2)) = 1.6 ms) can be assigned to Mn reduction and O(2) formation. The corresponding rate-determining step is the ET from the Mn complex to a tyrosine radical (Y(Z)(ox)). We find that this A(360) decrease is preceded by a lag phase with a duration of 170 ± 40 μs (τ(lag) at pH 6.2), indicating formation of an intermediate before ET and O-O bond formation and corroborating results obtained by time-resolved X-ray spectroscopy. Whereas τ(O(2)) exhibits a minor kinetic isotope effect and negligible pH dependence, formation of the intermediate is slowed significantly both in D(2)O (τ(lag) increase of ∼140% in D(2)O) and at low pH (τ(lag) of 30 ± 20 μs at pH 7.0 vs τ(lag) of 470 ± 80 μs at pH 5.5). These findings support the fact that in the oxygen evolution transition an intermediate is created by deprotonation and removal of a proton from the Mn complex, after Y(Z)(ox) formation but before the onset of electron transfer and O-O bond formation.

The Enzymatic Oxidation of Graphene Oxide

Science.gov (United States)

Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

2011-01-01

Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

Experimental and modeling study of the oxidation of n- and iso-butanal

KAUST Repository

Veloo, Peter S.; Dagaut, P.; Togbé , Casimir; Dayma, Guillaume; Sarathy, Mani; Westbrook, Charles K.; Egolfopoulos, Fokion N.

2013-01-01

Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

Experimental and modeling study of the oxidation of n- and iso-butanal

KAUST Repository

Veloo, Peter S.

2013-09-01

Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

Unfolding Simulations of Holomyoglobin from Four Mammals: Identification of Intermediates and β-Sheet Formation from Partially Unfolded States

DEFF Research Database (Denmark)

Dasmeh, Pouria; Kepp, Kasper Planeta

2013-01-01

simulations of holoMb and the first comparative study of unfolding of protein orthologs from different species (sperm whale, pig, horse, and harbor seal). We also provide new interpretations of experimental mean molecular ellipticities of myoglobin intermediates, notably correcting for random coil and number...... of helices in intermediates. The simulated holoproteins at 310 K displayed structures and dynamics in agreement with crystal structures (Rg ,1.48–1.51 nm, helicity ,75%). At 400 K, heme was not lost, but some helix loss was observed in pig and horse, suggesting that these helices are less stable......Myoglobin (Mb) is a centrally important, widely studied mammalian protein. While much work has investigated multi-step unfolding of apoMb using acid or denaturant, holomyoglobin unfolding is poorly understood despite its biological relevance. We present here the first systematic unfolding...

Bio-oil steam reforming, partial oxidation or oxidative steam reforming coupled with bio-oil dry reforming to eliminate CO{sub 2} emission

Energy Technology Data Exchange (ETDEWEB)

Hu, Xun [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Lu, Gongxuan [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

2010-07-15

Biomass is carbon-neutral and utilization of biomass as hydrogen resource shows no impact on atmospheric CO{sub 2} level. Nevertheless, a significant amount of CO{sub 2} is always produced in biomass gasification processes. If the CO{sub 2} produced can further react with biomass, then the biomass gasification coupled with CO{sub 2} reforming of biomass will result in a net decrease of CO{sub 2} level in atmosphere and produce the chemical raw material, syngas. To achieve this concept, a ''Y'' type reactor is developed and applied in bio-oil steam reforming, partial oxidation, or oxidative steam reforming coupled with CO{sub 2} reforming of bio-oil to eliminate the emission of CO{sub 2}. The experimental results show that the reaction systems can efficiently suppress the emission of CO{sub 2} from various reforming processes. The different coupled reaction systems generate the syngas with different molar ratio of CO/H{sub 2}. In addition, coke deposition is encountered in the different reforming processes. Both catalysts and experimental parameters significantly affect the coke deposition. Ni/La{sub 2}O{sub 3} catalyst shows much higher resistivity toward coke deposition than Ni/Al{sub 2}O{sub 3} catalyst, while employing high reaction temperature is vital for elimination of coke deposition. Although the different coupled reaction systems show different characteristic in terms of product distribution and coke deposition, which all can serve as methods for storage of the carbon from fossil fuels or air. (author)

Estimation of Oxidation Kinetics and Oxide Scale Void Position of Ferritic-Martensitic Steels in Supercritical Water

Directory of Open Access Journals (Sweden)

Li Sun

2017-01-01

Full Text Available Exfoliation of oxide scales from high-temperature heating surfaces of power boilers threatened the safety of supercritical power generating units. According to available space model, the oxidation kinetics of two ferritic-martensitic steels are developed to predict in supercritical water at 400°C, 500°C, and 600°C. The iron diffusion coefficients in magnetite and Fe-Cr spinel are extrapolated from studies of Backhaus and Töpfer. According to Fe-Cr-O ternary phase diagram, oxygen partial pressure at the steel/Fe-Cr spinel oxide interface is determined. The oxygen partial pressure at the magnetite/supercritical water interface meets the equivalent oxygen partial pressure when system equilibrium has been attained. The relative error between calculated values and experimental values is analyzed and the reasons of error are suggested. The research results show that the results of simulation at 600°C are approximately close to experimental results. The iron diffusion coefficient is discontinuous in the duplex scale of two ferritic-martensitic steels. The simulation results of thicknesses of the oxide scale on tubes (T91 of final superheater of a 600 MW supercritical boiler are compared with field measurement data and calculation results by Adrian’s method. The calculated void positions of oxide scales are in good agreement with a cross-sectional SEM image of the oxide layers.

Kinetic analysis of human CYP24A1 metabolism of vitamin D via the C24-oxidation pathway.

Science.gov (United States)

Tieu, Elaine W; Tang, Edith K Y; Tuckey, Robert C

2014-07-01

CYP24A1 is the multicatalytic cytochrome P450 responsible for the catabolism of vitamin D via the C23- and C24-oxidation pathways. We successfully expressed the labile human enzyme in Escherichia coli and partially purified it in an active state that permitted detailed characterization of its metabolism of 1,25-dihydroxyvitamin D3 [1,25(OH)2 D3] and the intermediates of the C24-oxidation pathway in a phospholipid-vesicle reconstituted system. The C24-oxidation pathway intermediates, 1,24,25-trihydroxyvitamin D3, 24-oxo-1,25-dihydroxyvitamin D3, 24-oxo-1,23,25-trihydroxyvitamin D3 and tetranor-1,23-dihydroxyvitamin D3, were enzymatically produced from 1,25(OH)2 D3 using rat CYP24A1. Both 1,25(OH)2 D3 and 1,23-dihydroxy-24,25,26,27-tetranorvitamin D3 were found to partition strongly into the phospholipid bilayer when in aqueous medium. Changes to the phospholipid concentration did not affect the kinetic parameters for the metabolism of 1,25(OH)2 D3 by CYP24A1, indicating that it is the concentration of substrates in the membrane phase (mol substrate·mol phospholipid(-1) ) that determines their rate of metabolism. CYP24A1 exhibited Km values for the different C24-intermediates ranging from 0.34 to 15 mmol·mol phospholipid(-1) , with 24-oxo-1,23,25-trihydroxyvitamin D3 [24-oxo-1,23,25(OH)3 D3] displaying the lowest and 1,24,25-trihydroxyvitamin D3 [1,24,25(OH)3 D3] displaying the highest. The kcat values varied by up to 3.8-fold, with 1,24,25(OH)3 D3 displaying the highest kcat (34 min(-1) ) and 24-oxo-1,23,25(OH)3 D3 the lowest. The data show that the cleavage of the side chain of 24-oxo-1,23,25(OH)3 D3 occurs with the highest catalytic efficiency (kcat /Km ) and produces 1-hydroxy-23-oxo-24,25,26,27-tetranorvitamin D3 and not 1,23-dihydroxy-24,25,26,27-tetranorvitamin D3, as the primary product. These kinetic analyses also show that intermediates of the C24-oxidation pathway effectively compete with precursor substrates for binding to the active site of the

Partially reduced graphene oxide based FRET on fiber-optic interferometer for biochemical detection.

Science.gov (United States)

Yao, B C; Wu, Y; Yu, C B; He, J R; Rao, Y J; Gong, Y; Fu, F; Chen, Y F; Li, Y R

2016-03-24

Fluorescent resonance energy transfer (FRET) with naturally exceptional selectivity is a powerful technique and widely used in chemical and biomedical analysis. However, it is still challenging for conventional FRET to perform as a high sensitivity compact sensor. Here we propose a novel 'FRET on Fiber' concept, in which a partially reduced graphene oxide (prGO) film is deposited on a fiber-optic modal interferometer, acting as both the fluorescent quencher for the FRET and the sensitive cladding for optical phase measurement due to refractive index changes in biochemical detection. The target analytes induced fluorescence recovery with good selectivity and optical phase shift with high sensitivity are measured simultaneously. The functionalized prGO film coated on the fiber-optic interferometer shows high sensitivities for the detections of metal ion, dopamine and single-stranded DNA (ssDNA), with detection limits of 1.2 nM, 1.3 μM and 1 pM, respectively. Such a prGO based 'FRET on fiber' configuration, bridging the FRET and the fiber-optic sensing technology, may serve as a platform for the realization of series of integrated 'FRET on Fiber' sensors for on-line environmental, chemical, and biomedical detection, with excellent compactness, high sensitivity, good selectivity and fast response.

The uptake and excretion of partially oxidized sulfur expands the repertoire of energy resources metabolized by hydrothermal vent symbioses.

Science.gov (United States)

Beinart, R A; Gartman, A; Sanders, J G; Luther, G W; Girguis, P R

2015-05-07

Symbiotic associations between animals and chemoautotrophic bacteria crowd around hydrothermal vents. In these associations, symbiotic bacteria use chemical reductants from venting fluid for the energy to support autotrophy, providing primary nutrition for the host. At vents along the Eastern Lau Spreading Center, the partially oxidized sulfur compounds (POSCs) thiosulfate and polysulfide have been detected in and around animal communities but away from venting fluid. The use of POSCs for autotrophy, as an alternative to the chemical substrates in venting fluid, could mitigate competition in these communities. To determine whether ESLC symbioses could use thiosulfate to support carbon fixation or produce POSCs during sulfide oxidation, we used high-pressure, flow-through incubations to assess the productivity of three symbiotic mollusc genera-the snails Alviniconcha spp. and Ifremeria nautilei, and the mussel Bathymodiolus brevior-when oxidizing sulfide and thiosulfate. Via the incorporation of isotopically labelled inorganic carbon, we found that the symbionts of all three genera supported autotrophy while oxidizing both sulfide and thiosulfate, though at different rates. Additionally, by concurrently measuring their effect on sulfur compounds in the aquaria with voltammetric microelectrodes, we showed that these symbioses excreted POSCs under highly sulfidic conditions, illustrating that these symbioses could represent a source for POSCs in their habitat. Furthermore, we revealed spatial disparity in the rates of carbon fixation among the animals in our incubations, which might have implications for the variability of productivity in situ. Together, these results re-shape our thinking about sulfur cycling and productivity by vent symbioses, demonstrating that thiosulfate may be an ecologically important energy source for vent symbioses and that they also likely impact the local geochemical regime through the excretion of POSCs.

The influence of deformation, annealing and recrystallisation on oxide nanofeatures in oxide dispersion strengthened steel

Energy Technology Data Exchange (ETDEWEB)

Dawson, Karl, E-mail: k.dawson@liverpool.ac.uk; Tatlock, Gordon J.

2017-04-01

This work demonstrates that Y-Ti oxide nanofeatures, observed in as-extruded oxide dispersion strengthened steel, are structurally modified by cold forging. A 950 °C heat treatment promoted restructuring of the deformed particles and partial recrystallisation of the cold forged alloy. Transmission electron microscopy revealed that cuboid shaped nanofeatures were deformed during forging, which resulted in high number densities of lens shaped yttrium-titanium oxide particles. Annealing the forged alloy promoted partial recrystallisation of the ferritic matrix. Particle morphology reverted from lens shaped, as witnessed in the deformed material, to cuboid shaped oxide nanofeatures, identical to those observed in as-extruded material. Precipitation distributions evaluated in both recrystallised and recovering grains were indistinguishable from those first measured in the as-extruded alloy. TEM images revealed a widespread orientation relationship between the oxide precipitates and the recrystallised grains; registration with the ferrite lattice was omnipresent in both recovering and recrystallised grains.

Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

Science.gov (United States)

Nouri-Nigjeh, Eslam; Bruins, Andries P; Bischoff, Rainer; Permentier, Hjalmar P

2012-10-21

Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

Science.gov (United States)

Gong, Wenquan

2005-07-01

The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization

Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

International Nuclear Information System (INIS)

Andrushkevich, T.V.

1997-01-01

Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

Incorporating Graphene Oxide into Alginate Polymer with a Cationic Intermediate To Strengthen Membrane Dehydration Performance.

Science.gov (United States)

Guan, Kecheng; Liang, Feng; Zhu, Haipeng; Zhao, Jing; Jin, Wanqin

2018-04-25

Two-dimensional graphene oxide (GO) in hybrid membranes provides fast water transfer across its surface due to the abundant oxygenated functional groups to afford water sorption and the hydrophobic basal plane to create fast transporting pathways. To establish more compatible and efficient interactions for GO and sodium alginate (SA) polymer chains, cations sourced from lignin are employed to decorate GO (labeled as cation-functionalized GO (CG)) nanosheets via cation-π and π-π interactions, providing more interactive sites to confer synergetic benefits with polymer matrix. Cations from CG are also functional to partially interlock SA chains and intensify water diffusion. And with the aid of two-dimensional pathways of CG, fast selective water permeation can be realized through hybrid membranes with CG fillers. In dehydrating aqueous ethanol solution, the hybrid membrane exhibits considerable performance compared with bare SA polymer membrane (long-term stable permeation flux larger than 2500 g m -2 h -1 and water content larger than 99.7 wt %, with feed water content of 10 wt % under 70 °C). The effects of CG content in SA membrane were investigated, and the transport mechanism was correspondingly studied through varying operation conditions and membrane materials. In addition, such a membrane possesses long-term stability and almost unchanged high dehydration capability.

A novel high performance composite anode with in situ growth of Fe-Ni alloy nanoparticles for intermediate solid oxide fuel cells

International Nuclear Information System (INIS)

Li, Jingcheng; Yu, Yan; Yin, Yi-Mei; Zhou, Ning; Ma, Zi-Feng

2017-01-01

Highlights: • A composite anode with endogenous Fe-Ni alloy nanoparticles has been prepared. • The redox reversibility of the anode has been confirmed by XRD. • The E_a of H_2 oxidation at the anode is much smaller than that at Ni-YSZ anode. • A ScSZ supported cell achieves MPD of 0.71 Wcm"−"2 and R_p of 0.16 Ω cm"2 at 800 °C. • The single cell shows stable output during 105 h testing at 800 °C 0.7 V in wet H_2". - Abstract: A redox reversible composite anode with Fe-Ni alloy nanoparticles in situ growth on SrLaFeO_4-type and LaFeO_3-type oxide substrates has been prepared for intermediate temperature solid oxide fuel cell (IT-SOFC) by reducing perovskite precursor La_0_._4Sr_0_._6Fe_0_._7_5Ni_0_._1Nb_0_._1_5O_3_-_δ (LSFNNb) in wet H_2 at 900 °C for 1 h. The anode has shown an excellent electrochemical catalytic activity for oxidation of hydrogen with much smaller E_a (25.1 ∼ 68.9 kJ mol"−"1) than the value (>160 kJ mol"−"1) at Ni-YSZ anode. A scandium stabilized zirconia (ScSZ) electrolyte supported SOFC with the anode achieves maximum power densities of 0.71, 0.52, 0.35, and 0.21 W cm"−"2 at 800, 750, 700 and 650 °C, respectively in wet H_2 (3% H_2O), and the corresponding R_p of 0.16, 0.21, 0.35, and 0.60 Ω cm"2 under OCV. Moreover, the single cell shows stable power output during ∼105 h operation at 800 °C under 0.7 V in wet H_2 after a initial degradation, indicating that R-LSFNNb is an excellent candidate as anode of IT-SOFC.

Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

Energy Technology Data Exchange (ETDEWEB)

Deshmukh, Ruchi; Mehra, Anurag; Thaokar, Rochish, E-mail: rochish@che.iitb.ac.in [Indian Institute of Technology-Bombay, Department of Chemical Engineering (India)

2017-01-15

Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra-methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe {sub 3}O{sub 4}) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe {sub 3}O{sub 4}) or a mixture of (γ-Fe {sub 2}O{sub 3} + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 {sup ∘}C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.

CO{sub 2} separation by calcium looping from full and partial fuel oxidation processes

Energy Technology Data Exchange (ETDEWEB)

Sivalingam, Senthoorselvan

2013-06-05

This thesis work deals with the research and development of calcium looping process for CO{sub 2} separation from full and partial fuel oxidation based power generation systems. CO{sub 2} is the main greenhouse gas and undoubtedly a major contributor to the global warming. It is estimated that more than one third of the total anthropogenic CO{sub 2} emissions come from fossil fuel based heat and power generation. Moreover, fossil fuels are unlikely to be phased out rapidly, since developing alternative energy sources not only take time but also require huge investments and infrastructure. An alternative way to reduce emissions in a medium term is to capture the CO{sub 2} from fossil fueled power plants and store it away from the atmosphere. This process system combining a bunch of technologies is called carbon capture and storage (CCS). CO{sub 2} capture is an important and costly part of CCS and an array of technologies is considered for this. Calcium looping (CaL) is one of such and seems to offer effective and efficient CO{sub 2} separation from fuel oxidation processes. CaL process involves separation of CO{sub 2} at high temperatures (600-700 C) by calcium sorbents (CaO). CO{sub 2} reacts with CaO in a carbonation process and produces CaCO{sub 3}. In a subsequent thermal regeneration (>850 C) called calcination, the CO{sub 2} is released from CaCO{sub 3}. By alternating carbonations and calcinations over multiple cycles, CO{sub 2} is separated from a gas stream. Moreover, the CaL is realised in industrial scale with dual fluidised bed reactors for CO{sub 2} capture (the carbonator) and sorbent regeneration (the calciner). As a process in the development, research is still required in many aspects from thermodynamic modeling to experimental studies. Research works have been carried out in process simulations, sorbent reactivity and optimisation studies in a controlled reactor environment and process parametric studies in a semi-pilot scale CaL test facility

Utilization of polymer enclosed intermediate class arresters to improve the performance of modern power systems

International Nuclear Information System (INIS)

Sakich, J.D.; Lenk, D.W.; Koepfinger, J.L.

1992-01-01

This paper introduces the first commercially available polymer enclosed intermediate class metal oxide surge arrester. It describes the unique construction of the design, including reduced size, increased flexibility, a collared seal on the polymer housing and an open webbed fiberglass-epoxy module which houses the metal oxide disc elements. Performance advantages are discussed. These include improved short term contamination performance of the insulator-like polymer design when compared to multi-unit porcelain housed designs. Data will show that polymer housed open-webbed fiberglass module construction extends the pressure relief capability beyond that of typical porcelain enclosed designs. The capability of the polymer enclosed design to withstand repeated pressure relief tests, simulating system reclose on a failed arrester, is also discussed. This paper discusses the circumstances at one utility which has considered utilizing polymer enclosed intermediate class arresters to effectively upgrade their system protection capabilities

The production of hydrogen through the uncatalyzed partial oxidation of methane in an internal combustion engine

Energy Technology Data Exchange (ETDEWEB)

Karim, Ghazi A.; Wierzba, I. [Department of Mechanical and Manufacturing Engineering, Schulich School of Engineering, University of Calgary, Calgary (Canada)

2008-04-15

The thermodynamic and kinetic limitations of the uncatalyzed partial oxidation of methane for the production of synthesis gas, which is made up of mostly hydrogen and carbon monoxide in a variety of proportions, are reviewed. It is suggested that such processes can be made to proceed successfully in a conventional internal combustion engine when operated on excessively rich mixtures of methane and oxygenated air. This is achieved while simultaneously producing power and regenerative exhaust gas heating. Experimental results are described that show a dual fuel engine of the compression ignition type with pilot liquid fuel injection can be operated on excessively rich mixtures of methane and air supplemented with oxygen gas to produce hydrogen rich gas with high methane conversion rates. Similarly, a spark ignition engine was reported to be equally capable of such production and performance. It is shown that there are viable prospects for the simultaneous production of synthesis gas in engines with efficient useful mechanical power and exhaust gas regenerative heating. (author)

Increased penile expression of transforming growth factor and elevated systemic oxidative stress in rabbits with chronic partial bladder outlet obstruction.

Science.gov (United States)

Lin, W-Y; Chang, P-J; Lin, Y-P; Wu, S-B; Chen, C-S; Levin, R M; Wei, Y-H

2012-02-01

There is a growing body of evidence to support the direct link between obstructive bladder dysfunction and erectile dysfunction (ED). However, there have been few pathophysiological studies to determine the relationship between lower urinary tract syndrome (LUTS) and ED. As the transforming growth factor-β1 (TGF-β1) that induces the synthesis of collagen in the penile tissues is critical for the development of ED, the first aim of this study was to investigate the expression of TGF-β1 in the penis from male rabbits with chronic partial bladder outlet obstruction (PBOO). Besides, it has been suggested that oxidative stress plays a significant role in the pathophysiological mechanism of ED. Thus, the second aim of this study was to further investigate whether the urinary or serum oxidative stress markers are involved in chronic PBOO-induced penile dysfunction. A total of 16 male New Zealand White rabbits were separated equally into four groups: a control group and PBOO groups obstructed for 2, 4 and 8 weeks respectively. Using the RT-PCR and Western blot analysis, a progressive increase of TGF-β1 in penis was found at 2, 4 and 8 weeks after obstruction. Moreover, the biomarkers for oxidative stress or oxidative damage were significantly detected in the penis of rabbits after PBOO, which include the enhancement of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in urine and plasma, plasma malondialdehyde (MDA) and total antioxidant capacity (TAC), as well as reduction of glutathione (GSH). On the basis of our results, the increase of TGF-β1 and elevated systemic oxidative stress may play key roles to contribute to penile dysfunction after chronic PBOO. © 2011 The Authors. International Journal of Andrology © 2011 European Academy of Andrology.

Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dong; Asadi, Kamal; Blom, Paul W. M.; Leeuw, Dago M. de, E-mail: deleeuw@mpip-mainz.mpg.de [Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany); Katsouras, Ilias [Holst Centre, High Tech Campus 31, 5656AE Eindhoven (Netherlands); Groen, Wilhelm A. [Holst Centre, High Tech Campus 31, 5656AE Eindhoven (Netherlands); Faculty of Aerospace Engineering, Delft University of Technology, Kluyverweg 1 2629 HS, Delft (Netherlands)

2016-06-06

A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O{sub 3}. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.

Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

Science.gov (United States)

Zhao, Dong; Katsouras, Ilias; Asadi, Kamal; Groen, Wilhelm A.; Blom, Paul W. M.; de Leeuw, Dago M.

2016-06-01

A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O3. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.

La{sub 0.84}Sr{sub 0.16}MnO{sub 3-{delta}} cathodes impregnated with Bi{sub 1.4}Er{sub 0.6}O{sub 3} for intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Li, Junliang; Wang, Shaorong; Wang, Zhenrong; Liu, Renzhu; Wen, Tinglian; Wen, Zhaoyin [The Key Laboratory of Energy Conversion Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2009-12-01

La{sub 0.84}Sr{sub 0.16}MnO{sub 3-{delta}}-Bi{sub 1.4}Er{sub 0.6}O{sub 3} (LSM-ESB) composite cathodes are fabricated by impregnating LSM electronic conducting matrix with the ion-conducting ESB for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performance of LSM-ESB cathodes is investigated at temperatures below 750 C by AC impedance spectroscopy. The ion-impregnation of ESB significantly enhances the electrocatalytic activity of the LSM electrodes for the oxygen reduction reactions, and the ion-impregnated LSM-ESB composite cathodes show excellent performance. At 750 C, the value of the cathode polarization resistance (R{sub p}) is only 0.11 {omega} cm{sup 2} for an ion-impregnated LSM-ESB cathode, which also shows high stability during a period of 200 h. For the performance testing of single cells, the maximum power density is 0.74 W cm{sup -2} at 700 C for a cell with the LSM-ESB cathode. The results demonstrate the ion-impregnated LSM-ESB is one of the promising cathode materials for intermediate-temperature solid oxide fuel cells. (author)

Kinetic and reaction pathways of methanol oxidation on platinum

International Nuclear Information System (INIS)

McCabe, R.W.; McCready, D.F.

1986-01-01

Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

Thermogravimetric control of intermediate compounds in uranium metallurgy; Control termogravimetrico de productos intermedios de la metalurgia del uranio

Energy Technology Data Exchange (ETDEWEB)

Gasco Sanchez, L; Fernandez Cellini, R

1959-07-01

The thermal decomposition of some intermediate compounds in the metallurgy of the uranium as uranium peroxide, ammonium uranate, uranium and ammonium penta-fluoride, uranium tetrafluoride and uranous oxide has been study by means of the Chevenard's thermo balance. Some data on pyrolysis of synthetic mixtures of intermediate compounds which may occasionally appear during the industrial process, are given. Thermogravimetric methods of control are suggested, usable in interesting products in the uranium metallurgy. (Author) 20 refs.

Partial oxidation of jet fuels over Rh/Al_2O_3. Design and reaction kinetics of sulfur-containing surrogates

International Nuclear Information System (INIS)

Baer, Julian Nicolaas

2016-01-01

The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al_2O_3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al_2O_3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An

Thermal processing and native oxidation of silicon nanoparticles

International Nuclear Information System (INIS)

Winters, Brandon J.; Holm, Jason; Roberts, Jeffrey T.

2011-01-01

In this study, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electron energy loss spectroscopy (EELS) were used to investigate in-air oxidation of silicon nanoparticles ca. 11 nm in diameter. Particle samples were prepared first by extracting them from an RF plasma synthesis reactor, and then heating them in an inert carrier gas stream. The resulting particles had varying surface hydrogen coverages and relative amounts of SiH x (x = 1, 2, and 3), depending on the temperature to which they had been heated. The particles were allowed to oxidize in-air for several weeks. FTIR, XPS, and EELS analyses that were performed during this period clearly establish that adsorbed hydrogen retards oxidation, although in complex ways. In particular, particles that have been heated to intermediate hydrogen coverages oxidize more slowly in air than do freshly generated particles that have a much higher hydrogen content. In addition, the loss of surface hydride species at high processing temperatures results in fast initial oxidation and the formation of a self-limiting oxide layer. Analogous measurements made on deuterium-covered particles show broadly similar behavior; i.e., that oxidation is the slowest at some intermediate coverage of adsorbed deuterium.

Hypochlorite-induced oxidation of thiols

DEFF Research Database (Denmark)

Davies, Michael Jonathan; Hawkins, C L

2000-01-01

-molecular-weight thiols such as reduced glutathione (GSH), and sulfur-containing amino acids in proteins, are major targets for HOCl. Radicals have not generally been implicated as intermediates in thiol oxidation by HOCl, though there is considerable literature evidence for the involvement of radicals in the metal ion......-, thermal- or UV light-catalysed decomposition of sulfenyl or sulfonyl chlorides which are postulated intermediates in thiol oxidation. In this study we show that thiyl radicals are generated on reaction of a number of low-molecular-weight thiols with HOCl. With sub-stoichiometric amounts of HOCl, relative...... to the thiol, thiyl radicals are the major species detected by EPR spin trapping. When the HOCl is present in excess over the thiol, additional radicals are detected with compounds which contain amine functions; these additional radicals are assigned to nitrogen-centered species. Evidence is presented...

Detection Identification and Quantification of Keto-Hydroperoxides in Low-Temperature Oxidation.

Energy Technology Data Exchange (ETDEWEB)

Hansen, Nils; Moshammer, Kai; Jasper, Ahren W.

2017-07-01

Keto-hydroperoxides are reactive partially oxidized intermediates that play a central role in chain-branching reactions during the low-temperature oxidation of hydrocarbons. In this Perspective, we outline how these short lived species can be detected, identified, and quantified using integrated experimental and theoretical approaches. The procedures are based on direct molecular-beam sampling from reactive environments, followed by mass spectrometry with single-photon ionization, identification of fragmentation patterns, and theoretical calculations of ionization thresholds, fragment appearance energies, and photoionization cross sections. Using the oxidation of neo-pentane and tetrahydrofuran as examples, the individual steps of the experimental approaches are described in depth together with a detailed description of the theoretical efforts. For neo-pentane, the experimental data are consistent with the calculated ionization and fragment appearance energies of the keto-hydroperoxide, thus adding confidence to the analysis routines and the employed levels of theory. For tetrahydrofuran, multiple keto-hydroperoxide isomers are possible due to the presence of nonequivalent O₂ addition sites. Despite this additional complexity, the experimental data allow for the identification of two to four keto-hydroperoxides. Mole fraction profiles of the keto-hydroperoxides, which are quantified using calculated photoionization cross sections, are provided together with estimated uncertainties as function of the temperature of the reactive mixture and can serve as validation targets for chemically detailed mechanisms.

Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

Science.gov (United States)

Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

2015-01-06

The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

Intermediate-range structure of amorphous GeSe{sub 2} alloy

Energy Technology Data Exchange (ETDEWEB)

Murakami, Y. [Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, Yamagata 990-8560 (Japan)], E-Mail: su105@kdeve.kj.yamagata-u.ac.jp; Usuki, T. [Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, Yamagata 990-8560 (Japan); Sakurai, M. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Kohara, S. [Japan Synchrotron Radiation Research Institute, Sayo, Hyogo 769-5198 (Japan)

2007-03-25

Neutron and high-energy X-ray diffraction measurements have been carried out at KENS-KEK and SPring-8, in order to investigate detailed structures of amorphous GeSe{sub 2} prepared by the rapid quenching method. Considerable intermediate-range ordering is evident from the presence of a first sharp diffraction peak at low magnetides of the scattering vector. Well-defined first and second peaks are found at around 2.36 and 3.90 A in the pair distribution function g(r). A small shoulder related to the existence of edge-sharing tetrahedral units is observed at a shorter r side of the second peak in g(r). Partial distribution functions, partial structure factors and bond-angle distributions can be obtained by Reverse Monte Carlo simulation. Results suggest that there are homo-polar bonds in tetrahedral structural units, and then the glass network is constructed by not only corner-sharing but also edge-sharing tetrahedra.

The 1.6 Å crystal structure of pyranose dehydrogenase from Agaricus meleagris rationalizes substrate specificity and reveals a flavin intermediate.

Directory of Open Access Journals (Sweden)

Tien Chye Tan

Full Text Available Pyranose dehydrogenases (PDHs are extracellular flavin-dependent oxidoreductases secreted by litter-decomposing fungi with a role in natural recycling of plant matter. All major monosaccharides in lignocellulose are oxidized by PDH at comparable yields and efficiencies. Oxidation takes place as single-oxidation or sequential double-oxidation reactions of the carbohydrates, resulting in sugar derivatives oxidized primarily at C2, C3 or C2/3 with the concomitant reduction of the flavin. A suitable electron acceptor then reoxidizes the reduced flavin. Whereas oxygen is a poor electron acceptor for PDH, several alternative acceptors, e.g., quinone compounds, naturally present during lignocellulose degradation, can be used. We have determined the 1.6-Å crystal structure of PDH from Agaricus meleagris. Interestingly, the flavin ring in PDH is modified by a covalent mono- or di-atomic species at the C(4a position. Under normal conditions, PDH is not oxidized by oxygen; however, the related enzyme pyranose 2-oxidase (P2O activates oxygen by a mechanism that proceeds via a covalent flavin C(4a-hydroperoxide intermediate. Although the flavin C(4a adduct is common in monooxygenases, it is unusual for flavoprotein oxidases, and it has been proposed that formation of the intermediate would be unfavorable in these oxidases. Thus, the flavin adduct in PDH not only shows that the adduct can be favorably accommodated in the active site, but also provides important details regarding the structural, spatial and physicochemical requirements for formation of this flavin intermediate in related oxidases. Extensive in silico modeling of carbohydrates in the PDH active site allowed us to rationalize the previously reported patterns of substrate specificity and regioselectivity. To evaluate the regioselectivity of D-glucose oxidation, reduction experiments were performed using fluorinated glucose. PDH was rapidly reduced by 3-fluorinated glucose, which has the C2

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

Science.gov (United States)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Selective oxidation of naphthalene in CO/H{sub 2} mixtures over Mo/V/W mixed oxides. A contribution to biomass gasification; Selektivoxidation von Naphthalin in CO/H{sub 2}-Mischungen an Mo/V/W-Mischoxiden. Ein Beitrag zur Biomassevergasung

Energy Technology Data Exchange (ETDEWEB)

Herrmann, Sonja

2007-11-26

The development of efficient and sustainable technologies for the production of biofuels of the second generation is one of the fundamental challenges of the beginning 21st century. In the first step of the so called Biomass-to-Liquid processes the biomass is transformed to syngas in a gasifier. Prior to fuel generation via Fischer-Tropsch, methanol or dimethyl ether synthesis a purification of the raw gas must take place. A main impurity of the gas is the tar formed during gasification. Besides desactivation of the catalyst in the following synthesis step, the tar condenses during cooling down of the syngas, leading to the formation of scaling in the plant and to a reduced syngas yield. In order to develop a energy efficient technology this work focuses on the development of a method for tar removal that can be performed at temperatures between 400 and 900 C while providing the required syngas purity for the subsequent fuel synthesis. First the potential of a Mo8V2W1Ox mixed oxide catalyst for selective tar oxidation was investigated using a thermo balance. By means of temperature programmed reductions of the oxidised catalyst with CO2, H2 and tar model compound naphthalene no activity regarding the oxidation of CO, only minor activity regarding the oxidation of H2, but high activity for naphthalene oxidation was determined. Based on these studies temperature programmed reactions in the presence of oxygen were performed employing a catalyst bed in a plug flow rector equipped with an online mass spectrometer. The complete conversion of naphthalene was observed at temperatures above 412 C. In the same temperature range no oxidation of CO and only a marginal oxidation of H2 occurred. Apart from the total oxidation products CO, CO2 and H2O partial oxidised products as maleic anhydride and phthalic anhydride were formed, though. Mechanical mixing of the catalyst with sodium carbonate lead to an optimization of the catalytic properties of the mixed oxide catalyst

Value Added Tax and price stability in Nigeria: A partial equilibrium analysis

Directory of Open Access Journals (Sweden)

Marius Ikpe

2013-12-01

Full Text Available The economic impact of Value Added Tax (VAT that was implemented in Nigeria in 1994 has generated much debate in recent times, especially with respect to its effect on the level of aggregate prices. This study empirically examines the influence of VAT on price stability in Nigeria using partial equilibrium analysis. We introduced the VAT variable in the framework of a combination of structuralist, monetarist and fiscalist approaches to inflation modelling. The analysis was carried out by applying multiple regression analysis in static form to data for the 1994-2010 period. The results reveal that VAT exerts a strong upward pressure on price levels, most likely due to the burden of VAT on intermediate outputs. The study rules out the option of VAT exemptions for intermediate outputs as a solution, due to the difficulty in distinguishing between intermediate and final outputs. Instead, it recommends a detailed post-VAT cost-benefit analysis to assess the social desirability of VAT policy in Nigeria.

Results of intermediate-scale hot isostatic press can experiments

International Nuclear Information System (INIS)

Nelson, L.O.; Vinjamuri, K.

1995-05-01

Radioactive high-level waste (HLW) has been managed at the Idaho Chemical Processing Plant (ICPP) for a number of years. Since 1963, liquid HLW has been solidified into a granular solid (calcine). Presently, over 3,800 m 3 of calcine is stored in partially-underground stainless steel bins. Four intermediate- scale HLW can tests (two 6-in OD x 12-in tall and two 4-in OD x 7-in tall) are described and compared to small-scale HIP can tests (1- to 3-in OD x 1- to 4.5-in tall). The intermediate-scale HIP cans were loaded with a 70/30 calcine/frit blend and HIPped at an off-site facility at 1050 degrees C; and 20 ksi. The dimensions of two cans (4-in OD x 7-in tall) were monitored during the HIP cycle with eddy-current sensors. The sensor measurements indicated that can deformation occurs rapidly at 700 degrees C; after which, there is little additional can shrinkage. HIP cans were subjected to a number of analyses including calculation of the overall packing efficiency (56 to 59%), measurement of glass-ceramic (3.0 to 3.2 g/cc), 14-day MCC-1 leach testing (total mass loss rates 2 day), and scanning electron microscopy (SEM). Based on these analyses, the glass-ceramic material produced in intermediate-scale cans is similar to material produced in small-scale cans. No major scale-up problems were indicated. Based on the packing efficiency observed in intermediate- and small-scale tests, the overall packing efficiency of production-scale (24-in OD x 36- to 190-in tall) cans would be approximately 64% for a pre-HIP right-circular cylinder geometry. An efficiency of 64% would represent a volume reduction factor of 2.5 over a candidate glass waste prepared at 33 wt% waste loading

Characterizing millisecond intermediates in hemoproteins using rapid-freeze-quench resonance Raman spectroscopy.

Science.gov (United States)

Matsumura, Hirotoshi; Moënne-Loccoz, Pierre

2014-01-01

The combination of rapid freeze quenching (RFQ) with resonance Raman (RR) spectroscopy represents a unique tool with which to investigate the nature of short-lived intermediates formed during the enzymatic reactions of metalloproteins. Commercially available equipment allows trapping of intermediates within a millisecond to second time scale for low-temperature RR analysis resulting in the direct detection of metal-ligand vibrations and porphyrin skeletal vibrations in hemoproteins. This chapter briefly discusses RFQ-RR studies carried out previously in our laboratory and presents, as a practical example, protocols for the preparation of RFQ samples of the reaction of metmyoglobin with nitric oxide (NO) under anaerobic conditions. Also described are important controls and practical procedures for the analysis of these samples by low-temperature RR spectroscopy.

Experimental and numerical investigation of the catalytic partial oxidation of methane to synthesis gas for power generation applications[Dissertation 17183

Energy Technology Data Exchange (ETDEWEB)

Schneider, A.

2007-07-01

The present work addresses the catalytic partial oxidation (CPO) of methane to synthesis gas, with particular emphasis on power generation applications. A combined experimental and numerical investigation of methane partial oxidation to synthesis gas (H{sub 2}, CO) over rhodium-based catalysts has been carried out at pressures of up to 10 bar. The reactivity of the produced hydrogen and the suitably-low light-off temperatures of the CPO reactor, greatly facilitate operation of power generation gas turbines with reduced NO{sub x} emissions, stable operation with low calorific value fuels, and new combustion strategies for efficient CO{sub 2} capture. Those strategies utilize CPO of methane with oxygen (separated from air) and large exhaust gas recycle (H{sub 2}O and CO{sub 2}). An optically accessible catalytic channel-flow reactor was used to carry out Raman spectroscopy of major gas-phase species and laser induced fluorescence (LIF) of formaldehyde, in order to gain fundamental information on the catalytic and gas-phase chemical pathways. Transverse concentration profiles measured by the spontaneous Raman scattering technique determined the catalytic reactivity, while the LIF provided flame shapes and anchoring positions that, in turn, characterized the gaseous reactivity. Comparison between measurements and 2-D CFD computations, led to the validation of detailed catalytic and gas-phase reaction mechanisms. Experiments in a subscale gas-turbine honeycomb catalytic reactor have shown that the foregoing reaction mechanisms were also appropriate under gas-turbine relevant conditions with short reactant residence times. The light-off behavior of the subscale honeycomb reactor was reproduced by transient 2-D CFD computations. Ignition and extinction in CPO was studied. It was shown that, despite the chemical impact of the H{sub 2}O diluent during the transient catalytic ignition event, the light-off times themselves were largely unaffected by the exhaust gas dilution

Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

Science.gov (United States)

Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

2011-11-01

By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

2014-01-01

Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration.

Science.gov (United States)

Sun, Yan; Lu, Wenchao; Liu, Jianbo

2017-02-09

8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a 1 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H] + , deprotonated [8-oxoG - H] - , and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (E col ) on reaction cross sections over a center-of-mass E col range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H] - was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H] - was captured as the main oxidation product. Reaction cross section for [8-oxoG - H] - ·W + 1 O 2 decreases with increasing E col and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H] + ·W 0,1 and [8-oxoG - H] - ·W 0

Thermogravimetric control of intermediate compounds in uranium metallurgy; Control termogravimetrico de productos intermedios de la metalurgia del uranio

Energy Technology Data Exchange (ETDEWEB)

Gasco Sanchez, L.; Fernandez Cellini, R.

1959-07-01

The thermal decomposition of some intermediate compounds in the metallurgy of the uranium as uranium peroxide, ammonium uranate, uranium and ammonium penta-fluoride, uranium tetrafluoride and uranous oxide has been study by means of the Chevenard's thermo balance. Some data on pyrolysis of synthetic mixtures of intermediate compounds which may occasionally appear during the industrial process, are given. Thermogravimetric methods of control are suggested, usable in interesting products in the uranium metallurgy. (Author) 20 refs.

Reversible solid oxide fuel cells (R-SOFCs) with chemically stable proton-conducting oxides

KAUST Repository

Bi, Lei

2015-07-01

Proton-conducting oxides offer a promising way of lowering the working temperature of solid oxide cells to the intermediate temperate range (500 to 700. °C) due to their better ionic conductivity. In addition, the application of proton-conducting oxides in both solid oxide fuel cells (SOFCs) and sold oxide electrolysis cells (SOECs) provides unique advantages compared with the use of conventional oxygen-ion conducting conductors, including the formation of water at the air electrode site. Since the discovery of proton conduction in some oxides about 30. years ago, the development of proton-conducting oxides in SOFCs and SOECs (the reverse mode of SOFCs) has gained increased attention. This paper briefly summarizes the development in the recent years of R-SOFCs with proton-conducting electrolytes, focusing on discussing the importance of adopting chemically stable materials in both fuel cell and electrolysis modes. The development of electrode materials for proton-conducting R-SOFCs is also discussed. © 2015 Elsevier B.V.

Reversibility of partial denaturation of DNA

International Nuclear Information System (INIS)

Acuna, M.I.; Mingot, F.; Davila, C.A.

1976-01-01

The recovery of hypochromicity in a partially denatured DNA sample when salt concentration is suddenly increased at a intermediate stage of the thermal transition is studied. The results of CsCl gradient analysis, PEG/DEX partition analysis, behaviour in a new thermal transition hydrodynamic properties and transforming ability, support the view that the process is an intramolecular double chain denaturation. The degree of denaturation irreversibility is dependent on single chain molecular weight of DNA (discontinuities denisty) and upon the helicity value at which salt concentration jump is performed. Both dependences are formally interpreted according to Elton's model for base distribution in DNA. Kinetically the process behaves as being an hydrodynamically limited rewinding. (author)

Partial structures in molten AgBr

Energy Technology Data Exchange (ETDEWEB)

Ueno, Hiroki [Department of Condensed Matter Chemistry and Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan)], E-mail: ueno@gemini.rc.kyushu-u.ac.jp; Tahara, Shuta [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Science, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Kawakita, Yukinobu [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan); Kohara, Shinji [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Takeda, Shin' ichi [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan)

2009-02-21

The structure of molten AgBr has been studied by means of neutron and X-ray diffractions with the aid of structural modeling. It is confirmed that the Ag-Ag correlation has a small but well-defined first peak in the partial pair distribution function whose tail penetrates into the Ag-Br nearest neighbor distribution. This feature on the Ag-Ag correlation is intermediate between that of molten AgCl (non-superionic melt) and that of molten AgI (superionic melt). The analysis of Br-Ag-Br bond angle reveals that molten AgBr preserves a rocksalt type local ordering in the solid phase, suggesting that molten AgBr is clarified as non-superionic melt like molten AgCl.

An investigation of the oxidized Ni/InAs interface

International Nuclear Information System (INIS)

Venter, A.; Botha, J.R.; Swart, H.C.; Naidoo, S.; Olivier, E.J.

2009-01-01

Ni was resistively deposited onto bulk InAs and subsequently oxidized in an O 2 atmosphere. The anneal temperature and time were 450 deg. C and 2.5 h, respectively. X-ray diffraction of the oxidized Ni/InAs sample revealed the formation of In 3 Ni 2 and In 2 O 3 on the front suggesting inter diffusion of In, Ni and O. NiO was not detected by X-ray diffraction. In a preliminary study, using glass as a substrate, NiO readily formed when using these oxidation parameters. Conductivity measurements of the oxidized Ni/InAs surface revealed a conducting front and insulating rear surface while TEM of the Ni/InAs interface revealed an intermediate amorphous diffusion zone between the 'oxidized' Ni layer and the bulk InAs. A closer investigation of the intermediate layer supports the X-ray diffraction results, suggesting compound formation due to diffusion of oxygen and nickel into the substrate, and out-diffusion of In and As from the bulk of the sample. AES was used to further elucidate these results.

Final Technical Report: Affordable, High-Performance, Intermediate Temperature Solid Oxide Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Blackburn, Bryan M. [Redox Power Systems, LLC, College Park, MD (United States); Bishop, Sean [Redox Power Systems, LLC, College Park, MD (United States); Gore, Colin [Redox Power Systems, LLC, College Park, MD (United States); Wang, Lei [Redox Power Systems, LLC, College Park, MD (United States); Correa, Luis [Redox Power Systems, LLC, College Park, MD (United States); Langdo, Thomas [Redox Power Systems, LLC, College Park, MD (United States); Deaconu, Stelu [Redox Power Systems, LLC, College Park, MD (United States); Pan, Keji [Redox Power Systems, LLC, College Park, MD (United States)

2018-02-15

In this project, we improved the power output and voltage efficiency of our intermediate temperature solid oxide fuel cells (IT-SOFCs) with a focus on ~600 °C operation. At these temperatures and with the increased power density (i.e., fewer cells for same power output), the stack cost should be greatly reduced while extending durability. Most SOFC stacks operate at temperatures greater than 800 °C. This can greatly increase the cost of the system (stacks and BOP) as well as maintenance costs since the most common degradation mechanisms are thermally driven. Our approach uses no platinum group metal (PGM) materials and the lower operating temperature allows use of simple stainless steel interconnects and commercial off-the-shelf gaskets in the stack. Furthermore, for combined heating and power (CHP) applications the stack exhaust still provides “high quality” waste heat that can be recovered and used in a chiller or boiler. The anticipated performance, durability, and resulting cost improvements (< $700/kWe) will also move us closer to reaching the full potential of this technology for distributed generation (DG) and residential/commercial CHP. This includes eventual extension to cleaner, more efficient portable generators, auxiliary power units (APUs), and range extenders for transportation. The research added to the understanding of the area investigated by exploring various methods for increasing power density (Watts/square centimeter of active area in each cell) and increasing cell efficiency (increasing the open circuit voltage, or cell voltage with zero external electrical current). The results from this work demonstrated an optimized cell that had greater than 1 W/cm2 at 600 °C and greater than 1.6 W/cm2 at 650 °C. This was demonstrated in large format sizes using both 5 cm by 5 cm and 10 cm by 10 cm cells. Furthermore, this work demonstrated that high stability (no degradation over > 500 hours) can be achieved together with high performance in large

Intermediate neutron spectrum problems and the intermediate neutron spectrum experiment

International Nuclear Information System (INIS)

Jaegers, P.J.; Sanchez, R.G.

1996-01-01

Criticality benchmark data for intermediate energy spectrum systems does not exist. These systems are dominated by scattering and fission events induced by neutrons with energies between 1 eV and 1 MeV. Nuclear data uncertainties have been reported for such systems which can not be resolved without benchmark critical experiments. Intermediate energy spectrum systems have been proposed for the geological disposition of surplus fissile materials. Without the proper benchmarking of the nuclear data in the intermediate energy spectrum, adequate criticality safety margins can not be guaranteed. The Zeus critical experiment now under construction will provide this necessary benchmark data

Chemical compatibility and properties of suspension plasma-sprayed SrTiO3-based anodes for intermediate-temperature solid oxide fuel cells

Science.gov (United States)

Zhang, Shan-Lin; Li, Cheng-Xin; Li, Chang-Jiu

2014-10-01

La-doped strontium titanate (LST) is a promising, redox-stable perovskite material for direct hydrocarbon oxidation anodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs). In this study, nano-sized LST and Sm-doped ceria (SDC) powders are produced by the sol-gel and glycine-nitrate processes, respectively. The chemical compatibility between LST and electrolyte materials is studied. A LST-SDC composite anode is prepared by suspension plasma spraying (SPS). The effects of annealing conditions on the phase structure, microstructure, and chemical stability of the LST-SDC composite anode are investigated. The results indicate that the suspension plasma-sprayed LST-SDC anode has the same phase structure as the original powders. LST exhibits a good chemical compatibility with SDC and Mg/Sr-doped lanthanum gallate (LSGM). The anode has a porosity of ∼40% with a finely porous structure that provides high gas permeability and a long three-phase boundary for the anode reaction. Single cells assembled with the LST-SDC anode, La0.8Sr0.2Ga0.8Mg0.2O3 electrolyte, and La0.8Sr0.2CoO3-SDC cathode show a good performance at 650-800 °C. The annealing reduces the impedances due to the enhancement in the bonding between the particles in the anode and interface of anode and LSGM electrolyte, thus improving the output performance of the cell.

Are zirconia corrosion films a form of partially stabilised zirconia (PSZ)?

International Nuclear Information System (INIS)

Cox, B.

1987-03-01

The problem of understanding the development of porosity in a zirconium oxide film still under biaxial compression is discussed. The oxide film is compared with partially stabilised zirconia (PSZ) where stress induced transformation of tetragonal zirconia has been observed to lead to microcracking of the structure. The similarities between PSZ and the thermal oxide films formed on zirconium alloys are enumerated, and an hypothesis is proposed that can both explain the penetration of pores or microcracks in oxides on Zircaloy-2 to a point very close to the oxide/metal interface, and explain the observation that such a phenomenon does not occur in oxide films on Zr-2.5%Nb. This hypothesis could be tested by laser Raman spectroscopy on oxide films during growth at elevated temperatures. 87 refs

Optimization of BSCF-SDC composite air electrode for intermediate temperature solid oxide electrolyzer cell

International Nuclear Information System (INIS)

Heidari, Dorna; Javadpour, Sirus; Chan, Siew Hwa

2017-01-01

Highlights: • Effect of BSCF-SDC composite air electrode on SOEC electrochemical performance. • Effects on performance of BSCF-SDC air electrode, fuel humidity and temperature. • Desired IT-SOEC performance by compositing the BSCF air electrode with SDC. - Abstract: Solid oxide electrolyzer cells (SOECs) are devises which recently have attracted lots of attention due to their advantages. Their high operating temperature leads to mechanical compatibility issues such as thermal expansion mismatch between layers of material in the cell. The aim of this study is to mitigate the issue of thermal expansion mismatch between Ba_0_._5Sr_0_._5Co_0_._8Fe_0_._2O_3_−_δ (BSCF) and samaria doped ceria, Sm_0_._2Ce_0_._8O_1_._9 (SDC), enhance the triple-phase boundaries and improve the adhesion of the electrode to the electrolytes, hence improve the cell performance. To make BSCF more thermo-mechanically compatible with the SDC electrolyte, the formation of a composite electrode by introducing SDC as the compositing material is proposed. In this study, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, and 50 wt.% of commercial SDC powder was mixed with BSCF powder, prepared by sol-gel method, to make the composite air electrode. After successfully synthesizing the BSCF-SDC/YSZ-SDC/Ni-YSZ electrolyzer cell, the electrochemical performance was tested for the intermediate-temperature SOEC (IT-SOEC), over the temperature range of 650–800 °C. The microstructure of each sample was studied by field emission electron microscopy (FESEM, JEOL, JSM 6340F) for possible pin holes. The result of this study proves that the sample with 20% SDC-80% BSCF shows the highest performance among the investigated cells.

Synthesis of LaCoO{sub 3} nano-powders by aqueous gel-casting for intermediate temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Cheng, Chia Siang; Zhang, Lan; Jiang, San Ping [School of Mechanical and Aerospace Engineering, Nanyang Technological University (Singapore); Zhang, Yu.Jun [Key Lab for Liquid Structure and Heredity of Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan (China)

2008-04-15

LaCoO{sub 3} (LC) perovskite powders for intermediate temperature solid oxide fuel cells (IT-SOFCs) are synthesized by a simple and cost-effective aqueous gel-casting technique using metal nitrates as raw materials. Effect of the ratio of organic precursors (acrylamide (AM) monomer and N,N'-Methylenebisacrylamide (MBAM) crosslinker) to metal nitrates (lanthanum nitrate, cobalt nitrate) and the ratio of AM to MBAM on the particle size are investigated in detail. TEM results indicate that the particle size of LC nano-powders is in the range of 31-60 nm and decreases with increasing ratio of organic precursor to metal nitrates but is not affected by the ratio of AM to MBAM. Preliminary results show that the nano-structured electrode approach based on wet impregnation is effective to combine the high electrocatalytic activity of LC nano-powders and the structural stability of La{sub 0.72}Sr{sub 0.18}MnO{sub 3} {sub -} {sub {delta}} (LSM) electrodes for the development of IT-SOFC cathodes. (author)

Photocatalytic oxidation of indoor toluene: Process risk analysis and influence of relative humidity, photocatalysts, and VUV irradiation

International Nuclear Information System (INIS)

Zhao, Weirong; Dai, Jiusong; Liu, Feifei; Bao, Jiaze; Wang, Yan; Yang, Yong; Yang, Yanan; Zhao, Dongye

2012-01-01

Concentrations of 13 gaseous intermediates in photocatalytic oxidation (PCO) of toluene in indoor air were determined in real-time by proton transfer reaction mass spectrometry and desorption intensities of 7 adsorbed intermediates on the surface of photocatalysts were detected by temperature‐programmed desorption‐mass spectrometry. Effects of relative humidity (RH), photocatalysts, and vacuum ultraviolet (VUV) irradiation on the distribution and category of the intermediates and health risk influence index (η) were investigated. RH enhances the formation rate of hydroxide radicals, leading to more intermediates with higher oxidation states in gas phase. N doping promotes the separation of photo-generated electrons and holes and enhances PCO activity accordingly. VUV irradiation results in higher mineralization rate and more intermediates with higher oxidation states and lower toxicity e.g. carboxylic acids. Health risk analysis indicates that higher RH, N doping of TiO 2 , and VUV lead to “greener” intermediates and smaller η. Finally, a conceptual diagram was proposed to exhibit the scenario of η varied with extent of mineralization for various toxicities of inlet pollutants. Highlights: ► 13 volatile intermediates in PCO of toluene were determined in real-time by PTR-MS. ► 7 adsorbed intermediates on surface of photocatalyst were determined by TPD-MS. ► Higher RH, N doping of TiO 2 , and VUV irradiation lead to “greener” intermediates. ► Health risk index relies on extent of mineralization and toxicities of inlet VOCs.

Preparation and characterization of La0,60Sr0,40Co0,20Fe0,80O3-δ powders for intermediate temperature solid oxide fuel cells (ITSOFC) cathode

International Nuclear Information System (INIS)

Vargas, R.A.; Chiba, R.; Bonturim, E.; Andreoli, M.; Seo, E.S.M.

2009-01-01

Nowadays a material that is studied as cathode in intermediate temperature solid oxide fuel cells (ITSOFC) is the mixing oxide La 0,60S r 0 , 40 Co 0 , 20 Fe 0 , 80 O 3-δ (LSCF), that possess pseudo-perovskite structure. The objective of this work is to present the physical, chemical and microstructural of LSCF powders characteristics, prepared by the citrate technique. The main analyses utilized were: X-ray diffraction, X-ray fluorescence spectroscopy, laser scattering granulometry, and scanning electron microscopy. The results show that the elimination of organic precursors is important for desired structure formation and that amount of this phase depends on cobalt content. Moreover, the chemical composition is next to stoichiometric calculated (x=0.40 and y=0.80) and the average sizes of particles are adjusted for ceramic suspensions preparation, contributing for the wet powder spraying step conformation. (author)

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

Science.gov (United States)

Chen, Ling; Zhou, Hai-Yun; Deng, Qin-Ying

2007-06-01

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

Strategies for Lowering Solid Oxide Fuel Cells Operating Temperature

Directory of Open Access Journals (Sweden)

Albert Tarancón

2009-11-01

Full Text Available Lowering the operating temperature of solid oxide fuel cells (SOFCs to the intermediate range (500–700 ºC has become one of the main SOFC research goals. High operating temperatures put numerous requirements on materials selection and on secondary units, limiting the commercial development of SOFCs. The present review first focuses on the main effects of reducing the operating temperature in terms of materials stability, thermo-mechanical mismatch, thermal management and efficiency. After a brief survey of the state-of-the-art materials for SOFCs, attention is focused on emerging oxide-ionic conductors with high conductivity in the intermediate range of temperatures with an introductory section on materials technology for reducing the electrolyte thickness. Finally, recent advances in cathode materials based on layered mixed ionic-electronic conductors are highlighted because the decreasing temperature converts the cathode into the major source of electrical losses for the whole SOFC system. It is concluded that the introduction of alternative materials that would enable solid oxide fuel cells to operate in the intermediate range of temperatures would have a major impact on the commercialization of fuel cell technology.

Method to reduce the nitrogen oxide content of gaseous wastes

Energy Technology Data Exchange (ETDEWEB)

Klopp, G.; Sueto, J.; Szasz, K.; Szebenyi, I.; Winkler, G.; Machacs, M.; Palmai, G.

1980-11-13

The proposed process is suited for the denitrification of waste gases from nitric acid plants. It proceeds without an additional energy source with an integrated adsorption unit which guaranties the complete recirculation of the produced nitrogen oxides and allows the regeneration of the adsorbents by the use of the energy from the oxidation of nitrous oxide to nitric oxide. The desorption is carried out by the intermediate passage of the hot gases from the oxidizer through the adsorber.

Challenge of non-precious metal oxide-based cathode for polymer electrolyte fuel cell

Energy Technology Data Exchange (ETDEWEB)

Ishihara, Akimitsu; Matsuzawa, Koichi; Mitsushima, Shigenori; Ota, Ken-ichiro [Yokohama National Univ. (Japan)

2010-07-01

The partially oxidized TaC{sub 0.58}N{sub 0.42} was investigated as non-platinum cathode for PEFC. In order to quantify the degree of oxidation, the degree of oxidation (DOO) was defined using the XRD peaks of Ta-CN and Ta{sub 2}O{sub 5}. The onset potential for the oxidation reduction reaction (ORR) had high value, that is, 0.9 V vs. RHE (reversible hydrogen electrode), at higher oxidation state of the TaC{sub 0.58}N{sub 0.42}. We found that the partial oxidation of TaC{sub 0.58}N{sub 0.42} was greatly useful to enhance the catalytic activity for the ORR. The volcano plot of the ionization potential vs. the E{sub ORR} suggested that there was a suitable interaction between the surface of the partially oxidized TaC{sub 0.58}N{sub 0.42} and oxygen. (orig.)

Study of propane partial oxidation on vanadium-containing catalysts

Energy Technology Data Exchange (ETDEWEB)

Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

1998-12-31

The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

Ni/SiO2 Catalyst Prepared with Nickel Nitrate Precursor for Combination of CO2 Reforming and Partial Oxidation of Methane: Characterization and Deactivation Mechanism Investigation

Directory of Open Access Journals (Sweden)

Sufang He

2015-01-01

Full Text Available The performance of Ni/SiO2 catalyst in the process of combination of CO2 reforming and partial oxidation of methane to produce syngas was studied. The Ni/SiO2 catalysts were prepared by using incipient wetness impregnation method with nickel nitrate as a precursor and characterized by FT-IR, TG-DTA, UV-Raman, XRD, TEM, and H2-TPR. The metal nickel particles with the average size of 37.5 nm were highly dispersed over the catalyst, while the interaction between nickel particles and SiO2 support is relatively weak. The weak NiO-SiO2 interaction disappeared after repeating oxidation-reduction-oxidation in the fluidized bed reactor at 700°C, which resulted in the sintering of metal nickel particles. As a result, a rapid deactivation of the Ni/SiO2 catalysts was observed in 2.5 h reaction on stream.

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

Science.gov (United States)

Carraher, Jack McCaslin

Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path

Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

International Nuclear Information System (INIS)

Rocek, J.; Peng, T.Y.

1977-01-01

Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

Catalytic Activity Studies of Vanadia/Silica–Titania Catalysts in SVOC Partial Oxidation to Formaldehyde: Focus on the Catalyst Composition

Directory of Open Access Journals (Sweden)

Niina Koivikko

2018-02-01

Full Text Available In this work, silica–titania supported catalysts were prepared by a sol–gel method with various compositions. Vanadia was impregnated on SiO2-TiO2 with different loadings, and materials were investigated in the partial oxidation of methanol and methyl mercaptan to formaldehyde. The materials were characterized by using N2 physisorption, X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, X-ray photoelectron spectroscopy (XPS, Scanning transmission electron microscope (STEM, NH3-TPD, and Raman techniques. The activity results show the high importance of an optimized SiO2-TiO2 ratio to reach a high reactant conversion and formaldehyde yield. The characteristics of mixed oxides ensure a better dispersion of the active phase on the support and in this way increase the activity of the catalysts. The addition of vanadium pentoxide on the support lowered the optimal temperature of the reaction significantly. Increasing the vanadia loading from 1.5% to 2.5% did not result in higher formaldehyde concentration. Over the 1.5%V2O5/SiO2 + 30%TiO2 catalyst, the optimal selectivity was reached at 415 °C when the maximum formaldehyde concentration was ~1000 ppm.

Use of ade1 and ade2 mutations for development of a versatile red/white colour assay of amyloid-induced oxidative stress in saccharomyces cerevisiae.

Science.gov (United States)

Bharathi, Vidhya; Girdhar, Amandeep; Prasad, Archana; Verma, Meenkshi; Taneja, Vibha; Patel, Basant K

2016-12-01

Mutations in adenine biosynthesis pathway genes ADE1 and ADE2 have been conventionally used to score for prion [PSI + ] in yeast. If ade1-14 mutant allele is present, which contains a premature stop codon, [psi - ] yeast appear red on YPD medium owing to accumulation of a red intermediate compound in vacuoles. In [PSI + ] yeast, partial inactivation of the translation termination factor, Sup35 protein, owing to its amyloid aggregation allows for read-through of the ade1-14 stop codon and the yeast appears white as the red intermediate pigment is not accumulated. The red colour development in ade1 and ade2 mutant yeast requires reduced-glutathione, which helps in transport of the intermediate metabolite P-ribosylaminoimidazole carboxylate into vacuoles, which develops the red colour. Here, we hypothesize that amyloid-induced oxidative stress would deplete reduced-glutathione levels and thus thwart the development of red colour in ade1 or ade2 yeast. Indeed, when we overexpressed amyloid-forming human proteins TDP-43, Aβ-42 and Poly-Gln-103 and the yeast prion protein Rnq1, the otherwise red ade1 yeast yielded some white colonies. Further, the white colour eventually reverted back to red upon turning off the amyloid protein's expression. Also, the aggregate-bearing yeast have increased oxidative stress and white phenotype yeast revert to red when grown on media with reducing agent. Furthermore, the red/white assay could also be emulated in ade2-1, ade2Δ, and ade1Δ mutant yeast and also in an ade1-14 mutant with erg6 gene deletion that increases cell-wall permeability. This model would be useful tool for drug-screening against general amyloid-induced oxidative stress and toxicity. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Neutral complexes as oxidants for the reduced form of parsley (Petroselinum crispum) [2Fe--2S] ferredoxin. Evidence for partial blocking by redox-inactive Cr(III) complexes.

Science.gov (United States)

Adzamli, I K; Kim, H O; Sykes, A G

1982-01-01

The 1 : 1 reactions of three neutral Co(III) oxidants, Co(acac)3, Co(NH3)3(NO2)3 and Co(acac)2(NH3)(NO2), with reduced parsley (Petroselinum crispum) [2Fe--2S] ferredoxin (which carries a substantial negative charge), have been studied at 25 degrees C, pH 8.0 (Tris/HCl), I0.10 (NaCl). Whereas it has previously been demonstrated that with Co(NH3)6+ as oxidant the reaction if completely blocked by redox-inactive Cr(NH3)63+, the neutral oxidants are only partially blocked by this same complex. The effects of three Cr(III) complexes, Cr(NH3)63+%, Cr(en)33+ and (en)2Cr . mu(OH,O2CCH3) . CR(en)24+ have been investigated. Kinetic data for the response of 3+, neutral, as well as 1--oxidants to the presence of 3+ (and 4+) Cr(III) complexes can now be rationalized in terms of a single functional site on the protein for electron transfer. Electrostatics have a significant influence on association at this site. PMID:7115307

Precise control of Si(001) initial oxidation by translational kinetic energy of O2 molecules

International Nuclear Information System (INIS)

Teraoka, Yuden; Yoshigoe, Akitaka

2002-01-01

The influence of translation kinetic energy of incident O 2 molecules on the passive oxidation of the clean Si(001) surface and the partially oxidized-Si(001) surface has been studied by high-resolution photoemission spectroscopy using synchrotron radiation. The incident energy of O 2 molecules was controlled up to 3 eV by a supersonic seeded molecular beam technique. Although two incident energy thresholds (1.0 eV and 2.6 eV) have been determined for the partially oxidized-surface oxidation in accordance with the first-principle calculation, the monotonic increase of oxygen saturation coverage was observed for the clean surface oxidation. The difference is caused by the initial dangling bond termination (Si-H and Si-OH) on the partially oxidized surface. Si-2p and O-1s photoemission spectra measured at representative incident energies showed the incident-energy-induced oxidation at the back bonds of Si dimers and the second-layer (subsurface) Si atoms. Moreover, the low-and high-binding-energy components in the O-1s photoemission spectra were assigned to bridge site oxygen and dangling bond site oxygen for the partially oxidized-surface oxidation. (author)

Continuous Hydrolysis and Liquid–Liquid Phase Separation of an Active Pharmaceutical Ingredient Intermediate Using a Miniscale Hydrophobic Membrane Separator

DEFF Research Database (Denmark)

Cervera Padrell, Albert Emili; Morthensen, Sofie Thage; Lewandowski, Daniel Jacob

2012-01-01

Continuous hydrolysis of an active pharmaceutical ingredient intermediate, and subsequent liquid–liquid (L-L) separation of the resulting organic and aqueous phases, have been achieved using a simple PTFE tube reactor connected to a miniscale hydrophobic membrane separator. An alkoxide product......, obtained in continuous mode by a Grignard reaction in THF, reacted with acidic water to produce partially miscible organic and aqueous phases containing Mg salts. Despite the partial THF–water miscibility, the two phases could be separated at total flow rates up to 40 mL/min at different flow ratios, using...

Mathematical modeling of oxygen transport in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Svensson, Ann Mari

1997-12-31

This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

Storage Stability and Improvement of Intermediate Moisture Foods, Phase 3

Science.gov (United States)

Labuza, T. P.

1975-01-01

Methods were determined for the improvement of shelf-life stability of intermediate moisture foods (IMF). Microbial challenge studies showed that protection against molds and Staphylococcus aureus could be achieved by a combination of antimicrobial agents, humectants and food acids. Potassium sorbate and propylene glycol gave the best results. It was also confirmed that the maximum in heat resistance shown by vegetative pathogens at intermediate water activities also occurred in a solid food. Glycols and sorbitol both achieve browning inhibition because of their action as a medium for reaction and effect on viscosity of the adsorbed phase. Chemical availability results showed rapid lysine loss before visual discoloration occurred. This is being confirmed with a biological test using Tetrahymena pyriformis W. Accelerated temperature tests show that effectiveness of food antioxidants against rancidity development can be predicted; however, the protection factor changes with temperature. BHA was found to be the best antioxidant for iron catalyzed oxidation.

Intermediate-range chemical ordering of cations in molten RbCl-AgCl

Energy Technology Data Exchange (ETDEWEB)

Tahara, S. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Kawakita, Y. [J-PARC Center, Japan Atomic Energy Agency (JAEA), Ibaraki 319-1195 (Japan); Shimakura, H. [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Sciences, Niigata 956-8603 (Japan); Ohara, K. [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Fukami, T. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Takeda, S. [Department of Physics, Faculty of Sciences, Kyushu University, Fukuoka 812-8581 (Japan)

2015-07-28

A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S{sub AgAg}(Q) and S{sub RbRb}(Q), show a positive contribution to the FSDP, while S{sub AgRb}(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM.

Intermediate-range chemical ordering of cations in molten RbCl-AgCl

International Nuclear Information System (INIS)

Tahara, S.; Kawakita, Y.; Shimakura, H.; Ohara, K.; Fukami, T.; Takeda, S.

2015-01-01

A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S AgAg (Q) and S RbRb (Q), show a positive contribution to the FSDP, while S AgRb (Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM

Ameliorative role of gemfibrozil against partial abdominal aortic constriction-induced cardiac hypertrophy in rats.

Science.gov (United States)

Singh, Amrit Pal; Singh, Randhir; Krishan, Pawan

2015-04-01

Fibrates are peroxisome proliferator-activated receptor-α agonists and are clinically used for treatment of dyslipidemia and hypertriglyceridemia. Fenofibrate is reported as a cardioprotective agent in various models of cardiac dysfunction; however, limited literature is available regarding the role of gemfibrozil as a possible cardioprotective agent, especially in a non-obese model of cardiac remodelling. The present study investigated the role of gemfibrozil against partial abdominal aortic constriction-induced cardiac hypertrophy in rats. Cardiac hypertrophy was induced by partial abdominal aortic constriction in rats and they survived for 4 weeks. The cardiac hypertrophy was assessed by measuring left ventricular weight to body weight ratio, left ventricular wall thickness, and protein and collagen content. The oxidative stress in the cardiac tissues was assessed by measuring thiobarbituric acid-reactive substances, superoxide anion generation, and reduced glutathione level. The haematoxylin-eosin and picrosirius red staining was used to observe cardiomyocyte diameter and collagen deposition, respectively. Moreover, serum levels of cholesterol, high-density lipoproteins, triglycerides, and glucose were also measured. Gemfibrozil (30 mg/kg, p.o.) was administered since the first day of partial abdominal aortic constriction and continued for 4 weeks. The partial abdominal aortic constriction-induced cardiac oxidative stress and hypertrophy are indicated by significant change in various parameters used in the present study that were ameliorated with gemfibrozil treatment in rats. No significant change in serum parameters was observed between various groups used in the present study. It is concluded that gemfibrozil ameliorates partial abdominal aortic constriction-induced cardiac oxidative stress and hypertrophy and in rats.

Highly Active, Carbon-supported, PdSn Nano-core, Partially ...

African Journals Online (AJOL)

Carbon-supported, Pt partially covered, PdSn alloy nanoparticles (Pt-PdSn/C) were synthesized via a metathetical reaction of PdSn alloy nanoparticles, and a platinum precursor. The electrochemical activity was evaluated by methanol oxidation. The Pt-PdSn/C catalysts were characterized by transmission electron ...

Oxidation reactions of bilirubin in aqueous solutions

International Nuclear Information System (INIS)

Mohan, Hari; Gopinathan, C.

1990-01-01

The radical cation of bilirubin (BR) has been tentatively identified as a transient intermediate in the reactions of BR with different oxidizing species such as Br 2 - , I 2 - and CH 3 I . OH. The rate constants for these reactions have been determined as 2.4 x 10 9 , l.0 x 10 9 and 2.7 x 10 9 dm 3 mol -1 s -1 , respectively. Biliverdin is likely to be among the stable products formed on oxidation of BR by these oxidizing species. (author)

The change of steel surface chemistry regarding oxygen partial pressure and dew point

Science.gov (United States)

Norden, Martin; Blumenau, Marc; Wuttke, Thiemo; Peters, Klaus-Josef

2013-04-01

By investigating the surface state of a Ti-IF, TiNb-IF and a MnCr-DP after several series of intercritical annealing, the impact of the annealing gas composition on the selective oxidation process is discussed. On behalf of the presented results, it can be concluded that not the general oxygen partial pressure in the annealing furnace, which is a result of the equilibrium reaction of water and hydrogen, is the main driving force for the selective oxidation process. It is shown that the amounts of adsorbed gases at the strip surface and the effective oxygen partial pressure resulting from the adsorbed gases, which is mainly dependent on the water content of the annealing furnace, is driving the selective oxidation processes occurring during intercritical annealing. Thus it is concluded, that for industrial applications the dew point must be the key parameter value for process control.

Molecular and morphological characterization of the cercariae of Lecithodendrium linstowi (Dollfus, 1931), a trematode of bats, and incrimination of the first intermediate snail host, Radix balthica.

Science.gov (United States)

Enabulele, Egie E; Lawton, Scott P; Walker, Anthony J; Kirk, Ruth S

2018-03-01

Lecithodendrium linstowi is one of the most prevalent and abundant trematodes of bats, but the larval stages and intermediate hosts have not been identified. We present the first molecular and morphological characterization of the cercariae of L. linstowi based on a phylogenetic analysis of partial fragments of LSU and ITS2 rDNA. The first intermediate host was incriminated as Radix balthica by DNA barcoding using cox1 and ITS2 sequences, although the snail morphologically resembled Radix peregra, emphasizing the requirement for molecular identification of lymnaeids as important intermediate hosts of medical and veterinary impact. The application of molecular data in this study has enabled linkage of life cycle stages and accurate incrimination of the first intermediate host.

Obtainment of zirconium oxide and partially stabilized zirconium oxide with yttrium and rare earth oxides, from Brazilian zirconite, for ceramic aim

International Nuclear Information System (INIS)

Ribeiro, S.

1991-05-01

This work presents experimental results for processing of brazilian zirconite in order to obtain zirconium oxide with Yttrium and Rare Earth oxide by mutual coprecipitation for ceramics purposes. Due to analysis of experimental results was possible to obtain the optimum conditions for each one of technological route stage, such as: alkaline fusion; acid leaching; sulfactation and coprecipitation. (author)

The influence of charge injection from intermediate connectors on the performance of tandem organic light-emitting devices

Energy Technology Data Exchange (ETDEWEB)

Zhou, Dong-Ying [Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou, Jiangsu 215123 (China); Department of Electrical and Computer Engineering and Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1 (Canada); Siboni, Hossein Zamani; Wang, Qi; Aziz, Hany, E-mail: lsliao@suda.edu.cn, E-mail: h2aziz@uwaterloo.ca [Department of Electrical and Computer Engineering and Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1 (Canada); Liao, Liang-Sheng, E-mail: lsliao@suda.edu.cn, E-mail: h2aziz@uwaterloo.ca [Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou, Jiangsu 215123 (China)

2014-12-14

Charge generation in a typical intermediate connector, composed of “n-type doped layer/transition metal oxide (TMO)/hole transporting layer (HTL),” of a tandem organic light-emitting device (OLED) has recently been found to arise from charge transfer at the TMO/HTL interfaces. In this paper, we investigate the effect of hole injection barriers from intermediate connectors on the performance of tandem OLEDs. The hole injection barriers are caused by the offset of the highest occupied molecular orbital (HOMO) energy levels between HTLs contained in the intermediate connector and the top electroluminescence (EL) unit. We also find that although charge generation can occur at the interfaces between the TMO and a wide variety of HTLs of different HOMO values, an increase in the hole injection barrier however limits the electroluminescence efficiency of the top EL units. In the case of large hole injection barriers, significant charge accumulation in the HTLs makes the intermediate connector lose its functionality gradually over operating time, and limits device stability.

An investigation of the oxidized Ni/InAs interface

Energy Technology Data Exchange (ETDEWEB)

Venter, A., E-mail: andre.venter@nmmu.ac.z [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031 (South Africa); Botha, J.R. [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031 (South Africa); Swart, H.C. [Department of Physics, University of the Free State, PO Box 339, Bloemfontein 9300 (South Africa); Naidoo, S.; Olivier, E.J. [Department of Physics, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031 (South Africa)

2009-12-01

Ni was resistively deposited onto bulk InAs and subsequently oxidized in an O{sub 2} atmosphere. The anneal temperature and time were 450 deg. C and 2.5 h, respectively. X-ray diffraction of the oxidized Ni/InAs sample revealed the formation of In{sub 3}Ni{sub 2} and In{sub 2}O{sub 3} on the front suggesting inter diffusion of In, Ni and O. NiO was not detected by X-ray diffraction. In a preliminary study, using glass as a substrate, NiO readily formed when using these oxidation parameters. Conductivity measurements of the oxidized Ni/InAs surface revealed a conducting front and insulating rear surface while TEM of the Ni/InAs interface revealed an intermediate amorphous diffusion zone between the 'oxidized' Ni layer and the bulk InAs. A closer investigation of the intermediate layer supports the X-ray diffraction results, suggesting compound formation due to diffusion of oxygen and nickel into the substrate, and out-diffusion of In and As from the bulk of the sample. AES was used to further elucidate these results.

Synthesis and analysis of Mo-Si-B based coatings for high temperature oxidation protection of ceramic materials

Science.gov (United States)

Ritt, Patrick J.

The use of Ni-based superalloys in turbine engines has all but been exhausted, with operating temperatures nearing the melting point of these materials. The use of ceramics in turbine engines, particularly ceramic matrix composites such as SiC/C and SiC/SiC, is of interest due to their low density and attractive mechanical properties at elevated temperatures. The same materials are also in consideration for leading edges on hypersonic vehicles. However, SiC-based composites degrade in high temperature environments with low partial pressures of oxygen due to active oxidation, as well as high temperature environments containing water or sand. The need for a protective external coating for SiC-based composites in service is obvious. To date, no coating investigated for SiC/C or SiC/SiC has been proven to be resistant to oxidation and corrosion at intermediate and high temperatures, as well as in environments deficient in oxygen. The Mo-Si-B coating shows great promise in this area, having been proven resistant to attack from oxidation at extreme temperatures, from water vapor and from calcia-magnesia-aluminosilicate (CMAS). The adaptation of the Mo-Si-B coating for ceramic materials is presented in detail here. Evaluation of the coating under a range of oxidation conditions as well as simulated re-entry conditions confirms the efficacy of the Mo-Si-B based coating as protection from catastrophic failure. The key to the oxidation and corrosion resistance is a robust external aluminoborosilica glass layer that forms and flows quickly to cover the substrate, even under the extreme simulated re-entry conditions. Suppression of active oxidation of SiC, which may occur during atmospheric re-entry and hypersonic flight trajectories, has also been examined. In order to adapt the Mo-Si-B based coating to low partial pressures of oxygen and elevated temperatures, controlled amounts of Al were added to the Mo-Si-B based coating. The resulting coating decreased the inward

Mechanism-Based Design of Green Oxidation Catalysts

Energy Technology Data Exchange (ETDEWEB)

Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

2015-03-16

In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

Limits and dynamics of methane oxidation in landfill cover soils

Science.gov (United States)

In order to understand the limits and dynamics of methane (CH4) oxidation in landfill cover soils, we investigated CH4 oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO2 concentration. The results indicate a signi...

Direct Partial Oxidation of Natural Gas to Liquid Chemicals

DEFF Research Database (Denmark)

Rasmussen, Christian Lund

2007-01-01

Direkte delvis oxidation af naturgas til flydende kemikalier er en attraktiv industriel proces, hvor naturgas omdannes til stoffer; primært methanol (CH3OH) som let kan transporteres over store afstande. Omdannelsen sker i en simpel et-trinsproces under højt tryk, lave forbrændingstemperaturer, s...

Separation medium containing thermally exfoliated graphite oxide

Science.gov (United States)

Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Herrera-Alonso, Margarita (Inventor)

2012-01-01

A separation medium, such as a chromatography filling or packing, containing a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g, wherein the thermally exfoliated graphite oxide has a surface that has been at least partially functionalized.

1 - Aromatization of n-hexane and natural gasoline over ZSM-5 zeolite, 2- Wet catalytic oxidation of phenol on fixed bed of active carbon; 1 - Aromatisation de n-hexane et d'essence sur zeolithe ZSM-5, 2 - Oxydation catalytique en voie humide du phenol sur charbon actif

Energy Technology Data Exchange (ETDEWEB)

Suwanprasop, S.

2005-04-15

I - The production of aromatic hydrocarbons from n-hexane and natural gasoline over Pd loaded ZSM-5 zeolite in a tubular reactor was achieved under the suitable conditions at 400 deg. C, and 0.4 ml/min reactant feeding rate, employing ZSM-5 (0.5% Pd content) as a catalyst. Under these conditions, n-hexane and natural gasoline conversions were found to be 99.7% and 94.3%, respectively (with respective aromatic selectivity of 92.3% and 92.6%). II - Wet catalytic air oxidation of phenol over a commercial active carbon was studied in a three phase fixed bed reactor under mild temperature and oxygen partial pressure. Exit phenol concentration, COD, and intermediates were analysed. Oxidation of phenol was significantly improved when increasing operating temperature, oxygen partial pressure, and liquid space time, while up or down flow modes had only marginal effect. A complete model involving intrinsic kinetics and all mass transfer limitations gave convenient reactor simulation. (author)

Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

Energy Technology Data Exchange (ETDEWEB)

Carriere, B.; Deville, J.P.; El Maachi, A.

1987-06-01

The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

Intermediality and media change

OpenAIRE

2012-01-01

This book is about intermediality as an approach to analysing and understanding media change. Intermediality and Media Change is critical of technological determinism that characterises 'new media discourse' about the ongoing digitalization, framed as a revolution and creating sharp contrasts between old and new media. Intermediality instead emphasises paying attention to continuities between media of all types and privileges a comparative perspective on technological changes in media over ti...

Health Assessment Document for Ethylene Oxide

Science.gov (United States)

The largest single use of ethylene oxide is as an intermediate in the synthesis of ethylene glycol. However, small amounts of this epoxide are used as a sterilant or pesticide in commodities, pharmaceuticals, medical devices, tobacco, and other items, representing a considerable ...

Nitrous oxide production pathways in a partial nitritation-anammox reactor: Isotopic evidence for nitrous oxide production associated anaerobic ammonium oxidation?

Science.gov (United States)

Wunderlin, P.; Harris, E. J.; Joss, A.; Emmenegger, L.; Kipf, M.; Mohn, J.; Siegrist, H.

2014-12-01

Nitrous oxide (N2O) is a strong greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment N2O can be produced via several pathways. This study investigates the dynamics of N2O emissions from a nitritation-anammox reactor, and links its interpretation to the nitrogen and oxygen isotopic signature of the emitted N2O. A 400-litre single-stage nitritation-anammox reactor was operated and continuously fed with digester liquid. The isotopic composition of N2O emissions was monitored online with quantum cascade laser absorption spectroscopy (QCLAS; Aerodyne Research, Inc.; Waechter et al., 2008). Dissolved ammonium and nitrate were monitored online (ISEmax, Endress + Hauser), while nitrite was measured with test strips (Nitrite-test 0-24mgN/l, Merck). Table 1. Summary of experiments conducted to understand N2O emissions Experimental conditions O2[mgO2/L] NO2-[mgN/L] NH4+[mgN/L] N2O/NH4+[%] Normal operation production pathway, which is hypothesized to be mediated by anammox activity (Figure 1). A less likely explanation is that the SP of N2O was increased by partial N2O reduction by heterotrophic denitrification. Various experiments were conducted to further investigate N2O formation pathways in the reactor. Our data reveal that N2O emissions increased when reactor operation was not ideal, for example when dissolved oxygen was too high (Table 1). SP measurements confirmed that these N2O peaks were due to enhanced nitrifier denitrification, generally related to nitrite build-up in the reactor (Figure 1; Table 1). Overall, process control via online N2O monitoring was confirmed to be an ideal method to detect imbalances in reactor operation and regulate aeration, to ensure optimal reactor conditions and minimise N2O emissions. ReferencesWaechter H. et al. (2008) Optics Express, 16: 9239-9244. Wunderlin, P et al. (2013) Environmental Science & Technology 47: 1339-1348.

Partial inelasticity coefficients of negative pions produced in hadron-nucleus and nucleus-nucleus collisions at high energies

International Nuclear Information System (INIS)

OLIMOV, K.; LUTPULLAEV, S.L.; PETROV, V.I.; OLIMOV, A.K.

2015-01-01

New experimental data on the partial inelasticity coefficients of negative pions produced in "1"6Op-collisions at 3.25 A GeV/s, pC-interactions at 4.2 and 9.9 GeV/s, and d,α,C(C)-collisions at 4.2 A GeV/s are presented. It is established that the behavior of partial inelasticity coefficients of pions at intermediate energies (<10 GeV) in hadron-nucleus collisions has a transitional character, reaching the limiting value at ultrahigh energies. It is shown that the mean values of partial inelasticity coefficients of pions produced in nucleus-nucleus collisions decrease with an increase in mass number of the projectile nucleus. (authors)

The oxidative p-dichlorobenzene dechlorinating in the presence of copper (ΙΙ complexes and nitrogen (ΙΙ, ΙV oxides

Directory of Open Access Journals (Sweden)

Valentina Yemelyanova

2012-12-01

Full Text Available The results of dechlorination in the solution CuCl2–TBP–NaNO2–О2–Н2О kinetics research are presented in the article. All system components influence to the dechlorination process is studied and quantitatively described. The composition of copper intermediate complexes participating in reaction is studied by the instrumentality of UV-spectroscopy. Established part of binuclear copper complexes in the catalytic intermediate complex constants of formation were estimated and compared with the kinetic and spectrophotometric methods. The composition of the intermediate complexes responsible for process is defined, the mechanism scheme is offered, the p-dichlorobenzene dechlorination limiting stage including redox-disintegration of the intermediate complex consisting of dimeric complex of copper (II, I chloride, nitrogen oxide and p-dichlorobenzene is defined.

Intermediate Fragment

DEFF Research Database (Denmark)

Kruse Aagaard, Anders

2015-01-01

This text and its connected exhibition are aiming to reflect both on the thoughts, the processes and the outcome of the design and production of the artefact ‘Intermediate Fragment’ and making as a contemporary architectural tool in general. Intermediate Fragment was made for the exhibition ‘Enga...... of realising an exhibition object was conceived, but expanded, refined and concretised through this process. The context of the work shown here is an interest in a tighter, deeper connection between experimentally obtained material knowledge and architectural design....

Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric optimization and mineralization pathway

Directory of Open Access Journals (Sweden)

Hicham Zazou

2017-01-01

Full Text Available Oxidative degradation of herbicide 2,4,5-T was studied by electrochemical advanced oxidation processes anodic oxidation and electro-Fenton (EF using Pt/carbon felt and BDD/carbon felt cells. The effect of main operating parameters on oxidation of 2,4,5-T and mineralization of its aqueous solution were investigated. The rate constant for oxidation of 2,4,5-T by ·≡OH was determined as (3.7 ± 0.2 × 109 M−1 s−1 using competition kinetics method. The EF process with BDD anode was shown to be very efficient reaching 94% mineralization in 3 h treatment. Based on identified aromatic intermediates, short-chain carboxylic acids, released inorganic ions and total organic carbon removal measurements, a plausible oxidation pathway for mineralization of 2,4,5-T by hydroxyl radical was proposed. In addition, the evolution of solution toxicity during treatment was monitored by Microtox method showing the formation of toxic aromatic/cyclic intermediates. The results showed also that EF process was able to remove efficiently toxic intermediates and consequently solution toxicity.

Governance-Default Risk Relationship and the Demand for Intermediated and Non-Intermediated Debt

Directory of Open Access Journals (Sweden)

Husam Aldamen

2012-09-01

Full Text Available This paper explores the impact of corporate governance on the demand for intermediated debt (asset finance, bank debt, non-bank private debt and non-intermediated debt (public debt in the Australian debt market. Relative to other countries the Australian debt market is characterised by higher proportions of intermediated or private debt with a lower inherent level of information asymmetry in that private lenders have greater access to financial information (Gray, Koh & Tong 2009. Our firm level, cross-sectional evidence suggests that higher corporate governance impacts demand for debt via the mitigation of default risk. However, this relationship is not uniform across all debt types. Intermediated debt such as bank and asset finance debt are more responsive to changes in governance-default risk relationship than non-bank and non-intermediated debt. The implication is that a firm’s demand for different debt types will reflect its governance-default risk profile.

Ionic Conductivity and its Role in Oxidation Reactions

Science.gov (United States)

Tamimi, Mazin Abdulla

In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

KAUST Repository

Hervier, Antoine

2011-11-24

Platinum films of 1 nm thickness were deposited by electron beam evaporation onto 100 nm thick titanium oxide films (TiOx) with variable oxygen vacancy concentrations and fluorine (F) doping. Methanol oxidation on the platinum films produced formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiOx was stoichiometric (TiO 2), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO1.9). These results correlate with the chemical behavior of the same types of catalysts in CO oxidation. Fluorine doping of stoichiometric TiO2 also increased selectivity toward partial oxidation of methanol to formaldehyde and methyl formate, but had an opposite effect in the case of nonstoichiometric TiOx. Introduction of oxygen vacancies and fluorine doping both increased the conductivity of the TiO x film. For oxygen vacancies, this occurred by the formation of a conduction channel in the band gap, whereas in the case of fluorine doping, F acted as an n-type donor, forming a conduction channel at the bottom of the conduction band, about 0.5-1.0 eV higher in energy. The higher energy electrons in F-doped stoichiometric TiOx led to higher turnover rates and increased selectivity toward partial oxidation of methanol. This correlation between electronic structure and turnover rate and selectivity indicates that the ability of the support to transfer charges to surface species controls in part the activity and selectivity of the reaction. © 2011 American Chemical Society.

Selective propene oxidation on mixed metal oxide catalysts

International Nuclear Information System (INIS)

James, David William

2002-01-01

Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

Method of manufacturing ceramic oxide nuclear fuels and intermediate products thereof

International Nuclear Information System (INIS)

Matous, V.; Pecak, V.; Baran, V.

1978-01-01

Uranyl nitrate or uranyl sulphate is extracted as a tributyl phosphate solvate into an organic solvent from aqueous solutions of uranium in sulphuric or nitric acid obtained from ore treatment or from wet reprocessing. Uranyl fluorides obtained from dry reprocessing should be hydrolysed and converted to uranyl sulphate or uranyl nitrate for such extraction. The tributyl phosphate solvate of the compound in the organic solvent (in a higher petrol fraction or in a chlorinated hydrocarbon) is directly precipitated using an aqueous solution of a hydroxide, preferably ammonium hydroxide as a hydrated oxide. Stoichiometric and overstoichiometric amounts of hydroxides lead to the formation of amorphous diuranates. Substoichiometric amounts of hydroxides used and of hydroxylamine solutions only lead to hydrolysis in which heavy macroscopic yellow crystalline precipitates are formed of the hydrated uranium oxide. Drying and annealing may result in UO 3 and UO 2 , respectively. (B.S.)

Investigation of structural and electrochemical properties of LaSrCo{sub 1−x}Sb{sub x}O{sub 4} (0≤x≤0.20) as potential cathode materials in intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Wang, Junkai; Zhou, Jun, E-mail: zhoujun@mail.xjtu.edu.cn; Fan, Weiwei; Wang, Wendong; Wu, Kai; Cheng, Yonghong

2017-03-15

The structural and electrochemical properties of the layered perovskite oxides LaSrCo{sub 1−x}Sb{sub x}O{sub 4} (0≤x≤0.20) were investigated to study the effects of substituting Sb for Co for application as cathode materials in intermediate temperature solid oxide fuel cells (IT-SOFCs). The results of crystal structure analyses show the maximum content of Sb in LaSrCo{sub 1−x}Sb{sub x}O{sub 4} to be 0.05 as a pure single phase. XPS shows that Co and Sb in LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} may possess mixed-oxidation states. The electrical conductivity increased greatly after Sb substitution. An improvement in the cathode polarization (R{sub p}) values is observed from the Sb-doped sample with respect to the undoped samples. For example, R{sub p} of LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} on LSGM was observed to be 0.16 Ω cm{sup 2} at 800 °C in air. The main rate-limiting step for LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} cathode is charge transfer of oxygen atoms. These results indicate that Sb can be incorporated into LaSrCo{sub 1−x}Sb{sub x}O{sub 4} based materials and can have a beneficial effect on the performance, making them potentially suitable for use as cathode materials in IT-SOFCs. - Graphical abstract: The oxygen partial pressure dependence of polarization resistances for a new layered perovskite cathode LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} at various temperatures was measured. - Highlights: • The maximum content of Sb was 0.05 mol in LaSrCo{sub 1−x}Sb{sub x}O{sub 4}. • The maximum electrical conductivity is 194 S cm{sup −1}for LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} at 800 °C. • A rate-limiting process of charge transfer presented.

High-pressure oxidation of methane

NARCIS (Netherlands)

Hashemi, Hamid; Christensen, Jakob M.; Gersen, Sander; Levinsky, Howard; Klippenstein, Stephen J.; Glarborg, Peter

2016-01-01

Methane oxidation at high pressures and intermediate temperatures was investigated in a laminar flow reactor and in a rapid compression machine (RCM). The flow-reactor experiments were conducted at 700–900 K and 100 bar for fuel-air equivalence ratios (Φ) ranging from 0.06 to 19.7, all highly

Partial oxidation of jet fuels over Rh/Al{sub 2}O{sub 3}. Design and reaction kinetics of sulfur-containing surrogates

Energy Technology Data Exchange (ETDEWEB)

Baer, Julian Nicolaas

2016-07-01

The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al{sub 2}O{sub 3} at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al{sub 2}O{sub 3}, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product

BL153 Partially Prevents High-Fat Diet Induced Liver Damage Probably via Inhibition of Lipid Accumulation, Inflammation, and Oxidative Stress

Directory of Open Access Journals (Sweden)

Jian Wang

2014-01-01

Full Text Available The present study was to investigate whether a magnolia extract, named BL153, can prevent obesity-induced liver damage and identify the possible protective mechanism. To this end, obese mice were induced by feeding with high fat diet (HFD, 60% kcal as fat and the age-matched control mice were fed with control diet (10% kcal as fat for 6 months. Simultaneously these mice were treated with or without BL153 daily at 3 dose levels (2.5, 5, and 10 mg/kg by gavage. HFD feeding significantly increased the body weight and the liver weight. Administration of BL153 significantly reduced the liver weight but without effects on body weight. As a critical step of the development of NAFLD, hepatic fibrosis was induced in the mice fed with HFD, shown by upregulating the expression of connective tissue growth factor and transforming growth factor beta 1, which were significantly attenuated by BL153 in a dose-dependent manner. Mechanism study revealed that BL153 significantly suppressed HFD induced hepatic lipid accumulation and oxidative stress and slightly prevented liver inflammation. These results suggest that HFD induced fibrosis in the liver can be prevented partially by BL153, probably due to reduction of hepatic lipid accumulation, inflammation and oxidative stress.

Effects of inoculum type and bulk dissolved oxygen concentration on achieving partial nitrification by entrapped-cell-based reactors.

Science.gov (United States)

Rongsayamanont, Chaiwat; Limpiyakorn, Tawan; Khan, Eakalak

2014-07-01

An entrapment of nitrifiers into gel matrix is employed as a tool to fulfill partial nitrification under non-limiting dissolved oxygen (DO) concentrations in bulk solutions. This study aims to clarify which of these two attributes, inoculum type and DO concentration in bulk solutions, is the decisive factor for partial nitrification in an entrapped-cell based system. Four polyvinyl alcohol entrapped inocula were prepared to have different proportions of nitrite-oxidizing bacteria (NOB) and nitrite-oxidizing activity. At a DO concentration of 3 mg l(-1), the number of active NOB cells in an inoculum was the decisive factor for partial nitrification enhancement. However, when the DO concentration was reduced to 2 mg l(-1), all entrapped cell inocula showed similar degrees of partial nitrification. The results suggested that with the lower bulk DO concentration, the preparation of entrapped cell inocula is not useful as the DO level becomes the decisive factor for achieving partial nitrification. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxidative cleavage of a phenolic diarylpropane lignin model dimer by manganese peroxidase from Phanerochaete chrysosporium

International Nuclear Information System (INIS)

Wariishi, Hiroyuki; Valli, K.; Gold, M.H.

1989-01-01

In the presence of Mn II and H 2 O 2 , homogeneous manganese peroxidase oxidized 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1,3-dihydroxypropane (I) to yield 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1-oxo-3-hydroxypropane (II), 2,6-dimethoxy-1,4-benzoquinone (III), 2,6-dimethoxy-1,4-dihydroxybenzene (IV), 1-(4-methoxyphenyl)-1-oxo-2-hydroxyethane (V), 1-(4-methoxyphenyl)-1,2-dihydroxyethane (VI), syringaldehyde (VIII), and 2-(4-methoxyphenyl)-3-hydroxypropanal (IX). Chemically prepared manganese(III) malonate catalyzed the same reactions. Oxidation of I in H 2 18 O under argon resulted in >80% incorporation of 18 O into the phenylglycol VI, the hydroquinone IV, and the quinone III. Oxidation of I in H 2 18 O under aerobic conditions resulted in 40% incorporation of 18 O into VI but no 18 O incorporation into V. Finally, oxidation of I under 18 O 2 resulted in 89% and 28% incorporation of 18 O into V and VI, respectively. These results are explained by mechanisms involving the one-electron oxidation of the substrate I by enzyme-generated Mn III to produce a phenoxy radical intermediate I'. Subsequent C α -C β bond cleavage of the radical intermediate yields syringaldehyde (VIII) and a C 6 -C 2 benzylic radical. Syringaldehyde is oxidized by Mn III in several steps to a cyclohexadiene cation intermediate I double-prime, which is attacked by water to yield the benzoquinone III. The C 6 -C 2 radical is scavenged by O 2 to form a peroxy radical that decomposes to V and VI. In these reactions, Mn III generated by manganese peroxidase catalyzes both formation of the substrate phenoxy radical and oxidation of carbon-centered radical intermediates, to yield reactive cations

Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature

DEFF Research Database (Denmark)

Gorbanev, Yury; Kegnæs, Søren; Woodley, John

2009-01-01

The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 degrees C). The selectivity of the reaction towords 2,5-furandicarboxylic acid and the intermediate oxidation...

Survival outcome of intermediate risk neuroblastoma at Children Cancer Hospital Egypt.

Science.gov (United States)

Elzomor, Hossam; Ahmed, Gehad; Elmenawi, Salma; Elkinaai, Naglaa; Refaat, Amal; Soliman, Sonya; Abdelwahab, Mai Amr; Zaghloul, Mohamed Saad; Fawzy, Mohamed

2018-03-01

The study aims to evaluate survival outcome in newly diagnosed pediatric intermediate risk neuroblastoma patients treated at the Children Cancer Hospital - Egypt and their relation to various clinical and pathological factors. The study included stage 3 patients INSS) stage 4 disease, stage 4 children 1-1.5 years with favorable biology, and infants stage 4 s (with unfavorable biologic features). Patients received systemic chemotherapy, in the form of etoposide and carboplatin alternating with cyclophosphamide, doxorubicin and vincristine, administered at 3-week intervals, with a total of 6 or 8 cycles guided by reaching objective overall response (complete/very good partial/partial response). The study included 136 patients, 67 males and 69 females. 101 patients had abdominal primary tumors, 28 had mediastinal masss and 7 with masses in the neck; 68% were stage 3 and the remaining (n = 44) had metastatic disease. The three-year overall survival (OS) and event-free survival (EFS) estimates were 94% ± 2% and 90.9% ± 2.5%, respectively. OS and EFS by gender, age, pathology and INPC were all statistically not significantly different. Moreover, OS for patients having surgery versus no surgery (inoperable residual only) was statistically significant (98.4% ± 1.6% & 88.7% ± 5.3%, respectively, p = .034). A very high rate of survival is currently achievable in patients with intermediate risk neuroblastoma by chemotherapy or chemotherapy and surgery. In addition to response, our plan is to adopt biologically-based treatment to reduce treatment-induced complications among survivors. Copyright © 2018 National Cancer Institute, Cairo University. Production and hosting by Elsevier B.V. All rights reserved.

Oxidation of Helix-3 methionines precedes the formation of PK resistant PrP.

Directory of Open Access Journals (Sweden)

Tamar Canello

2010-07-01

Full Text Available While elucidating the peculiar epitope of the alpha-PrP mAb IPC2, we found that PrPSc exhibits the sulfoxidation of residue M213 as a covalent signature. Subsequent computational analysis predicted that the presence of sulfoxide groups at both Met residues 206 and 213 destabilize the alpha-fold, suggesting oxidation may facilitate the conversion of PrPC into PrPSc. To further study the effect of oxidation on prion formation, we generated pAbs to linear PrP peptides encompassing the Helix-3 region, as opposed to the non-linear complexed epitope of IPC2. We now show that pAbs, whose epitopes comprise Met residues, readily detected PrPC, but could not recognize most PrPSc bands unless they were vigorously reduced. Next, we showed that the alpha-Met pAbs did not recognize newly formed PrPSc, as is the case for the PK resistant PrP present in lines of prion infected cells. In addition, these reagents did not detect intermediate forms such as PK sensitive and partially aggregated PrPs present in infected brains. Finally, we show that PrP molecules harboring the pathogenic mutation E200K, which is linked to the most common form of familial CJD, may be spontaneously oxidized. We conclude that the oxidation of methionine residues in Helix-3 represents an early and important event in the conversion of PrPC to PrPSc. We believe that further investigation into the mechanism and role of PrP oxidation will be central in finally elucidating the mechanism by which a normal cell protein converts into a pathogenic entity that causes fatal brain degeneration.

Gas phase deposition of oxide and metal-oxide coatings on fuel particles

International Nuclear Information System (INIS)

Patokin, A.P.; Khrebtov, V.L.; Shirokov, B.M.

2008-01-01

Production processes and properties of oxide (Al 2 O 3 , ZrO 2 ) and metal-oxide (Mo-Al 2 O 3 , Mo-ZrO 2 , W-Al 2 O 3 , W-ZrO 2 ) coatings on molybdenum substrates and uranium dioxide fuel particles were investigated. It is shown that the main factors that have an effect on the deposition rate, density, microstructure and other properties of coatings are the deposition temperature, the ratio of H 2 and CO 2 flow rates, the total reactor pressure and the ratio of partial pressures of corresponding metal chlorides during formation of metal-oxide coatings

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

Science.gov (United States)

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Periapical tissue response after use of intermediate restorative material, gutta-percha, reinforced zinc oxide cement, and mineral trioxide aggregate as retrograde root-end filling materials: a histologic study in dogs.

Science.gov (United States)

Wälivaara, Dan-Åke; Abrahamsson, Peter; Isaksson, Sten; Salata, Luiz Antonio; Sennerby, Lars; Dahlin, Christer

2012-09-01

To investigate the periapical tissue response of 4 different retrograde root-filling materials, ie, intermediate restorative material, thermoplasticized gutta-percha, reinforced zinc oxide cement (Super-EBA), and mineral trioxide aggregate (MTA), in conjunction with an ultrasonic root-end preparation technique in an animal model. Vital roots of the third and fourth right mandibular premolars in 6 healthy mongrel dogs were apicectomized and sealed with 1 of the materials using a standardized surgical procedure. After 120 days, the animals were sacrificed and the specimens were analyzed radiologically, histologically, and scanning electron microscopically. The Fisher exact test was performed on the 2 outcome values. Twenty-three sections were analyzed histologically. Evaluation showed better re-establishment of the periapical tissues and generally lower inflammatory infiltration in the sections from teeth treated with the intermediate restorative material and the MTA. New root cement on the resected dentin surfaces was seen on all sections regardless of the used material. New hard tissue formation, directly on the surface of the material, was seen only in the MTA sections. There was no statistical difference in outcome among the tested materials. The results from this dog model favor the intermediate restorative material and MTA as retrograde fillings when evaluating the bone defect regeneration. MTA has the most favorable periapical tissue response when comparing the biocompatibility of the materials tested. Copyright © 2012 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.

A density functional theory study of partial oxidation of propylene on Cu2O(0 0 1) and CuO(0 0 1) surfaces

International Nuclear Information System (INIS)

Düzenli, Derya; Atmaca, Deniz Onay; Gezer, Miray Gülbiter; Onal, Isik

2015-01-01

Graphical abstract: - Highlights: • Propylene epoxidation mechanism on Cu 2 O(0 0 1) and CuO(0 0 1) surfaces is investigated using DFT method. • Acrolein is found to be a thermodynamically more favorable product for both surfaces especially over CuO surface. • The more basic property of the surface oxygen increases the probability of acrolein formation over CuO(0 0 1) surface. - Abstract: This work theoretically investigates propylene epoxidation reaction on Cu 2 O(0 0 1) and CuO(0 0 1) surfaces using periodical DFT method to determine the active copper species within the reaction mechanism. The transition states and energy profiles are calculated for the formation of surface intermediates such as oxametallopropylene (OMP) over Cu 2 O(0 0 1) and oxygen bridging (OB) over CuO(0 0 1) and allylic H-stripping reaction (AHS) over both surfaces as well as for formation of products. Propylene oxide (PO) and acetone are obtained through OMP and OB surface intermediates and acrolein generation is observed through allylic H-stripping reaction (AHS). The calculations revealed that the corresponding surface intermediates for epoxidation reaction need to overcome an activation barrier of 13 kcal/mol over CuO surface whereas they occur without an energy barrier over Cu 2 O surface indicating the higher activity of Cu + species. Acrolein is also found to be a thermodynamically more favorable product for both surfaces especially over CuO surface due to the presence of more surface oxygen atoms on which the basicity has been evaluated by the adsorption of sulfur dioxide. This indicates that the lattice oxygen inherent in both surface types does not participate in PO production.

RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

Directory of Open Access Journals (Sweden)

Florea Cristina A.

2017-01-01

Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

Meson widths and form factor at intermediate momentum transfer in nonperturbative QCD

International Nuclear Information System (INIS)

Ioffe, B.L.; Smilga, A.V.

1982-01-01

A general method is proposed for the QCD based calculations of form factors at intermediate momentum transfer Q 2 and of the partial widths of the low-lying meson resonances. The basic idea is to use the QCD sum rules for the vertex functions. With this method the pion electromagnetic form factor along with electromagnetic form factors of rho- and A 1 mesons and transition form factors γπ → A 1 at 0.5 2 2 are calculated. The widths rho+2π and A 1 → rhoπ are also determined. +.he results are in a good agreement with experiment

The impact of partial manganese superoxide dismutase (SOD2)-deficiency on mitochondrial oxidant stress, DNA fragmentation and liver injury during acetaminophen hepatotoxicity

International Nuclear Information System (INIS)

Ramachandran, Anup; Lebofsky, Margitta; Weinman, Steven A.; Jaeschke, Hartmut

2011-01-01

Acetaminophen (APAP) hepatotoxicity is the most frequent cause of acute liver failure in many countries. The mechanism of cell death is initiated by formation of a reactive metabolite that binds to mitochondrial proteins and promotes mitochondrial dysfunction and oxidant stress. Manganese superoxide dismutase (SOD2) is a critical defense enzyme located in the mitochondrial matrix. The objective of this investigation was to evaluate the functional consequences of partial SOD2-deficiency (SOD2+/-) on intracellular signaling mechanisms of necrotic cell death after APAP overdose. Treatment of C57Bl/6J wild type animals with 200 mg/kg APAP resulted in liver injury as indicated by elevated plasma alanine aminotransferase activities (2870 ± 180 U/L) and centrilobular necrosis at 6 h. In addition, increased tissue glutathione disulfide (GSSG) levels and GSSG-to-GSH ratios, delayed mitochondrial GSH recovery, and increased mitochondrial protein carbonyls and nitrotyrosine protein adducts indicated mitochondrial oxidant stress. In addition, nuclear DNA fragmentation (TUNEL assay) correlated with translocation of Bax to the mitochondria and release of apoptosis-inducing factor (AIF). Furthermore, activation of c-jun-N-terminal kinase (JNK) was documented by the mitochondrial translocation of phospho-JNK. SOD2+/- mice showed 4-fold higher ALT activities and necrosis, an enhancement of all parameters of the mitochondrial oxidant stress, more AIF release and more extensive DNA fragmentation and more prolonged JNK activation. Conclusions: the impaired defense against mitochondrial superoxide formation in SOD2+/- mice prolongs JNK activation after APAP overdose and consequently further enhances the mitochondrial oxidant stress leading to exaggerated mitochondrial dysfunction, release of intermembrane proteins with nuclear DNA fragmentation and more necrosis.